Vibrational Spectroscopy 123 (2022) 103459

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Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

The detection of SF6 decomposition components SO2F2, SOF2 using

mid-infrared TDLAS at 6.635 µm and 7.462 µm
Xiaoxing Zhang a, Zhengyi Zhu a, Yin Zhang a, *, Yi Huang b, Xiaobei Zhang b, Shunli Lv c,
Jin Yan a, Junyu Hu a
a
Hubei Engineering Research Center for Safety Monitoring of New Energy and Power Grid Equipment, Hubei University of Technology, Wuhan 430068, PR China
b
Key Laboratory of Specialty Fiber Optics and Optical Access Networks, Joint International Research Laboratory of Specialty Fiber Optics and Advanced Communication,
Shanghai University, Shanghai 200444, PR China
c
NARI Group Corporation, Ltd. (State Grid Electric Power Research Institute Co., Ltd.), Nanjing 211000, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: SO2F2 and SOF2 are the main SF6 decomposition products, and the accurate detection of trace SO2F2 and SOF2 is
SF6 electrical equipment fault diagnosis of great significance to evaluate the internal insulation of the electrical equipment. In general, gas molecules
SO2F2 and SOF2 have strong absorption coefficient in the mid-infrared spectral range, which can achieve very low detection limit
Mid-infrared laser spectroscopy
and has great advantages in the detection of trace gases. In this paper, the quantum cascade lasers at 6.635 µm
Quantum cascade laser
TDLAS
and 7.462 µm in the mid-infrared band are used as the light source of tunable diode laser absorption spectroscopy
Quantitative detection (TDLAS) to detect trace SO2F2 and SOF2. The results show that the second harmonic signal peak values of SO2F2
and SOF2 have a good linear relationship with the gas concentration. The linear fits of SO2F2 and SOF2 are
excellent at 0.99374 and 0.99785 respectively. The experimental platform has good stability, and the maximum
errors are 0.00109 V, 0.00208 V, and 0.00125 V. Allan analysis shows that the detection limit of SO2F2 is 0.1628
μL/L when the integration time is 7.44 s. The detection limit of SOF2 is 0.0167 μL/L at 2.8 s. The research results
can provide technical reference and support for the effective detection of SF6 decomposition components.

1. Introduction be evaluated, which has positive significance for equipment mainte­

In the modern electricity systems, electrical equipment is an
important part of the power systems [1]. Among the electrical equip­
ment, SF6 electrical equipment has the advantages of rapid installation,
small footprint, low operating cost, high reliability and small mainte­
nance workload. Therefore, it is widely used in the electricity industry
[2], such as gas insulated substation (GIS), gas insulated transmission
line (GIL), etc. In the long-term operation of the equipment, the inevi­
table internal insulation defects lead to partial discharge or partial
overheating in the equipment [3], which leads to the decomposition of
SF6 gas. During the decomposition process of SF6, a series of stable
chemical components are produced by reacting with the trace water and
oxygen inside the electrical equipment, such as SO2F2, SOF2 [4–6], etc.
These chemical species are the main decomposition components of SF6.
The decomposition components are corrosive and toxic, which pose a
threat to the safe and stable operation of equipment and the personal
safety of on-site maintenance personnel. Through the effective detection
of SO2F2 and SOF2, the internal situation of SF6 electrical equipment can
nance and personal safety.
At present, a lot of research has been carried out on the detection of
SF6 decomposition components. The main detection method is to
determine the type and severity of the discharge by analyzing the
composition and concentration of SF6 decomposition gas [7–10], which
includes gas chromatography, Fourier transform infrared spectroscopy,
mass spectrometry and detector tube method. Gas chromatography can
detect various SF6 decomposition components such as SO2F2, SOF2, CF4,
etc. It has high detection accuracy and sensitivity [11]. However, gas
chromatography has high requirements for the detection environment
which is mostly used in laboratory detection. Fourier transform infrared
spectroscopy can detect a wide range of SF6 decomposition components,
but it is affected by cross-interference between components and the high
number of precision parts of the equipment [12,13], which is not suit­
able for on-site inspection. Mass spectrometry can detect a wide range of
gases with high detection accuracy. However, the equipment operation
requirements are high, which will cause certain damage to the gas
components in the detection process [14,15]. The detection tube method

* Corresponding author.
E-mail address: yinzhangyz@outlook.com (Y. Zhang).

