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Article
Determination of carbon content in steels using laser-induced breakdown
spectroscopy assisted with laser-induced radical fluorescence
Jiaming Li, Zhihao Zhu, Ran Zhou, Nan Zhao, Rongxing Yi, Xinyan
Yang, Xiangyou Li, Lianbo Guo, Xiaoyan Zeng, and Yongfeng Lu
Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.7b01932 • Publication Date (Web): 01 Jul 2017
Downloaded from http://pubs.acs.org on July 4, 2017

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Page 1 of 16 Analytical Chemistry

1
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7 Determination of carbon content in steels using laser-induced break-
8
9
down spectroscopy assisted with laser-induced radical fluorescence
10
11
Jiaming Li, Zhihao Zhu, Ran Zhou, Nan Zhao, Rongxing Yi, Xinyan Yang, Xiangyou Li*, Lianbo Guo,
12 Xiaoyan Zeng, Yongfeng Lu
13
Wuhan National Laboratory for Optoelectronics (WNLO), Huazhong University of Science and Technology, Wuhan, Hubei
14
430074, P. R. China
15
16 ABSTRACT: Carbon is a key element for steel properties, but hard to be determined by laser-induced breakdown spectroscopy
17 (LIBS). Utilizing the combination of carbon in analytes and nitrogen in ambient gas to generate carbon-nitrogen (CN) radicals,
18 LIBS assisted with laser-induced radical fluorescence (LIBS-LIRF) was proposed to resonantly excite radicals instead of atoms in
19 plasmas. The CN radicals in the B2Σ-A2Π band were stimulated by a 421.60 nm laser wavelength, and emitted 388.34 nm fluores-
20 cence. The results show that the spectral intensity of the CN radicals was enhanced by two orders of magnitude using LIBS-LIRF.
21 Then carbon content in steels was accurately and sensitively determined without spectral interference. The limits of detection
(LoDs) were 0.039 and 0.013 wt.% in air and nitrogen gas, respectively. The limits of quantification (LoQs) were 0.130 and 0.043
22
wt.% in air and nitrogen gas, respectively. This work demonstrated the feasibility of LIBS to realize reliable carbon determination
23
in steel industry.
24
25
26
27 Carbon element has always been a key element for steel vacuum ultraviolet (VUV) lines to detect carbon in steels,21-29
28 properties. With low carbon contents, steels have high plastici- but gas-tight tubes or chambers with noble gas and ultra-low
29 ty, ductility, tenacity, and thermal stability, suitable for weld- pressure were necessary for optical probes to increase VUV
30 ments, rebars, pipelines, and hoisting cables. With high carbon transmittance, which makes it not feasible for industrial analy-
31 contents, steels have high strength, hardness, and abrasive sis in open air. In addition, carbon near-IR line was also used
32 resistance, suitable for rails, tools, gear, and bearings. There- for steel analysis, but not sensitive enough for low-carbon
33 fore, it is crucial to determine carbon contents in steels for steels.30
34 quality assurance. The conventional methods for carbon de- LIBS assisted with laser-induced fluorescence (LIBS-LIF)
termination in steel include chemical titrimetry,1,2 spark source is a spectral enhancement method for LIBS signals. In LIBS-
35
atomic emission spectrometry (SS-AES) in pure argon,3 parti- LIF, target atoms were resonantly excited by a wavelength-
36
cle-induced gamma-ray emission (PIGE)4,5 etc. These methods tunable laser, whilst other atoms in plasma were almost un-
37 are so lengthy, complicated, short detective distance, time-
38 changed. Therefore, the emission intensity of the target atoms
material consuming, or harmful for health, which makes them is selectively enhanced. Detections of lead,31-33 cobalt,34,35
39 only be used in laboratories for offline analysis. In contrast, a phosphorus,36,37 iron,32 boron,38 ytterbium,39 and thallium40
40 rapid and online technique for carbon determination can not using LIBS-LIF were reported, which demonstrate high effec-
41 only evaluate product quality, but also provide real-time feed- tiveness in improving analytical sensitivity and accuracy. Be-
