Analysis of Infrared Spectrum Characteristic and
Variation Trend of SF6 PD Decomposition
Fan LIU, Degang GAN, Siyu ZHOU, Can HU,
Ping LIU
Sichuan Electirc Power Test & Research Institute
Chengdu, P.R.China
Liufan2003@yahoo.com.cn
Abstract—SF6 decomposition components have a close
relationship with the insulation defects in GIS. And the inner
insulation state could be evaluated by monitoring the internal
gas decomposition components. Fourier transform infrared
spectroscopy (FTIR) and gas chromatography (GC) were used
to detect the SF6 partial discharge decomposition products.
The sample interval was 12 hours, total discharge time was 96
hours. It’s found that the components were varied in
discharge time. The gas were detected by FTIR , such as SOF2
、 SO2F2 、 SO2 、 SOF4 、 SF4 , different gas kinds and the
trend of concentration changes can be detected in different
periods. The gas kinds which the FTIR detected were more
than that of GC. Then, Quantitative analysis was finished by
using the absorbance value of each absorption peak. The
paper found that there were different components and gas
formation rates in different discharge time, so the method
could be used for real-time online monitoring of GIS.
I. INTRODUCTION
Gas-insulated switchgear had compact structure, high
reliability, so it has been widely used. In the manufacturing
and assembly process left some potential insulation defects
which difficult to discover,these defects caused the different
levels of partial discharge within GIS.The energy of partial
discharge can make SF6 gas decomposed,produced SF4, SF3,
SF2, S2F10 Low-fluoride sulfide, which reacted with the
trace moisture, oxygen in the SF6 gas and generated SOF2,
SOF4, SO2F2, SO2, HF, H2S and other compounds[1-2]. The
active gas PD (partial discharge, PD) generated can
accelerate insulation aging and corrosion of metal surfaces,
which may eventually lead to failure of GIS. Therefore, in
international gas component monitoring was proposed to
control the content of corrosive gas, determined the overall
level of PD and inferred causes of partial discharge [3].
Currently ,both at home and abroad for SF6 gas
discharge detection methods were mainly used gas
chromatography, test tube method and infrared absorption
spectroscopy [4]: gas chromatography can detect SOF2,
SO2F2, SO2, and CF4, detection accuracy can reach ul / l
level, but the chromatographic characteristics of injection
determined the detection time was longer, so it can not do
continuous on-line monitoring, Chromatographic column
which used for a period of time need clean, such a feature
determine chromatography technology with high
requirements of the environment,it was not suitable for on-
line monitoring applications;, the only practical test tube
978-1-4244-8286-3/10/$26.00 ©2010 IEEE
Xiaoxing ZHANG
State Key Laboratory of Power Transmission Equipment &
System Security and New Technology,
Chongqing University,Chongqing, P.R.China
method at home and abroad were HF, SO2, SOF2 test tube,
test accuracy was up to ul / l level, but its stability was
vulnerable to temperature/humidity, existed cross-
interference, HF had corrosion to test tube,so it can not be
used for partial discharge on-line monitoring; Fourier
transform infrared absorption spectrometry had fast
detection speed, multi-component detection and high
precwasion, strong anti-interference ability.Absorbence and
component concentration were in a linear relationship etc,
so it can be effectively applied to real-time on-line
monitoring [5].
In this paper, the main components of SF6
decomposition gas were SOF2, SO2F2, SF4, SOF4, SO2, SF6
gas discharge decomposition test device can be used for
partial discharge decomposition, simulated metal
protrusions defects generated by PD, made the
decomposition of components for infrared absorption
spectrum. Through each component gas infrared spectral
absorption characteristics of different periods, analyzed the
characteristics of SOF2 concentrations and the association
between discharge time, made a foundation for SF6
discharge decomposition of infrared real-time on-line
monitoring system.
II. INFRARED DETECTION PRINCIPLE
All molecules were moving, the molecules obey the
rules of quantum mechanics[6]. In accordance with quantum
mechanics, Born-Oppenheimer approximation of molecular
energy was:
E = E f + Er + Ev + Ee
(1)
In which translational motion was continuous, while the
rotation, vibration, and electronic movement have been
quantized. When infrared light through the sample, the
sample selected absorption of infrared light, the selection
was:
ΔE = E2 − E1 = =ν (2)
In which = =6.624 × 10
-34
J .s , v was the photons’
frequency.
