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An efficient procedure in quantitative analysis using laser-induced

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Plasma Sci. Technol. 21 (2019) 034012 (6pp) https://doi.org/10.1088/2058-6272/aaf50f

An efficient procedure in quantitative

analysis using laser-induced breakdown
spectroscopy
Congyuan PAN (潘从元)1 , Jiao HE (何娇)1, Guangqian WANG (王广谦)1,
Xuewei DU (杜学维)2, Yongbin LIU (刘永斌)1 and Yahui SU (苏亚辉)1
1
College of Electrical Engineering and Automation, Anhui University, Hefei 230601, People’s Republic of
China
2
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei
230029, People’s Republic of China

E-mail: cypan@ahu.edu.cn

Received 30 July 2018, revised 23 November 2018

Accepted for publication 1 December 2018
Published 27 December 2018

Abstract
Laser-induced breakdown spectroscopy has become a general-purpose technique, and internal
standard calibration is a common method for quantitative analysis. Calibration models should be
reconstructed for different systems and application environments. This study presents an efficient
procedure in the construction and selection of calibration models for LIBS analysis. The
procedure concludes data preprocess, calibration model construction, and concentration
calculation. These steps can be programmed without manual intervention. Results of the
quantitative analysis of Ni-based alloys using the proposed procedure are presented in this study.
Ten elements are calibrated, and most have an average relative standard error of less than 10%.
The proposed procedure is an effective process for constructing and selecting calibration models.

Keywords: laser-induced breakdown spectroscopy, quantitative analysis, procedure, alloys

(Some figures may appear in colour only in the online journal)

1. Introduction This study presents an efficient procedure for selecting

Laser-induced breakdown spectroscopy (LIBS) has become
an extensively used technique. Internal standard calibration is
a reliable method for quantitative analysis, and its measure-
ment accuracy depends on the calibration model. Performance
of the calibration model is related to the analytical emission
lines. Most LIBS detection systems are based on charge-
coupled devices (CCD) or intensified CCD, wherein the entire
spectrum can be recorded and thousands of characteristic
emission lines obtained [1–3]. With the selected reliable
analytical lines, different quantitative and qualitative analysis
methods were presented [4–6]. The selection of analytical
lines is tedious and time consuming even though we can
obtain examples from spark optical emission spectrometry
and inductively coupled plasma. Measurement environments,
sample types, and calibration models may be different for
different LIBS systems [7–10].
analytical lines and calibration models in LIBS analysis. The
method automatically selects lines according to the perfor-
mance of the calibration model based on these lines. With
LIBS data of certain standard samples, the proposed proce-
dure can automatically select analytical lines without manual
intervention and enhance the efficiency of the selecting
process.
2. Method
The proposed procedure obtains the LIBS spectra of the
standard sample at different delay times and determines the
peaks of these spectra. Possible spectral character lines are
confirmed by referring to the atomic emission spectrum
database and wavelength deviation. A calibration model of
each character line is constructed individually, and the

1009-0630/19/034012+06$33.00 1
Plasma Sci. Technol. 21 (2019) 034012 C Pan et al

Table 1. Parameters of the LIBS system.

Nd:YAG laser Wavelength 1064 nm

Pulse width 10 ns
Pulse energy 50 – 500 mJ
Repetition 20 Hz
Stability 3%
Spectrometer (Avantes, Range 186 – 496 nm
Holland)
Resolution 0.1 @ 200 nm
Integration time 1.1 ms – 10 min
Energy Meter Range 1.5 mJ – 3 J
(Coherent, USA)