42 back in the steel manufacture.6 In past decades, researchers all cause the addition is another laser beam compared with con-
43 around the world are making the efforts to develop new ana- ventional LIBS, LIBS-LIF can keep most of the attractive
44 lytical methods to realize the goal. advantages of LIBS, and is suitable for steel real-time analysis
45 Laser-induced breakdown spectroscopy (LIBS) is an in the manufacture. However, all resonant lines of carbon at-
46 atomic spectrometry based on laser-ablation,7-9 in which ele- oms are in deep ultraviolet range under 170 nm, where the
47 mental information is deduced by analyzing spectra emitted light is severely absorbed by air, and few commercial wave-
48 from laser-induced plasmas. With attractive advantages of in length-tunable lasers are available in this range. Therefore, it
49 situ, remote detection, minimal sample preparation, rapid and is infeasible to resonantly excite carbon atoms to improve
50 multi-elemental detections, LIBS shows great potential in real- analytical accuracy and sensitivity.
51 time analysis of steels, and has been tentatively applied in In this work, an alternative was proposed that carbon-
52 many fields, such as environmental protection,10 nuclear reac- nitrogen (CN) radicals instead of carbon atoms in plasmas
53 tion monitoring,11 solar cells,12 special fibers,13 space explora- were resonantly excited. To be differentiated from conven-
tion,14 archaeological verification,15 etc. In previous works tional LIBS-LIF, this proposed approach was called LIBS
54
about carbon determination by LIBS, some researchers chose assisted with laser-induced radical fluorescence (LIBS-LIRF).
55
C I 247.86 nm as an analytical line,16-19 but weak emission of Though the CN radical emission was used to analyze organics
56 carbon atoms and strong spectral interference from iron lines
57 (e.g. coal,41,42 bio-tissue,43 and polymers44) with high carbon
make it difficult to realize accurate and sensitive determination contents, it is too weak to observe in steels with low carbon
58 of carbon contents in steels.20 Some other researchers utilized contents using conventional LIBS. In the proposed LIBS-LIRF,
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the CN radical emission was greatly enhanced by laser reso- Shamrock 500i, grating of 1800 lines per mm) through a mul-
1 nant excitation to detect carbon contents in steels. ticore fiber. Pure nitrogen (Wuhan Xiangyun Industry, 99.999%
2 purity) gas was blown to cover the plasma for improving reac-
3 tion efficiency between carbon and nitrogen atoms. An inten-
4 EXPERIMENTAL SETUP AND SAMPLES sified charge-coupled device (ICCD) (Andor Technology,
5 Physical process of LIBS-LIRF. In our work, the CN radi- iStar 320T) was equipped to record the spectra. Both lasers
6 cals in the plasmas were used as the resonantly excited target. and the ICCD were sequentially triggered by a digital delay
7 The physical process is shown in Figure 1 and described be- generator (Stanford Research Systems, DG535). The OPO
8 low. laser and the ICCD gate were simultaneously switched. The
9 (a) Breakdown: the sample and ambient gas were simultane- ICCD gate width was 10 ns. The interpulse delay was opti-
ously heated by the focused laser pulses, then produced plas- mized to be 2 µs. The signals generated by 100 pulses of the
10
mas. ablation laser and enhanced by 100 pulses of the OPO laser
11 were accumulated on the detector to generate one spectrum.
12 (b) Atomization: carbon in the sample and nitrogen in the am- Each sample was measured repeatedly for ten times.
13 bient gas were atomized in the plasma.
14 (c) Combination: carbon and nitrogen atoms combined to form
15 CN radicals in the plasmas.
16 (d) Excitation: the CN radicals were resonantly excited by the
17 421.60 nm laser, and then emitted 388.34 nm fluorescence.
18
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30 Figure 2. Schematic diagram of the experimental setup.
31
32 Samples. Eight low-alloy steel samples from National Insti-
33 tute of Standards and Technology (1264a, 1270, 1761a, 1762a,