According to the election laws of quantum mechanics
laws, if and only if the molecular dipole moment produced a
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change in infrared absorption, such a molecule known as the
infrared active molecules. Molecular rotational absorption
of infrared light section was far-infrared, the vibration
absorption of infrared light section was mid-infrared, multi-
atom molecule existed pure rotational absorption spectra,
but the pure vibrational absorption spectrum was not
available, the vibration absorption accompanied by rotation
absorption. In accordance with the Maxwell - Boltzmann
dwastribution law, most of the vibrational level transitions
were from the electronic ground state n=0 to n=1 transitions,
it can be drawn pairs of atomic and molecular vibration of
the classical equation.
1 k (3)
ν =
1
2π c μ TABLE I.
In which v1 was the wave number, c was the speed of
light, k was the vibration force constants, u was the
equivalent quality.
Many of the atom molecule infrared absorption formula
was:
V v − r = V v + B [( J ' + 1) − J ( J + 1)] (4)
In which vv-r was the vibration - rotation wave number,
B was the rotational constant, J was the rotational quantum
number. When the group vibrated, if the dipole moment
change paralleled to the axis of symmetry group,
then ΔJ = J ' − J = ±1 .if the dipole moment change
perpendiculared to the axis of symmetry group, then,
ΔJ = 0, ±1 . Due to ΔJ had different values, a few
absorption lines occured around the same absorption, the
spectra obtained was not an absorption line, but rather an
absorption band.
Infrared spectra of gas species detection can take
advantage of Lambert - Beer law to achieve quantitative
terms, the expression was as follows:
A = a×b×c (5)
Where A was the absorbance value, a was the absorption
coefficient, b was a measure of the optical path, c was the
gas concentration. The measuring principle of Fourier
transform infrared spectrometer was
I0 (6)
A = lg
I
In which I0 was the background light intensity, I was the
sampling intensity.
III. EXPERIMENT AND ANALYSIS
A. Experimental device
410
Figure 1. Test device of SF6 discharge decomposition Uu
The author used SF6 gas decomposition test device to
make SF6 decomposition of partial discharge testing[7], test
connection shown in Figure 1.
The experiment used Needle - plate electrode defect
model, the electrode spacing was 10mm, making the
experimental device vacuumized and filling three
atmospheric pressure SF6 gas, the applied voltage was
24kV, discharge time was 96 hours, gas production interval
was 12 hours.
B. Infrared Detection and Analysis
CLASSICAL IMBIBITION WAVE NUMBER OF SF6 AND ITS
DECOMPOSITION PRODUCTS
Gas species Wave number/ cm-1cm-1
SOF2 530,1330,1340
SO2F2 539,544,552
SOF4 752
SO2 1167,1360
SF4 746
CF4 1280,1283
HF 3644
H2S 2625
SF6 610,946,1270,1595,1720
Using Nicolet6700 Fourier transform infrared
spectrometer, Specac 20-meter-long optical path for
infrared analysis of gas pool. H2O and CO2 had a great
impact to infrared absorption spectra ,the mathod to avoid
their effects in the measure was: the first making the tank
cacuumized and then passing into the vacuum with
nitrogen, applied again and again , after the above operation
repeated then led to the decomposition of SF6 component.
Gas tank vacuum limit was 4kpa, residual gas was the
nitrogen, the gas tank sampling atmospheric pressure was
100kpa, resolution was 0.5cm-1, scanning frequency was
32, the room temperature was 19oC, humidity was 27%.
Since SF6 gas has high concentration, and its had
similar properties with its decomposition , so spectral
overlap was more serious. To be able to detect small
amounts of decomposition of gas components, the position
must be selected in the absence of SF6 absorption bands for
analysis. SF6 and its decomposition products were mainly
dwastributed in the absorption peak of 2000cm-1 ~ 480cm-1,
the specific circumstances was shown in Table I[8] .