https://doi.org/10.1016/j.vibspec.2022.103459
Received 9 May 2022; Received in revised form 20 October 2022; Accepted 23 October 2022
Available online 31 October 2022
0924-2031/© 2022 Elsevier B.V. All rights reserved.
X. Zhang et al. Vibrational Spectroscopy 123 (2022) 103459

Fig. 1. Infrared spectrum of SO2F2 in the range of 400–2000 cm-1. Fig. 2. Infrared spectrum of SOF2 in the range of 400–2000 cm-1.

can detect SOF2, SO2 and other gases, which has good detection sensi­
Table 1
tivity, excellent operability and portability. But its detection is greatly
SOF2 vibrational assignments [20].
affected by the environment. It cannot be the main detection method of
SF6 decomposition components [16]. These detection methods have v (cm-1) assignment

their own advantages for the detection of SF6 decomposition compo­
nents. However, there are some shortcomings and deficiencies when
they combined with the practical application. Based on this, the effective
detection of SF6 decomposition components in the field environment is
of positive significance.
Tunable diode laser absorption spectroscopy (TDLAS) technology
controls the output wavelength and linewidth of the laser by changing
the current and temperature, which can lock the absorption band of the
gas to be measured more accurately. TDLAS technology has the ad­
vantages of high detection sensitivity, no damage to the measured gas,
and easy operation. In recent years, laser light source has become
increasingly mature. The laser light source with high-power, miniatur­
ization, low cost and long life has become the ideal light source for gas
detection. It can meet the requirements of gas detection on power en­
gineering [17,18].
Infrared spectroscopy is based on the difference of molecular bonds
with different vibrational frequencies. This difference can be used to
carry out qualitative and quantitative studies of the gas. The vibrational
transition frequency of molecules in the mid-infrared region is stronger
than that in the near-infrared region. The sensitivity of gas detection in
the mid-infrared band is higher than that in the near-infrared band [19].
SO2F2 and SOF2 have strong absorption peaks in the mid-infrared region
of 1000–2000 cm-1. It can be detected in the mid-infrared region to
improve the detection sensitivity.
SO2F2 and SOF2 are two important decomposition components of
SF6. The detection of SO2F2 and SOF2 in the mid-infrared region has
rarely been reported. Considering the advantages of detection in the
mid-infrared band, this paper adopts the mid-infrared tunable diode
laser absorption spectroscopy technology for the detection of SOF2 and
SO2F2. An experimental platform for the detection of SOF2 and SO2F2
based on mid-infrared TDLAS technology was established. The absorp­
tion waveforms of SOF2 and SO2F2 are obtained, and the linear rela­
tionship between the detection signal and the gas concentration, the
stability of the platform and the detection limit are experimentally
analyzed to determine the detection effect of the TDLAS technology on
SOF2 and SO2F2. It provides technical reference and support for the
development of SOF2 and SO2F2 detection equipment based on mid-
infrared TDLAS technology in the future.
756.9 S–F antisymmetric stretch, v5(a”)
807.5 S–F symmetric stretch, v2(a’)
1330.1 the Fermi resonance and between the S-O symmetric stretching vibration
and the combination of the S-F symmetric stretching vibration and the
symmetric deformation mode involving the OSF angles of the molecule,
v1(a’) and v2+v3(A’)
1339.8 the Fermi resonance and between the S-O symmetric stretching vibration
and the combination of the S-F symmetric stretching vibration and the
symmetric deformation mode involving the OSF angles of the molecule,
v1(a’) and v2+v3(A’)
2. Detection principle
2.1. SOF2 and SO2F2 detection band study
Since the mid-infrared band has high sensitivity for gas detection, the
detection effect can be improved. In order to investigate the detection
bands that can be used for the detection of SOF2 and SO2F2, the infrared
spectra of SOF2 and SO2F2 were obtained using the Fourier infrared
spectrometer combined with a long-range gas cell in the mid-infrared
region from 400 to 2000 cm-1 in this paper. The results are shown in
Fig. 1 and Fig. 2.
It can be seen that the infrared spectra of SO2F2 and SOF2 are basi­
cally concentrated in the range of 400–2000 cm-1. The main infrared
absorption peaks of SOF2 gas are in the 700–850 cm-1 and 1300-
1
~1400 cm-1. Vibration assignments analysis was carried out according
to the main absorption peak of SOF2, and the results are shown in
Table 1.
In these SOF2 absorption peaks, 756.9 cm-1 is assigned to the S-F
antisymmetric stretching vibration v5(a”). 807.5 cm-1 is assigned to the
S-F symmetric stretching vibration v2(a’). 1330.1 cm-1 and 1339.8 cm-1
are assigned to the Fermi resonance and between the S-O symmetric
stretching vibration v1 and the combination of the S-F symmetric
stretching vibration v2 and the symmetric deformation mode v3
Table 2
SO2F2 vibrational assignments [21].
v (cm-1) assignment