34 1763a, 1764a, 1766, and C1285, carbon contents: 0.015-1.05
35 Figure 1. Schematic diagram of LIBS-LIRF experimental process: wt.% listed in Table 1) were used to build a quantitative model
36 breakdown (a), atomization (b), combination (c), and excitation (d) in our work. One pig iron sample from Ansteel Research Insti-
37 tute (GSB03-2582-2010-7, carbon content: 4.13 wt.%), and
38 one polyvinyl chloride (PVC) pellet ([CH2-CH-Cl]n carbon
Experimental Setup. A schematic diagram of the LIBS-LIF content: 38.4 wt.%) were used to observe CN radical spectra.
39 setup used in this work is shown in Figure 2. A Q-switched
40 Nd:YAG laser (Beamtech Optronics, Nimma 400, pulse dura-
41 tion of 6 ns, flattened Gaussian beam) operating at 532 nm and Table 1. Carbon contents (wt.%) in low-alloy steels
42 10 Hz was used as an ablation source. The laser beam was NIST Content NIST Content
43 reflected by a mirror, and then focused onto sample surfaces to
44 1264a 0.871 1763a 0.202
generate plasmas. To mitigate the laser damage to samples, the
45 laser pulse energy and focal length for ablation were set at 2 1270 0.077 1764a 0.592
46 mJ and 25 mm, respectively. The focal spot diameter on the 1761a 1.050 1766 0.015
47 sample is about 100 µm. The laser ablation fluence was 25.5 1762a 0.341 C1285 0.058
48 J/cm2. A wavelength-tunable laser, equipped with an optical
49 parametric oscillator (OPO) (OPOTEK Inc., wavelength range
50 of 410-710 nm) pumped by a Q-switched Nd:YAG laser RESULTS AND DISCUSSION
51 (Quantel, Brilliant b, wavelength of 355 nm, repetition rate of The resonant photons can excite CN radicals in only
10 Hz), was used as an excitation source. The excitation laser one specific state. Because the X2Σ+ electronic state is the
52
beam was focused and covered the plasma by a UV-grade
53 ground state in CN radicals45, the largest number of radi-
quartz lens (f = 150 mm). The pulse energy and irradiation
54 cals were in the X2Σ+. Therefore, the CN radicals in the
density of the excitation laser at the plasma was about 15 mJ
55 and 21.2 MW/cm2, respectively. The fluorescent light emis-
X2Σ+ state were chosen as the targets in the plasmas. Dif-
56 sion from the plasma was collected by a light collector (Ocean ferent from those in the atoms, electronic states in radicals
57 Optics, 84-UV-25, wavelength range: 200-2000 nm) and cou- were consisted of several vibrational and rotational levels.
58 pled into a Czerny-Turner spectrometer (Andor Technology, In this work, heads in vibrational bands were used, there-
59 fore rotational levels were not discussed.
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Violet system B2Σ+-X2Σ+ is easily excited and of frequent
1 occurrence in CN spectra.46 Transitions of (0, 0) 388.34 nm
2 and (0, 1) 421.60 nm have the strongest emission in the violet
3 system. The wavelength-tunable laser beam in our experiment
4 was obtained from the OPO pumped by 355 nm laser (third
5 harmonic of an Nd:YAG laser). The wavelength range of out-
6 put from the OPO is 410-710 nm, where the B2Σ+-X2Σ+ (0, 1)
7 421.60 nm is in that range. However, a 388.34 nm laser beam
8 requires mixing another 1064 nm and a 611.54 nm laser beams.
9 Not only the pulse energy and stability will be greatly de-
creased, but also the cost will be raised. Moreover, the mixing
10
model is sensitive to the ambient temperature, which makes it
11 not suitable for application in industry. Therefore, (0, 1)
12
421.60 nm transition in the B2Σ+-X2Σ+ system was chosen as
The synchronicity between OPO light and CN fluores-
cence was studied, shown in Figure 5. In conventional LIBS-
LIF with atomic excitation, the laser-induced fluorescence is
synchronic.34,47 In LIBS-LIRF, the OPO light and CN fluores-
cence rose and reached the peak synchronically. Then the fluo-
rescence decayed 1-2 ns slower than OPO light. The result
indicated the lifetime of the level B2Σ+ (ν=0) is about 1-2 ns.
The whole lifetime of the CN fluorescent in this work is about
10 ns. Therefore, the gate width of the detector was set to be
10 ns in LIBS-LIRF signal acquisition.
OPO laser light
1.2