evaluation factors are considered. The diagram of the pro-

Figure 1. Data preprocessing procedure.
character line is considered the analysis line based on the
estimation of the calibration model until all the analysis lines
are obtained. Concentration information of the analytical
element can be calculated using the calibration model that
was previously constructed. The procedure can be pro-
grammed with three sections, namely, data preprocessing,
calibration model construction, and concentration calculation.
2.1. Data preprocessing
After measuring the LIBS spectra at different delay times, the
original data should be preprocessed for calibration. First,
laser pulse energy should normalize each spectrum. Second,
the following procedure is performed in sequence: baseline
correction, peak finding, and fitting, and character line con-
firmation. Finally, useful data with species, wavelength, and
intensity are exported for the next section. Figure 1 shows the
data preprocessing procedure.
Normalization of each spectrum via laser pulse energy
contributes to the reduced influence of the fluctuation of the
energy on each spectrum [11]. A LIBS spectrum is a fair
superimposition of continuum background and numerous
spectral lines. The continuum background can be deducted
using the baseline obtained from sectional polynomial fitting
after determining the minima by derivation [12]. Finding
peaks and fitting spectra are based on multi-peak Lorentz
fitting. Spectral lines are identified from the optimized data-
base extracted from the national Institute of Standards and
Technology (NIST) atomic spectra database [13] and con-
firmed by the weight factor based on the wavelength devia-
tion, transition probability, and degeneracy.
posed procedure is shown in figure 2. The calibration curve
will be constructed with line pairs or line clusters which
consists of several line pairs. The constructed model satisfy-
ing the selection criteria will be added to the confirmed
database. Line pairs or clusters with the largest fitness sorted
by different evaluation functions for calibration construction
at this delay time are selected for quantitative analysis.
Figure 2 presents that the percentage reflected for each
line for the same sample should be larger than the existing
factor kExist after confirming all spectral lines. Otherwise, the
line is discarded. The existing factor kExist depends on the
experiment. For example, the factor can be 1 under a rela-
tively stable environment, whereas it may be 0.5 or less for
online measurement under dust environment. A possible
calibration line pair, an analytical line, and an inner reference
line are then obtained, wherein the wavelength deviation is
restricted within an appropriate region LMD_Range. The
parameter is used to reduce the fluctuation caused by the
optical system response efficiency variation. The ordinate of
each line pair should conform to k-σ check and the unavail-
able ordinates discarded. The factor depends on the con-
fidence in statistical analysis. A calibration curve is
constructed for each line pair and the line pair is added to the
confirmed database if the line pair satisfies the pre-selection
criteria. Otherwise, the line pair is discarded. The criterion is
that the correlation coefficient R2 is larger than a default value
R_Threshold. The line pairs are sorted by the fitness and the
largest N line pairs are saved. M line pairs are then selected
freely in the largest N line pairs as a cluster, thereby forming
Q = å m = 1 Cnm clusters. The evaluation indicator fitness can
m
be the following functions or their combination [15, 16].
2
R2 =
(n å x y - å x · å
n
i=1 i i
n
i=1 i
n
y
i=1 i )
,
(
nå
n
x - (å x ) ) · (nå y
i=1 i
2 n
i=1 i
2 n
i=1 i
2
- (å
n
y
i=1 i))
2

2.2. Calibration model construction 1 

å
N
RMSE (wt%) = (c - ci )2 ,
i=1 i
N
In our previous work, a multiline internal standard calibration
method (MLISC) is presented to obtain stable and accurate
1 N ci - ^ci
calibration curves [14]. The following calibration construc- ARE (%) = å
N i=1 ^ci
´ 100,
tion procedure is based on the MLISC method, wherein

2
Plasma Sci. Technol. 21 (2019) 034012 C Pan et al

Figure 2. Flowchart of calibration model construction algorithm.

3
Plasma Sci. Technol. 21 (2019) 034012 C Pan et al

Table 2. Compositions of Ni-based alloy samples.

Element #1 #2 #3 #4 #5 #6 #7 #8 #9 #10 #11 #12

C 0.125 0.125 0.099 0.129 0.103 0.12 0.119 0.128 0.126 0.093 0.125 0.123
Cr 12.95 12.91 12.87 12.82 12.77 12.75 12.45 12.88 12.96 13.06 13.23 12.87
Mo 4.19 4.19 4.21 4.2 4.31 4.44 4.4 4.11 4.18 4.15 4.06 4.17
Al 5.62 6.18 6.16 6.1 5.89 5.85 5.95 6.14 6.21 6.14 6.16 6.16
Nb 2.16 2.13 2.07 2.14 2.08 2.2 2.18 2.01 2.07 2.09 2.08 2.02
Ti 0.751 0.783 0.744 0.797 0.735 0.83 0.81 0.816 0.796 0.742 0.783 0.778
Zr 0.1 0.085 0.092 0.082 0.096 0.11 0.11 0.082 0.086 0.095 0.087 0.086
Fe 0.865 0.293 0.135 0.45 0.086 0.034 0.032 0.778 0.462 0.084 0.46 0.596
V 0.0193 0.019 0.024 0.0355 0.0142 0.0158 0.0241 0.0293
Cu 0.0026 0.0018 0.0016 0.0025 0.0021 0.0016 0.0016 0.0022 0.0023 0.0018 0.0019 0.0019

Table 3. Calibration accuracy and parameters of the calibration models of the 10 elements.