552 Rocking, v7(B1)

855.6 S-F symmetric stretch, v2(A1)
1269.9 S-O symmetric stretch, v1(A1)
1504 S-O antisymmetric stretch, v6(B1)

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X. Zhang et al. Vibrational Spectroscopy 123 (2022) 103459

Fig. 3. Schematic diagram of the experimental platform for the detection of SF6 decomposition components by mid-infrared TDLAS technology.

involving the OSF angles of the molecule. wavelength modulation amplitude, and ω is the sinusoidal modulation
The main infrared absorption peaks of SO2F2 gas are in the frequency coefficient.
500–600 cm-1, 800–920 cm-1, 1220–1320 cm-1 and 1450–1550 cm-1. Bringing the above formulas (2) and (3) into Beer-Lambert law for­
Vibration assignments analysis was carried out according to the main mula (1), the output laser light intensity signal can be obtained as:
absorption peak of SO2F2, and the results are shown in Table 2. ( ) [ ] [ ( ) ]
I v, t = I0[(1 + n sin ωt )exp −( α v0 + vf sin)ωt ]LC
In these SO2F2 absorption peaks, 552 cm-1 is assigned to the rocking (4)
≈ I0 1 + n sin ωt − α v0 + vf sin ωt LC
vibration v7(B1) of SO2F2. 855.6 cm-1 is assigned to the S-F symmetric
stretching vibration v2(A1). 1269.9 cm-1 is assigned to S-O symmetric Under a standard atmospheric pressure, the collisional broadening of
stretching vibration v1(A1). 1504 cm-1 is assigned to the S-O antisym­ particles in the infrared spectrum plays a major role. The normalized
metric stretching vibration v6(B1). Lorentz line can be used to describe the gas absorption coefficient α(v),
In these main absorption bands, SOF2 high infrared absorption peaks and the Lorentz absorption coefficient line is brought into the tuning
in the range of 700–850 cm-1 and 1220–1320 cm-1, and SO2F2 has high intensity expression, we can get:
infrared absorption peaks in the 700–850 cm-1 and 1220–1320 cm-1. ⎛ ⎞ ⎡⎛ ⎞ ⎤
The detection bands of SO2F2 and SOF2 can be determined for these
⎜ ⎟ ⎢⎜ ⎟ ⎥
bands combined with the existing laser output bands. I⎜ ⎟ ⎢⎜1 + n sin ωt⎟ a0 LC
)2 ⎥ (5)
⎝v, t⎠ = I0 ⎣⎜
⎝
⎟−
⎠
(
v0 − vc − vf sin ωt
⎦
1+ Δv
2.2. TDLAS detection principle
Among them: a0 is the absorption cross section of the pure gas at the
The detection principle of TDLAS technology for gas is based on Beer- center of the absorption line, vc is the central absorption peak, and Δv is
Lambert law [22]: the full width at half maximum of the absorption line.
I(v) = I0 (v)exp( − α(v)LC) (1) When the output center wavelength of the light source is precisely
locked at the absorption peak of the gas, v0 =vc, then:
where I0(v) is the intensity of incident light, I(v) is the intensity of out­ ( ) (
a0 LC
)
going light, α(v) is the absorption cross section of the medium per unit I v, t = I0 1 + n sin ωt − 2
(6)
1 + w2 sin ωt
concentration and unit length at wavelength v, L is the total optical path
of the absorption path, and C is the concentration of the gas to be Among them: w=vf/Δv.
measured. In the TDLAS detection process, I0(v), α(v), and L are deter­ Expanding formula (6) according to the Fourier series, each har­
mined values, and the change of the outgoing light intensity I(v) is monic signal can be obtained as the detection signal. In the harmonic
related to the concentration C of the gas to be measured. The gas con­ signal, the even-order harmonic waveform is axisymmetric to the central
centration which is to be measured can be determined by detecting the wavelength [23], which can effectively respond to the signal amplitude
change of the outgoing light intensity. offset caused by the change of gas concentration at the central wave­
The wavelength modulation technology can scan the gas absorption length. Even harmonics can be used as the detection signal. However,
peak position and extract high frequency signal as detection signal for with the increase of even harmonic order, the sensitivity of harmonic
analysis, which can effectively suppress the low-frequency noise and signal to the change of gas concentration becomes stronger, but at the
improve the detection sensitivity. In this paper, the combination of same time, the amplitude of harmonic signal decreases sharply [24]. It
wavelength modulation and harmonic detection are combined for the places high demands on the signal acquisition and processing. Based on
gas concentration detection. this, this paper adopts the second harmonic signal as the detection signal
The driving current of the quantum cascade laser is sinusoidally of gas concentration.
modulated. Its light intensity and wavelength produce corresponding The coefficients of the second harmonic term (2 f) can be obtained by
modulation effects, which are proportional to the modulation injection Fourier expansion from formula (6) as follows:
current:
I2f = − ka0 LCI0 (7)
′ ( ) ( )[ ( )]
I 0 v, t = I0 v, t 1 + n sin ωt (2) Among them:
( ) [ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ ]
v = v0 + vf sin ωt (3) 2 2 + w2 − 2 (1 + w2 )
k= √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ (8)
w2 (1 + w2 )
Among them: n is the light intensity modulation coefficient, v0 is the
central wavelength of the light source when it is not modulated, vf is the