Normalized intensity
Fluorescence
13 excitation in our work, while (0,0) 388.34 nm was the obser-
14 vation line. 0.9
15
16 0.6
17
18
0.3
19
20
0.0
21
22 0 2 4 6 8 10 12 14
23 Time (ns)
24 Figure 5. Synchronicity between OPO laser and CN fluorescence
25 Figure. 3. Schematic diagram of LIRF in CN radicals of B2Σ+-X2Σ+ (0,0) in LIBS-LIRF.
26 In the excitation process shown in Figure 3, the CN radi-
27 cals in X2Σ+ (ν=1) were stimulated. When the photon energy
28 Figure 6 shows the spectra of the pig iron sample in air
of the OPO laser (421.60 nm) is equal to the energy gap (2.94 and nitrogen by LIBS and LIBS-LIRF. No CN B2Σ+-X2Σ+ (0,0)
29 eV) between X2Σ+ (ν=1) and B2Σ+ (ν=0), the CN radicals in 388.34 nm signal was observed in LIBS. However, strong sig-
30 X2Σ+ (ν=1) transited up to B2Σ+ (ν=0). The CN radicals in B2Σ+ nals without spectral interference were observed in LIBS-
31 (ν=0) were not stable, then transited down to X2Σ+ (ν=0) and LIRF with 421.60 nm laser excitation. Moreover, the spectral
32 emitted 388.34 nm fluorescence. intensity of CN radicals in nitrogen gas was significantly
33 To prove the effectiveness of LIBS-LIRF, the CN radical greater than that in air, because nitrogen gas provided more
34 spectra of the PVC sample acquired by LIBS and LIBS-LIRF sufficient nitrogen source for carbon-nitrogen generation than
35 were shown in Figure 4. The head intensity of B2Σ+-X2Σ+ (0, 0) air, and it can prevent carbon from oxidization by oxygen at-
36 388.3 nm in LIBS-LIRF was much greater than that in LIBS oms in air. In addition, there was a line of iron atoms in 421.62
37 under the same experimental condition. This proved that the nm, close to CN excitation line 421.60 nm. Therefore, the iron
38 CN radicals were significantly stimulated by the 421.60 nm lines with the same upper level configuration as Fe I 421.62
39 laser, and their emission in 388.34 nm can be effectively en- nm were also enhanced in Figure 6.
40 hanced.
41
20
42 25 LIBS in air
CN B2Σ+-X2Σ+ (0,0)
43 LIBS LIBS in nitrogen
Intensity (x104 counts)