From the Table 1 we can see SF6 had a lot of absorption
peaks, multi-infrared absorption spectra was the result of
joint action by molecular rotation and vibration, from the
formula (4) we can know that the multi-cellular spectra was
an absorption band rather than an absorption line, in the
above experiment, intensive absorption bands occured at a
few wave numbers, the basic analysis of other components
can not be used, it must avoid the detection of SF6
absorption band.
C. FTIR spectra and concentration trend analysis
In the experiment, first using infrared absorption
spectroscopy analyzed pre-discharge decomposition of SF6
gas, as compared spectra; then collected post-discharge
decomposition of SF6 gas for various time periods, made
infrared spectrum analysis of the components.Made
comparative analysis of the two spectra overlap,the result
was shown in Figure 2, what we can find in the spectra of
the two peaks in the situation was different. Specifically
expressed in SF6 decomposition of the infrared absorption
spectra of the absorption peak increased.
Figure 2. The infrared spectroscopy of pure SF6 and its decomposition
products
In order to overcome the impact of SF6, this paper used
the spectrum of geographical segment analysis method, that
was: extracted the clear difference between the absorption
peaks of absorption bands from the several sub-plans. Each
sub-graph corresponded to 1~2 kinds of characteristics of
decomposition of gas composition.
Removed the SF6 absorption band, made decomposition
of components compared with the infrared absorption
spectra of pure SF6, obtained the decomposition products
absorption spectra of the five sections:they were:529 cm-1 ~
560 cm-1; 720 cm-1 ~ 760 cm-1; 1096 cm-1 ~ 1104 cm-1; 1156
cm-1 ~ 1186 cm-1; 1320 cm-1 ~ 1360 cm-1, as shown in
Figure 3,4. Detected gases were SOF2, SO2F2, SF4, SOF4,
SO2.
a: SOF2,b: SO2F2,c: SF4
Figure 3. The infrared spectroscopy of conponents after 12 hours
discharge
a: SOF2,b: SO2F2,c: SF4,d: SOF4,e: SO2
Figure 4. The infrared spectroscopy of conponents after 96 hours
discharge
Figure 3 was the infrared spectroscopy of conponents
after 12 hours discharge, this time the component which
we can detect only SOF2, SO2F2, SF4 three kinds. Figure 4
was the infrared spectroscopy of conponents after 96 hours
discharge, this time we can detect five kinds of
components. From the diagram we can see :as the discharge
time increased, the absorption peak of the peak increased,
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and the decomposition of component species also
increased, new SOF4 and SO2 were the major components
of SF6 discharge decomposition, according to the
absorption peak of the peak of SO2 we can determine the
concentration of the gas.
Using OMNIC softwwere can read the absorbance peak
of the absorption peak ,then we can make table 2.Currently
the decomposition components of SF6 in the absorption peak
of the absorption’s coefficient was unknown , therefore
according to the absorption peak of each decompositon
component we can not use Lambert - Beer law for accurate
quantitative calculation. However, infrared absorption
spectroscopy had good linear relationship , the absorption
coefficient of gas molecules was only relevant to pressure,
temperature, In order to maintain the above conditions the
same in this experiment , so in equation (5), the absorption
coefficient a was a constant volume, so the decomposition
of component concentration trend analysis was feasible.
From Table II we can find with different discharge time ,
the components and concentration were also different. After
12 hours discharge we can detect SOF2, SO2F2, SF4, with 36
hours discharge we can detect SO2, while the SOF4 only
after 72 hours discharge can be detected. Although after 36
hours discharge we can detect SO2, its concentration change
little after 60 hours discharge, but after 84 hours discharge,
its concentration increased rapidly. The total trend SO2F2
peak was to increase, but compared with SOF2 and SO2 ,its
trend change gently. Based on the above phenomenon we
can use the gas production rate as discharge time, gas
production rate per unit time was defined as the increasing
amount of gas species concentration, in this paper c was
used to indicate the quantity:
c =
∂A
=
A i 2 − A i1 (7)
∂t Δt
In which A was the absorbance value, Ai 2 was the second
measured absorbance value, Ai1 was the first time measured
absorbance value Δt was the sampling time interval.