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X. Zhang et al. Vibrational Spectroscopy 123 (2022) 103459

Table 3
SO2F2 and SOF2 laser parameters.
Type of laser performance parameter

SOF2 laser modulation range ≥ 5 cm-1

power ≥ 5 mW
line width ≤ 0.5 cm-1
SO2F2 laser modulation range ≥ 8 cm-1
power ≥ 5 mW
line width ≤ 0.5 cm-1

Since w=vf/Δv is a constant, k is also a constant associated with the

absorption center peak. The gas concentration which is to be measured
can be determined by the change of the second harmonic.

3. Experiment system

In this paper, the experimental platform for the detection of SF6

decomposition components based on mid-infrared TDLAS technology is
established for the detection of SO2F2 and SOF2. The experimental Fig. 4. SOF2 original signal waveform.
platform is mainly composed of the mid-infrared laser, laser driver, gas
absorption cell, photodetector, data acquisition card, gas mixing
equipment, host computer and other parts. The schematic diagram of
the experimental platform is shown in Fig. 3.
SO2F2 and SOF2 lasers are selected from the quantum cascade lasers.
According to the detection bands of SO2F2 and SOF2 obtained in Section
2.1 and the output band of the existing laser, the quantum cascade lasers
are used as the light sources to detect SO2F2 and SOF2. The HHL-992
QCL laser produced by Alpes Laser is used as the SO2F2 light source.
Its output wave band of is 1503.4–1511.5 cm-1. The resolution of SO2F2
laser is less than 0.5 cm-1. The HHL-994 QCL laser produced by Alpes
Laser is used as the SOF2 light source. Its output wave band is
1336.7–1342.8 cm-1. The resolution of SOF2 laser is less than 0.5 cm-1.
Other parameters of the laser are shown in Table 3.
In the experiment, the temperature of the SO2F2 laser is 50 ℃, and
the driving current of the laser is 0.41 A, so that the output wavelength
of the SO2F2 laser is at 1503.9 cm-1. The temperature of the SOF2 laser is
20 ℃, the driving current of the laser is 0.47 A, so that the output
wavelength of the SOF2 laser is at 1340 cm-1. In the case of determining
the central wavelengths of the SO2F2 and SOF2 laser, the WMS tech­ Fig. 5. SO2F2 original signal waveform.
nology is used to scan the absorption peaks of SO2F2 and SOF2 to ensure
that QCL lasers are resonant on the rotational lines of SO2F2 and SOF2. is first cleaned by using high purity helium gas at a constant flow rate of
The gas absorption cell is of Herriot construction and the optical 200 mL/min for a few minutes to remove impurity from the gas cell.
path-length is 15 m. The inner wall of the gas absorption cell is coated After the gas cell is cleaned, different concentrations of SO2F2 and SOF2
with corrosion-resistant materials to prevent damage from SO2F2 and are respectively introduced into the gas cell at a constant flow rate of
SOF2. The optical path of the device adopts a spatial optical path, which 200 mL/min. The optical signal is detected by a photoelectric sensor,
allows the position of the infrared laser to be adjusted as it is injected which is processed and displayed in the upper machine.
into the gas absorber cell. The gas mixing equipment can be configured
for experimental gases at the μL/L level.
The laser driving signal and detection signal processing of the
experimental platform is completed by the host computer. The laser
drive signal is generated by the host computer as a sawtooth wave signal
with a frequency of 600 Hz and an amplitude of 10 V as the scanning
signal. A sine wave signal with a frequency of 40 kHz and an amplitude
of 70 mV as the modulating signal and the reference channel signal of
the lock-in amplifier with the lock-in amplifier to process and extract the
second harmonic signal.