Head 16 LIBS-LIRF in air

LIBS-LIRF
Intensity (x104 counts)

44 20
LIBS-LIRF in nitrogen
Fe I 388.63 nm

CN B2Σ+-X2Σ+ (0,0)
45
Fe I 385.99 nm

Fe I 387.86 nm
OPO idler light

12
Fe I 385.64 nm

46 15
Fe I 387.25 nm
CN B2Σ+-X2Σ+ (1,1)
Fe I 386.55 nm

47 8
10
48 Rotational spectra
49 4
5
50
51 0
0
52 385.7 386.4 387.1 387.8 388.5 389.2
53 382 384 386 388 Wavelength (nm)
54 Wavelength (nm)
Figure 6. CN B2Σ+-X2Σ+ (0,0) 388.34 nm signals acquired by
55 2 + 2 +
Figure 4. B Σ -X Σ (0,0) spectra of the PVC sample using LIBS LIBS in air (black line), LIBS in nitrogen (green line), LIBS-
56 (black line) and LIBS-LIRF (blue line). LIRF in air (blue line), and LIBS-LIRF in nitrogen (red line).
57
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Influences of the interpulse delays between the two lasers
1 on CN B2Σ+-X2Σ+ (0,0) fluorescence intensity were investigat-
2 ed and shown in Figure 7. In the early stage (1 µs), the plas-
3 mas were just generated and the CN radicals started to form.
4 The number of CN radicals in the plasmas was not large. Then
5 the emission intensities reached the peaks at the interpulse
6 delay of 2 µs, where the numbers of CN radicals maximized.
7 With plasmas expanding and CN radicals combining with
8 other particles in late stage, the intensities of CN fluorescence
9 decayed. To acquire better fluorescence signals, the interpulse
delay was optimized to be 2 µs in the determination of carbon
10
content in steels.
11
12 Moreover, comparing the intensities of CN fluorescence
LoQ were 0.043 wt.% in nitrogen gas and 0.130 wt.% in air.
The RMSECV values were 0.046 and 0.078 wt.% in nitrogen
gas and air, respectively, much better the 0.226 wt.% in LIBS.
The results proved that LIBS-LIRF has a significantly higher
sensitivity and accuracy than atomic LIBS for carbon content
determination in steels. Furthermore, the excitation and obser-
vation windows for CN radical fluorescence are both in the
visible range, where transmittance and efficiency of optical
systems are satisfactory, and tubes or chambers with noble gas
and ultra-low pressure are not necessary. That makes it suita-
ble for online analyses of steels.
3.0