Observed in Table II we can easily find after 96 hours
discharge ,the absorption peaks were not saturate, some
components of the gas production rate continues to increase,
which indicates that the longer discharge,the more intense
decomposition ,the greater impact of the insulation.
According to IEC 60480 standards available we can find
:SOF2, SO2F2, SO2 were stable decomposition product of
PD .For the experiment we knew:the absorption peak of
SOF2 was 530 cm-1, SO2F2 was 544 cm-1, SO2 was 1167 cm-
1
.the absorption peak affected by other peaks was small, the
peak was sensitive to the concentration changes of
substances . the peak concentration can be characterized by
peak change, so selected them to make a preliminary
quantitative analysis. With curve-fitting we can obtain more
than three kinds of gas component concentration with time-
varying trends in discharge.The trend was shown in Figure
5-7, SOF2 increased slowly before 60 hours dicharge, then
the absorption peak increased rapidly as the the discharge
time raised. The SO2F2 production rate was high within 24
hours discharge, followed by up to 84 hours discharge, gas
production rate changed little, after discharge 84 hours
discharge the gas production rate increased once again; SO2
discharged to 84 hours, gas production rate changed little,
component concentration was low, but after 84 hours
discharge gas production rate increased suddenly ,thus
according to the law we can use SO2 concentration and gas Figure 8 The infrared spectroscopy of SF6 decomposition products by
production rate to determine the defects’ discharge time. experiment and IEC standard drawing

Figure 5 Figure 6
Figure 7 the variation of SO2’s absorbance with time
Figure 5 shows the variation of SOF2’s absorbance with
time. Figure 6 shows the variation of SO2F2’s absorbance
with time. Figure 8 shows the infrared spectroscopy of SF6
decomposition products by experiment and IEC standard
drawing, we can easily find the infrared spectroscopy of SF6
decomposition products obtained by experiment was fully
conswastent to the peak position of each component which
IEC standard layout, there were a number of small
interfering peaks which affected by micro-water actions,
they were also conswastent to standard drawing.
a: SOF2,b: SO2F2
IV. CONCLUSION
In this paper, using Fourier transform infrared absorption
spectrometry and gas chromatography analyed SF6
decomposition of component species , the concentration of
each component trends and made the following findings:
(1)The infrared absorption spectrometry and gas
chromatography test results were similar, but the
components which the former detected was more than the
latter ,FTIR can detect more intuitive and judge under the
spectrum of qualitative changed in component
concentration, its also had strong anti-interference ability, so
this mathod can be used for real-time online monitoring.
(2)SF6 with different discharge time had different
components, each component was not the same
concentration change rate ,based on these characteristics we
can determine the extent of discharge within GIS.
(3)Detected SOF2, SO2F2, SF4, SOF4, SO2 five kinds of
gas components,SOF2, SO2F2, SO2 had strong regularity
,which can be used as discharge decomposition of the
characteristics of SF6 gas, according to their changes which
can be diagnosed GIS within the state of the insulation.
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TABLE II. EACH PEAKS’ PEAK VALUES AT EACH MOMENT

Corresonding Discharge time/h

Wave number of peak/ cm-1
components 12 24 36 48 60 72 84 96
530 SOF2 0.211 0.215 0.274 0.282 0.325 0.399 0.560 0.845
539 SO2F2 0.188 0.197 0.205 0.208 0.173 0.208 0.225 0.333
544 SO2F2 0.108 0.224 0.232 0.249 0.277 0.239 0.289 0.390
552 SO2F2 0.134 0.175 0.169 0.182 0.172 0.182 0.212 0.264
746 SF4 0.118 0.140 0.114 0.148 0.239 0.175 0.330 0.553
752 SOF4 0 0 0 0 0 0.026 0.082 0.188
1103 unknown 0.066 0 0 0.140 0.264 0.164 0.189 0.698
1167 SO2 0 0 0.065 0.133 0.188 0.208 0.342 3.406
1330 SOF2 0 0 0 0.133 0.168 0.342 0.131 0.342
1340 SOF2 0.140 0.145 0.175 0.211 0.167 0.290 0.335 0.431

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