4. Experiment system

4.1. SO2F2, SOF2 concentration detection

The concentration of 1.05, 3.02, 5.02, 6.99, 8.98 μL/L SO2F2 gas,
1.05, 3.06, 5.01, 6.99, 9.01 μL/L SOF2 gas is used for testing the
detection performance of the experimental platform for SO2F2 and SOF2.
During the experiment, the temperature is kept at 25 ◦ C, and the gas cell
Fig. 6. SOF2 laser output band range.

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X. Zhang et al. Vibrational Spectroscopy 123 (2022) 103459

Table 5
The average value of the second harmonic peak corresponding to different
concentrations of SOF2.
SOF2 concentration (μL/L) Second harmonic peak average (V)
1.05 0.11565312
3.06 0.122231196
5.01 0.127529629
6.99 0.134416985
9.01 0.141617554

Fig. 7. SO2F2 laser output band range.

Table 4
The average value of the second harmonic peak corresponding to different
concentrations of SO2F2.
SO2F2 concentration (μL/L) Second harmonic peak average (V)
1.05 0.007278073
3.02 0.007452086
5.02 0.00760457
6.99 0.007762913
Fig. 8. SO2F2 Curve fitting.
8.98 0.007993613

After the SOF2 experimental gas is introduced, the original signal

waveforms of different concentrations of SOF2 are shown in Fig. 4.
Fig. 6 shows the original signal waveforms of SOF2 of each concen­
tration collected by the sensor. It can be seen that the original absorption
waveform has an absorption depression due to the influence of SOF2.
With the increase of SOF2 concentration, the concave degree increased.
This trend is particularly obvious in the range of 2000–3200, which can
be used to detect SOF2.
Fig. 5 shows the original absorption waveform of SO2F2, which is
somewhat different from that of SOF2. There are some reasons for the
difference. Firstly, the original waveform signal of SO2F2 is weaker than
that of SOF2. The amplitude of each concentration signal of SO2F2 is
little change, resulting in less variation in the waveforms. Therefore,
there is a difference between the original waveforms of SO2F2 and SOF2.
Secondly, in the experiment, the central wavelength of the outputs of
SO2F2 and SOF2 laser are aligned with the absorption peaks of SO2F2 and
SOF2. The absorption spectra of SOF2 and SO2F2 and the output band
range of the corresponding laser are marked in Fig. 6 and Fig. 7. It can be Fig. 9. SOF2 Curve fitting.
seen that compared with SOF2, the absorption peak of SO2F2 is closer to
the limit of the output band of the laser. Because the experiment uses
Table 4 and Table 5.
wavelength modulation technology (WMS), the gas absorption band
The fitting curve of SO2F2 and SOF2 gas concentration with the
should to be scanned. The SO2F2 absorption peak is close to the output
second harmonic peak is shown in Fig. 8 and Fig. 9. The abscissa axis is
limit of the SO2F2 laser, which leads to the difference between the
the gas concentration of SO2F2, SOF2, and the ordinate axis is the
original waveform of SO2F2 and the original waveform of SOF2.
measured peak value of the second harmonic signal. The solid black
As the concentration of SO2F2 experimental gas increases, the orig­
points are the second harmonic peaks corresponding to SO2F2 and SOF2
inal waveform amplitude of SO2F2 gradually decreases. In the range of
concentrations. The solid red lines are the fitted curves for SO2F2 and
800–1400, an obvious waveform decreasing trend can be seen in gen­
SOF2.
eral. This range can be used for SO2F2 concentration detection.
The fitted relationship between the concentration of SO2F2 and SOF2
The second harmonic signal is extracted according to the original
and the average value of the second harmonic peak can be obtained from
waveform extraction range of SO2F2 and SOF2. 1000 peak data points
the data in the Table 1 and Table 2:
are collected for each concentration of each gas and the average value is
taken as the second harmonic detection value for that concentration to CSO2F2=11313(2 f)− 81⋅171 (9)
avoid the influence of errors caused by isolated samples on the experi­
mental results. The average value of the second harmonic peak corre­ CSOF2=308⋅879(2 f)− 34⋅601 (10)
sponding to each concentration of SO2F2 and SOF2 is shown in the The goodness-of-fit of SO2F2 and SOF2 is above 0.99. The second