Normalized intensity (C I 193.1 nm)

Normalized intensity (C I 247.9 nm)

13 in air and nitrogen, the ratio between the fluorescence intensity (a)
C I 193.1 nm
in nitrogen kept increasing before 8 µs, which indicated the 2.8 0.60
14 C I 247.9 nm
CN radicals decayed more slowly in nitrogen gas. Therefore,
15 the nitrogen gas provided a more stable condition for CN radi-
2.6
16 0.55
cals. 2.4
17
18 2.2 0.50
19 21
In air 35
20 18 2.0 0.45
In nitrogen
30
Intensity (x104 counts)

21 15 Ratio (Initrogen/Iair) 1.8

22
Ratio (Initrogen/Iair)

25
23 12 0.0 0.2 0.4 0.6 0.8 1.0 1.2
20
24 9 Carbon content (wt.%)
15
25
6
26 10
0.6
27 3 5 (b)
CN 388.3 nm in nitrogen
28 0 CN 388.3 nm in air
0 0.5
29
Normalized Intensity

0 2 4 6 8 10
30
Interpulse delay (µ
µs) 0.4
31
32 Figure 7. Influences of the interpulse delays on CN B2Σ+-X2Σ+
0.3
33 (0,0) fluorescence intensity acquired by LIBS-LIRF in air (blue
34 scatters and line) and nitrogen (red scatters and line); and the ratio
35 (green scatters and line) between fluorescence intensity in nitro- 0.2
36 gen and air.
37 0.1
0.0 0.2 0.4 0.6 0.8 1.0 1.2
38 After investigations on the mechanism and behavior of
Carbon content (wt.%)
39 laser-induced CN radical fluorescence in plasmas, the carbon
40 contents in steels were determined. The internal calibration Figure 8. (a) Internal calibration curves of carbon in steels meas-
41 curves were established by LIBS and LIBS-LIRF, as shown in ured by LIBS with atomic lines 193.1 nm (purple scatters and
42 Figure 8. To reduce spectral fluctuation, C I 193.1 nm, C I line) and 247.9 nm (orange scatters and line); (b) internal calibra-
247.9 nm, and CN 388.34 nm were normalized by Fe II tion curves of carbon in steels measured by LIBS-LIRF in nitro-
43
188.87 nm, Fe I 248.3 nm, and Fe I 388.7 nm, respectively. gen gas (red scatters and line) and air (blue scatters and line).
44
The analytical performances were listed in Table 2. The limit
45
of detections (LoDs) and limit of qualification (LoQs), which Table 2. Carbon contents (wt.%) in low-alloy steels
46 were calculated according to the 3σ/s and 10σ/s criteria, were
47 used to evaluate sensitivity. Determination coefficient R2 rep- Gas Line LoD LoQ R2 RMSECV
48 resents analytical linearity. Accuracy was evaluated by calcu- (nm) (wt.%) (wt.%) (wt.%)
49 lating the root mean square error of cross-validation Air 193.1 0.060 0.200 0.871 0.226
50 (RMSECV) in leave-one-out cross-validation (LOOCV) LIBS
Air 247.9 - - 0.088 -
51 method. In atomic LIBS analyses, C I 193.1 nm line had an
52 LIBS- N2 388.3 0.013 0.043 0.991 0.046
unreliable calculated LoD of 0.060 wt.% and LoQ of 0.200 wt.%
53 due to the poor accuracy with an R2 factor of 0.871, and C I LIRF Air 388.3 0.039 0.130 0.974 0.078
54 247.9 nm intensity had no relation with the carbon content.
55 Nevertheless, in LIBS-LIRF analyses, the R2 factors were The conventional methods and LIBS-LIRF in carbon de-
56 greatly improved to 0.991 and 0.974 in nitrogen gas and air, termination were compared in Table 3. After developing for
57 respectively. It was demonstrated that LIBS-LIRF has a signif- decades, the conventional methods have better analytical per-
58 icantly higher analytical linearity than atomic LIBS. The LoDs formances than LIBS-LIRF in this work. However, these ex-
59 were 0.013 wt.% in nitrogen gas and 0.039 wt.% in air. And
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Table 3. Comparison of conventional methods and LIBS-LIRF in carbon determination