Element Concentration (wt%) Line cluster Delay time (μs) R2 ARSE

C 0.093 – 0.129 C II 299.26/Ni II 241.61 0 0.7323 5.10%
Cr 12.45 – 13.23 Cr I 385.42/Ni 337.20 0.4 0.8085 0.803%
Cr I 299.66/Ni 333.19
Mo 4.06 – 4.44 Mo I 346.92/Ni I 345.29 2.0 0.6653 1.48%
Al 5.62 – 6.21 Al I 309.27/Ni I 351.51 0.4 0.6668 1.50%
Nb 2.01 – 2.2 Nb II 314.54/Ni I 332.23 2.0 0.8164 1.12%
Nb I 371.70/Ni I 385.83
Nb II 314.54/Ni I 301.91
Ti 0.735 – 0.83 Ti II 325.29/Ni I 352.45 1.2 0.8615 0.944%
Ti I 319.99/Ni I 301.91
Zr 0.082 – 0.11 Zr I 325.04/Ni I 345.29 2.0 0.7920 3.86%
Fe 0.032 – 0.865 Fe I 363.15/Ni II 333.19 2.4 0.9943 13.4%a
Fe I 371.99/Ni I 349.30
Fe I 371.99/Ni I 377.56
V 0.0142 – 0.0355 V II 327.61/ Ni I 310.16 0.2 0.8976 7.70%
V II 327.61/ Ni I 323.29
Cu 0.0016 – 0.0026 Cu I 406.26/Ni I 351.51 0.2 0.7826 12.0%
a
ARSE of Fe will be 4.901% if the abnormal points are excluded.

(ci - c )2
å i=1
N
n-1
RSD (%) = ´ 100,
c
3sB
LOD (wt%) = ,
S

1 
å
N
RMSECV (wt%) = (c
i = 1 i,CV
- ci,CV)2
N
,
1 N ci,CV - ^ ci,CV
ARECV (%) = å
N i=1 ^
ci,CV
´ 100

Figure 3. Concentration calculation procedure.

where n is the number of calibration samples; ĉi , ci,CV are the
actual concentration of the ith sample; ci is the predicted
concentration of the ith sample; and ci,CV are the predicted
concentration of the ith sample with the calibration curve
constructed by the left n−1 samples. S is the standard

4
Plasma Sci. Technol. 21 (2019) 034012 C Pan et al

Figure 4. Diagram of the experimental LIBS system.

Figure 5. Preprocessed LIBS spectrum and confirmed lines of

Ni-based alloy.

deviation of intensity ratios and sB is the slope of the cali-

bration curve.

2.3. Concentration calculation

Delay time, calibration model, and useful information with

the largest fitness are obtained for each analytical line. After
preprocessing the spectra and confirming the spectral lines,
concentration information of the analytical line can be cal-
culated using the constructed calibration model. The details
Figure 6. MLISC curves (a) and measurement results (b) of Fe.
are shown in figure 3.

3. Experiment energy meter, reflective mirror, focus lens, collection lens,

fiber, and spectrometer. The internal timing module of the
Figure 4 shows a diagram of the LIBS system, which is spectrometer is used to control the time sequence. The
composed of Q-switched Nd:YAG laser, optical window, detailed parameters are presented in table 1.

5
Plasma Sci. Technol. 21 (2019) 034012
Twelve solid samples of Ni-based alloy with certificated
composition were used in the current experiments. The
compositions of these samples are presented in table 2. The
experiments were conducted under a laser energy of 65 mJ,
pulse repetition of 5 Hz, integration time of 5 ms, and inte-
gration delay time of 0 to 3 μs using a step delay of 0.2 μs.
Each recorded spectrum was the average of 10 measurements,
which was normalized using the corresponding pulse energy,
and 10 spectra were collected under the same conditions and
used for the following process.
4. Results and discussion
Figure 5 shows the preprocessed LIBS spectrum at a delay
time of 0 μs. Concerning the trace elements in the samples,
seventeen elements were identified, including carbon, phos-
phorus, chromium, copper, aluminum, and iron. Other ele-
ments can be detected but are difficult to calibrate. The line
database was obtained from the Handbook of Basic Atomic
Spectroscopic Data (eBook Version) of NIST.
Ten elements, including C, Cr, Mo, Al, Nb, Ti, Zr, Fe, V,
and Cu, were calibrated using the proposed procedure.
Figure 6 presents the MLISC curves and the repeated mea-
surement results of Fe. The number presented before the line
pair is corresponding weight in calibration model construc-
tion. The calibration model used the summary of three line
pairs, with each line pair having a weight that is the fitness of
a single line pair. The metrical accuracy and parameters of the
optimal calibration models are presented in table 3. Most of
the average relative standard errors (ARSEs) were lower
than 10%.
5. Conclusion
The proposed procedure contributes to the automatic and
efficient construction of calibration curves and determines
best performance without considering the plasma physics.
Ten elements were calibrated using the proposed procedure
by LIBS. Most measurements have an ARSE value of less
View publication stats
C Pan et al
than 10%. The results show the high efficiency of the pro-
posed procedure in quantitative analysis using LIBS and
confirm the feasibility and advantage of metallurgical analysis
using LIBS.
Acknowledgments
The authors are grateful for the financial support provided by
National Natural Science Foundation of China (11704372) and
Anhui Provincial Natural Science Foundation (1708085QF130).
ORCID iDs
Congyuan PAN (潘从元) https://orcid.org/0000-0002-
8006-3049
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