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X. Zhang et al. Vibrational Spectroscopy 123 (2022) 103459

Table 6
Error Analysis of Different Concentrations of SO2F2.
SO2F2 concentration (μL/L) Second harmonic peak detection value (V) Second harmonic peak fit value (V) Detection deviation (V) Detection error
1.05 0.007278073 0.0072945 0.000016427 0.226%
3.02 0.007452086 0.0074718 0.000019714 0.265%
5.02 0.00760457 0.0076518 0.00004723 0.621%
6.99 0.007762913 0.0078291 0.000066187 0.853%
8.98 0.007993613 0.0080082 0.000014587 0.182%

Table 7
Error Analysis of Different Concentrations of SOF2.
SOF2 concentration (μL/L) Second harmonic peak detection value (V) Second harmonic peak fit value (V) Detection deviation (V) Detection error
1.05 0.11565312 0.11546 -0.00019312 0.167%
3.06 0.122231196 0.121892 -0.000339196 0.278%
5.01 0.127529629 0.128132 0.000602371 0.472%
6.99 0.134416985 0.134468 0.000051015 0.038%
9.01 0.141617554 0.140932 -0.000685554 0.484%

Fig. 10. 40,000 points of SO2F2 second harmonic peak data under back­
ground gas. Fig. 12. SO2F2 Allan variance.

maximum error is 0.853%. The maximum deviation between the SOF2

detection data and the fitting curve is − 0.000685554 V, and the
maximum error is 0.484%. The error between the actual detection value
of the detection platform and the fitted value is small. The detection
platform can effectively characterize the measured gas concentration
through linear fitting.

4.2. System stability

The system stability is an important indicator of the detection sys­

Fig. 11. 40,000 points of SOF2 second harmonic peak data under back­
ground gas.
harmonic detection value of the detection platform has a good linear
relationship with the detected gas concentration.
Through the curve fitting of each gas, the platform error analysis is
carried out. The error analysis results are shown in Table 6 and Table 7.
According to the test results, the maximum deviation between the SO2F2
detection data and the fitting curve is 0.000066187 V, and the
tem. In this paper, helium gas is used to test the stability of the system.
The experimental environment is normal temperature and pressure. The
flow rate of the experimental gas is 200 mL/min. The experimental gas
is continuously detected. During the detection process, the second har­
monic peaks are recorded. The detection results are as follows.
As shown in Fig. 10 and Fig. 11, the abscissa axis is the number of
sampling points, and the ordinate axis is the peak value of the second
harmonic signal. In the 40000 points of collected data, the second har­
monic peak of SO2F2 is between 0.006 and 0.0085 V, of which more than
99.59% of the sampling points are concentrated between 0.0065 and
0.008 V. The measurement fluctuation is ± 0.0005 V. The average value
of the measurement results is 0.00717 V, and the maximum error with
the actual data is 0.00109 V. The second harmonic peak of SOF2 is be­
tween 0.105 and 0.11 V, of which more than 99.93% of the sampling
points are concentrated between 0.106 and 0.109 V, and the measure­
ment fluctuation is ± 0.001 V. The average value of the measurement
results is 0.1075 V, and the maximum error with the actual data is