1 LoD Gas Sample preparation Response time Distance Online detection
2
Titrimetry1,2 Wt.10-4 Air Complicated Minutes None Unavailable
3
4 SS-AES3 Wt.10-5 Vacuum/He/Ar in whole probes Simple Minutes Millimeters Unavailable
5 PIGE4,5 Wt.10-5 Vacuum/He/Ar in whole probes Simple Seconds Millimeters Unavailable
6 LIBS21-29 Wt.10-5 Vacuum/He/Ar in whole probes Dispensable Seconds Tunable Unavailable
7 LIBS-LIRF Wt.10-4 Air/N2 on samples Dispensable Seconds Tunable Available
8 isting methods are not suitable for online detection, because of (6) Sun, L. X.; Yu, H. B.; Cong, Z. B.; Xin, Y.; Li, Y.; Qi, L. F.
9 complicated operation, lengthy process, or short detective Spectrochim Acta B 2015, 112, 40-48.
10 distance. In contrast, the proposed method LIBS-LIRF has (7) Singh, J. P.; Thakur, S. N. Laser-induced breakdown
11 spectroscopy; Elsevier, 2007.
incomparable advantages of rapid response, tunable detective
(8) Li, J. M.; Guo, L. B.; Li, C. M.; Zhao, N.; Yang, X. Y.; Hao, Z.
12 distance, in-situ detection no or simple sample preparation, Q.; Li, X. Y.; Zeng, X. Y.; Lu, Y. F. Opt. Lett. 2015, 40, 5224-5226.
13 and small detection spot, which provide LIBS-LIRF great (9) Wang, Z.; Yuan, T. B.; Hou, Z. Y.; Zhou, W. D.; Lu, J. D.; Ding,
14 potentials and competitiveness in online detection. Sensitivity H. B.; Zeng, X. Y. Frontiers of Physics 2014, 9, 419-438.
15 improvement of LIBS-LIRF is the key of our further work. (10) Popov, A. M.; Colao, F.; Fantoni, R. J. Anal. At. Spectrom. 2010,
16 25, 837-848.
(11) Martin, M. Z.; Allman, S.; Brice, D. J.; Martin, R. C.; Andre, N.
17
CONCLUSIONS O. Spectrochim Acta B 2012, 74-75, 177-183.
18 (12) Lee, S. H.; Shim, H. S.; Kim, C. K.; Yoo, J. H.; Russo, R. E.;
19 In this work, a novel approach was established to deter-
Jeong, S. Appl. Opt. 2012, 51, B115-B120.
20 mine carbon contents in steels using laser-induced CN radical (13) Li, J.; Guo, L.; Zhao, N.; Chen, Q.; Wu, B.; Wang, Y.; Li, X.; Li,
fluorescence in LIBS. Different from conventional LIBS-LIF, J.; Zeng, X.; Lu, Y. J. Anal. At. Spectrom. 2016, 31, 492-496.
21
LIBS-LIRF in this work takes CN radicals as the resonantly (14) Vaniman, D.; Dyar, M.; Wiens, R.; Ollila, A.; Lanza, N.; Lasue,
22
excited targets. The results show that CN emission intensity in J.; Rhodes, J.; Clegg, S.; Newsom, H. Space science reviews 2012,
23 LIBS-LIRF was two orders of magnitude stronger than that in 170, 229-255.
24 LIBS. For the carbon determination in steels, R2 values of (15) Giakoumaki, A.; Melessanaki, K.; Anglos, D. Anal. Bioanal.
25 0.991 and 0.974, LoDs of 0.013 and 0.039 wt.%, LoQs of Chem. 2007, 387, 749-760.
26 0.043 and 0.130 wt.%, were achieved using LIBS-LIRF in (16) Noda, M.; Deguchi, Y.; Iwasaki, S.; Yoshikawa, N. Spectrochim.
27 Acta, Part B 2002, 57, 701-709.
nitrogen gas and air, respectively, which are significantly bet- (17) Yuan, T.; Wang, Z.; Li, Z.; Ni, W.; Liu, J. Anal. Chim. Acta
28 ter than those in atomic LIBS. This work opens up a new area 2014, 807, 29-35.
29 for LIBS to realize a highly accurate and sensitive determina- (18) Abdulmadjid, S. N.; Idris, N.; Pardede, M.; Jobiliong, E.;
30 tion of carbon contents in steels. It also suggests that radical Hedwig, R.; Lie, Z. S.; Suyanto, H.; Tjia, M. O.; Kurniawan, K. H.;
31 excitation is a meaningful alternative when atomic excitation Kagawa, K. Spectrochim Acta B 2015, 114, 1-6.
32 is not available in LIBS-LIF. (19) Li, X.; Wang, Z.; Fu, Y.; Li, Z.; Liu, J.; Ni, W. Appl. Spectrosc.
2014, 68, 955-962.
33 (20) Zaytsev, S. M.; Popov, A. M.; Zorov, N. B.; Labutin, T. A.
34 Spectrochim Acta B 2016, 118, 37-44.
35 AUTHOR INFORMATION (21) Jiang, X.; Hayden, P.; Laasch, R.; Costello, J. T.; Kennedy, E. T.
36 Spectrochim Acta B 2013, 86, 66-74.
Corresponding Author
37 (22) Jiang, X.; Hayden, P.; Costello, J. T.; Kennedy, E. T.
* Phone: 86-27-87544774. Fax: +86-27-87541423. Spectrochim Acta B 2014, 101, 106-113.
38 E-mail: xyli@mail.hust.edu.cn (23) Sturm, V.; Peter, L.; Noll, R. Appl. Spectrosc. 2000, 54, 1275-
39 1278.
40 Author Contributions (24) Aragon, C.; Aguilera, J.; Campos, J. Appl. Spectrosc. 1993, 47,
41 The manuscript was written with contributions of all authors. All 606-608.