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X. Zhang et al.
Fig. 13. SOF2 Allan variance.
Fig. 14. SOF2 voltage and avg power vs current in continuous-wave operation.
Fig. 15. SO2F2 voltage and avg power vs current in continuous-wave operation.
0.00208 V.
4.3. System detection limit
Allan variance is the common indicator for TDLAS detection limit
evaluation [25]. In this paper, helium gas is used as the experimental gas
and the gas flow rate was 200 mL/min. The experimental gas was
continuously measured for 500 s by using the detection device, and the
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Vibrational Spectroscopy 123 (2022) 103459
sampling rate of the detection data is 50 Hz. According to the experi­
mental data, the Allan variance curve is plotted, and the Allan variance
curve of each gas is shown in Fig. 12 and Fig. 13.
According to the Allan variance curve, when the integration time of
SO2F2 is 7.44 s, and the corresponding detection limit was 0.1628 μL/L.
When the integration time of SOF2 is 2.8 s, and the corresponding
detection limit was 0.0167 μL/L. It can be found in Allan variance
analysis results that the detection limit of SO2F2 is higher than the
detection limit of SOF2. Figs. 14 and 15 show the relationship between
temperature current and average output power in the laser manual. In
the experiment, the driving current of SO2F2 is 0.41 A, the temperature
is 50 ℃, the output center wave number of the SO2F2 laser is 1503.9 cm-
1
, and the corresponding average output power of the laser is about
34.7 mW. SOF2 driving current is 0.47 A, the temperature is 20 ℃, the
output center wave number of the SOF2 laser is 1340 cm-1, the corre­
sponding average output power of the laser is about 50.8 mW. The laser
intensity of SO2F2 is weaker than that of SOF2, so the detection limit of
SO2F2 is higher than that of SOF2.
The experimental platform for the detection of SF6 decomposition
components based on mid-infrared TDLAS technology has a good
detection limit and it can detect trace SO2F2 and SOF2.
5. Conclusion
In this paper, the experimental platform for the detection of SO2F2
and SOF2 based on TDLAS was established by using the mid-infrared
band with strong absorption line shape intensity and the quantum
cascade lasers with high sensitivity and easily adjustable excitation
wavelength. The concentration fitting effect, stability and detection
limit of the experimental platform were analyzed.
1. Five different concentrations of SO2F2, SOF2 were detected. The
experimental results showed that the second harmonic peak of
SO2F2, SOF2 had a better relationship with the gas concentration.
The goodness of fit reached 0.994 and 0.998, with maximum errors
of 0.853% and 0.484%.
2. The stability test was carried out with Helium gas at the constant
flow rate of 200 mL/min. The maximum errors of SO2F2, SOF2 gas
detection in the stability test of the experimental platform were
0.00109 V and 0.00208 V. The error was small, and the detection
had better stability.
3. Helium gas was used for continuous ventilation measurement, and
the allan variance was used to analyze the lower detection limit of
the experimental platform. The experimental results showed that at
7.44 s, the corresponding lower detection limit of SO2F2 was
0.1628 μL/L. At 2.8 s, the corresponding detection limit of SOF2 was
0.0167 μL/L.
After experimental analysis, mid-infrared TDLAS technology can
effectively detect trace SO2F2 and SOF2, which can be used as a reference
for future design and development.
Author statement
Xiaoxing Zhang conceived and designed the study, Zhengyi Zhu
conductedthe experiments and wrote the manuscript, Yin Zhang, Yi
Huang, Xiaobei Zhanghelped analyze the data and Jin Yan, Junyu Hu
helped with the experiment. Allauthors read and approved the final
manuscript.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
X. Zhang et al.
Data Availability
The data that has been used is confidential.
Acknowledgment
This work is supported by the Natural Science Foundation of
Shanghai (22ZR1423000), Advanced Optical Waveguide Intelligent
Manufacturing and Testing Professional Technical Service Platform of
Shanghai (19DZ2294000) and the 111 Project (D20031), the Open Fund
of the State Key Laboratory of Smart Grid Protection and Operation
Control (SGNR0000KJJS2200301) and Hubei Natural Science Fund
Innovation Group ’New Energy and Power Grid Equipment Safety Key
Technology’ (2021CFA025).
References
[1] M. Dong, C. Zhang, M. Ren, R. Albarracín, R. Ye, Electrochemical and infrared
absorption spectroscopy detection of SF6 decomposition products, Sensors 17 (11)
(2017) 2627.
[2] Shengya Qiao, Wenjun Zhou, Yong Wang, Jun Xiong, Yu Zheng, Effect of typical
adsorbents on gas change characteristics of gas insulated switchgear solid
insulation dielectric, Trans. China Electrotech. Soc. 33 (19) (2018) 4627–4635.
[3] Y. Wu, D. Ding, Y. Wang, et al., Defect recognition and condition assessment of
epoxy insulators in gas insulated switchgear based on multi-information fusion,
Measurement 190 (2022), 110701.
[4] J.S. Pearson, O. Farish, B.F. Hampton, M.D. Judd, D. Templeton, B.W. Pryor, I.
M. Welch, Partial discharge diagnostics for gas insulated substations, IEEE Trans.
Dielectr. Electr. Insul. vol. 2 (5) (1995) 893–905.
[5] Ju Tang, Dong Yang, Fuping Zeng, Xiaoxing Zhang, Research status of SF6
insulation equipment fault diagnosis method and technology based on decomposed
components analysis, Trans. China Electrotech. Soc. 31 (20) (2016) 41–54.
[6] Lingyun Song, Study on SF6 decomposition properties under partial discharge of
internal defects in GIS, Insul. Mater. 50 (06) (2017) 53–58.
[7] Yansong Ji, Chengyu Wang, Ren Yang, Xianglian Yan, Qiang Yao, Zhao Li,
Measuring technique of SF6 decomposition products and its application to fault
diagnosis of GIS, High. Volt. Appar. 47 (02) (2011) 100–103, https://doi.org/
10.13296/j.1001-1609.hva.2011.02.023.
[8] Zehong Fu, Application of laser gas analyzer in RFCC regenerated flue gas
measurement, Control Instrum. Chem. Ind. 39 (11) (2012) 1418–1422.
[9] Feng Qi, Wenqing Liu, Bin Zhou, et al., Forecasting of the real-time data monitored
by different optical absorption spectroscopy method, Acta Phys. Sci. 52 (2003)
2197.
Vibrational Spectroscopy 123 (2022) 103459
[10] Zhen Li, Zhou Zhou, Shangkun Gong, Bing Feng, Tiexiang He, Tao Wan, Research
development of detection method for SF6 decomposition characteristic and
decomposition products, Guangdong Electr. Power 29 (05) (2016) 67–76.
[11] Zhang Xiaoxing, Ren Jiangbo, Tang Ju, Xiong Hao, Infrared spectrum
characteristic and discharge trend of SF6 decomposition products, High. Volt. Eng.
35 (12) (2009) 2970–2976, https://doi.org/10.13336/j.1003-6520.
hve.2009.12.029.
[12] S. Tominaga, H. Kuwahara, K. Hirooka, et al., SF6 gas analysis technique and its
application for evaluation of internal conditions in SF6 gas equipment, IEEE Trans.
Power Appar. Syst. 23 (9) (1981) 4196–4206.
[13] Y. Wang, D. Ding, Y. Zhang, et al., Research on infrared spectrum characteristics
and detection technology of environmental-friendly insulating medium C5F10O,
Vib. Spectrosc. 118 (2022), 103336.
[14] Xiaoxing Zhang, Heng Liu, Jiangbo Ren, et al., Fourier transform infrared
spectroscopy quantitative analysis of SF6 partial discharge decomposition
components, Spectrochimica ACTA Part A-Mol. Biomol. Spectrosc. 136 (2015)
884–889.
[15] Shengchang Ji, Lipeng Zhong, Kai Liu, Jinyu Li, Yanjie Cui, Yuanyuan Wang,
Jinglong Guo, Guolong Ji, Research status and development of SF6 decomposition
components analysis under discharge and its application, Proc. CSEE 35 (09)
(2015) 2318–2332.
[16] R.J. Brunt, Production rates for oxyfluorides SOF2, SO2F2, and SOF4 in SF6 corona
discharge, Natl. Bur. Stand. 90 (3) (1985) 229–253.
[17] Li Ma, Xinli Sha, Shuo Zhang, Weifeng Wang, Gaoming Wei, Research on CH4 gas
detection and temperature correction based on tdlas technology, Spectrosc. Spectr.
Anal. 41 (11) (2021) 3632–3638.
[18] M.R. McCurdy, Y. Bakhirkin, G. Wysocki, et al., Recent advances of laser-
spectroscopy-base techniques for applications in breath analysis, J. Breath. Res. 1
(1) (2007), 014001.
[19] Yajun Yu, Study on Theory and Technology of TraceGas Detection Based on Mid-
Infrared Laser Absorption Spectroscopy[D], Wuhan University, Wuhan, 2017,
pp. 1–3.
[20] J.K. O’Loane, M.K. Wilson, Infrared Spectrum of SOF2, J. Chem. Phys. 23 (7)
(1955) 1313–1315.
[21] W.D. Perkins, M.K. Wilson, The Infrared Spectrum of SO2F2, J. Chem. Phys. 20
(11) (1952) 1791–1794.
[22] Shuyuan Lv, Feng Wang, Congqi Liu, Research on CO2 detection system based on
TDLAS-WMS, Transducer Microsyst. Technol. 40 (03) (2021) 52–54.
[23] Sun Haiyue, Ma Yufei, He Ying, et al., Highly sensitive acetylene detection based
on a compact multi-pass gas cell and optimized wavelength modulation technique,
INFRARED Phys. Technol. 102 (2019), 103012.
[24] Pan Weidong, Zhang Jiawei, Dai Jingmin, Song Kai, Tunable diode laser absorption
spectroscopy system for trace ethylene detection, Spectrosc. Spectr. Anal. 32 (10)
(2012) 2875–2878.
[25] Mu Ye, Hu Tianli, Gong He, Ni Ruiwen, Li Shijun, A Trace C2H2 sensor based on an
absorption spectrum technique using a mid-infrared interband cascade laser,
MICROMACHINES 9 (10) (2018) 530.