42 authors have given approval to the final version of the manuscript. (25) Aragon, C.; Aguilera, J. A.; Penalba, F. Appl. Spectrosc. 1999,
Notes 53, 1259-1267.
43 (26) Khater, M. A.; Costello, J. T.; Kennedy, E. T. Appl. Spectrosc.
The authors declare no competing financial interest.
44 2002, 56, 970-983.
45 ACKNOWLEDGMENT (27) Khater, M. A.; van Kampen, P.; Costello, J. T.; Mosnier, J. P.;
46 Kennedy, E. T. J Phys D Appl Phys 2000, 33, 2252-2262.
National Instrumentation Program of China (No. 2011YQ160017) (28) Hemmerlin, M.; Meilland, R.; Falk, H.; Wintjens, P.; Paulard, L.
47
and National Natural Science Foundation of China (No. Spectrochim Acta B 2001, 56, 661-669.
48 61575073). (29) Peter, L.; Sturm, V.; Noll, R. Appl. Opt. 2003, 42, 6199-6204.
49 (30) Labutin, T. A.; Zaytsev, S. M.; Popov, A. M.; Zorov, N. B. Opt.
50 REFERENCES Express 2014, 22, 22382-22387.
51 (1) Jones, R.; Gale, P.; Hopkins, P.; Powell, L. Analyst 1965, 90, 623- (31) Goueguel, C.; Laville, S.; Loudyi, H.; Chaker, M.; Sabsabi, M.;
52 629. Vidal, F. In Photonics North 2008; International Society for Optics
53 (2) Boniface, H.; Jenkins, R. Analyst 1971, 96, 37-46. and Photonics: Montréal, 2008, p 709927.
(3) Song, Z.-f.; Mou, X.-y.; Cheng, J.-p.; Cheng, X.-f.; Zhang, P. (32) Loudyi, H.; Rifai, K.; Laville, S.; Vidal, F.; Chaker, M.; Sabsabi,
54 M. J. Anal. At. Spectrom. 2009, 24, 1421-1428.
Metallurgical Analysis 2008, 10, 003.
55 (4) Ene, A.; Popescu, I.; Badica, T. J Optoelectron Adv M 2006, 8, (33) Laville, S.; Goueguel, C.; Loudyi, H.; Vidal, F.; Chaker, M.;
56 222-224. Sabsabi, M. Spectrochim. Acta, Part B 2009, 64, 347-353.
57 (5) Xu, Y.; Xu, M.; Wang, G.-F.; Zheng, C.-L.; Qiu, M.-L.; Chu, Y.- (34) Li, J.; Guo, L.; Zhao, N.; Yang, X.; Yi, R.; Li, K.; Zeng, Q.; Li,
58 J. Nuclear Science and Techniques 2016, 27, 137. X.; Zeng, X.; Lu, Y. Talanta 2016, 151, 234-238.
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(35) Gornushkin, I.; Kim, J.; Smith, B.; Baker, S.; Winefordner, J. (43) Baudelet, M.; Guyon, L.; Yu, J.; Wolf, J. P.; Amodeo, T.;
1 Appl. Spectrosc. 1997, 51, 1055-1059. Frejafon, E.; Laloi, P. Appl. Phys. Lett. 2006, 88.
2 (36) Kondo, H.; Hamada, N.; Wagatsuma, K. Spectrochim. Acta, Part (44) Yu, Y.; Guo, L. B.; Hao, Z. Q.; Li, X. Y.; Shen, M.; Zeng, Q. D.;
B 2009, 64, 884-890. Li, K. H.; Zeng, X. Y.; Lu, Y. F.; Ren, Z. Opt. Express 2014, 22,
3
(37) Shen, X. K.; Wang, H.; Xie, Z. Q.; Gao, Y.; Ling, H.; Lu, Y. F. 3895-3901.
4 Appl. Opt. 2009, 48, 2551-2558. (45) Knowles, P. J.; Werner, H. J.; Hay, P. J.; Cartwright, D. C. The
5 (38) Li, C.; Hao, Z.; Zou, Z.; Zhou, R.; Li, J.; Guo, L.; Li, X.; Lu, Y.; Journal of Chemical Physics 1988, 89, 7334-7343.
6 Zeng, X. Opt. Express 2016, 24, 7850-7857. (46) Pearse, R. W. B.; Gaydon, A. G.; Pearse, R. W. B.; Gaydon, A.
7 (39) Li, J.-M.; Chu, Y.-B.; Zhao, N.; Zhou, R.; Yi, R.-X.; Guo, L.-B.; G. The identification of molecular spectra; Chapman and Hall
8 Li, J.-Y.; Li, X.-Y.; Zeng, X.-Y.; Lu, Y.-F. Chinese J Anal Chem London, 1976; Vol. 297.
2016, 44, 1042-1046. (47) Li, J.; Hao, Z.; Zhao, N.; Zhou, R.; Yi, R.; Tang, S.; Guo, L.; Li,
9 (40) Hilbk-Kortenbruck, F.; Noll, R.; Wintjens, P.; Falk, H.; Becker, X.; Zeng, X.; Lu, Y. Opt. Express 2017, 25, 4945-4951.
10 C. Spectrochim. Acta, Part B 2001, 56, 933-945.
11 (41) Yao, S. C.; Shen, Y. L.; Yin, K. J.; Pan, G.; Lu, J. D. Energy
12 Fuels 2015, 29, 1257-1263.
13 (42) Li, X. W.; Yin, H. L.; Wang, Z.; Fu, Y. T.; Li, Z.; Ni, W. D.
Spectrochim Acta B 2015, 111, 102-107.
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Figure 2. Schematic diagram of the experimental setup.
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Figure. 3. Schematic diagram of LIRF in CN radicals
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Figure 4. B2Σ+-X2Σ+ (0,0) spectra of the PVC sample using LIBS (black line) and LIBS-LIRF (blue line).
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Figure 5. Synchronicity between OPO laser and CN fluorescence of B2Σ+-X2Σ+ (0,0) in LIBS-LIRF.
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Figure 6. CN B2Σ+-X2Σ+ (0,0) 388.34 nm signals acquired by LIBS in air (black line), LIBS in nitrogen
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Figure 7. Influences of the interpulse delays on CN B2Σ+-X2Σ+ (0,0) fluorescence intensity acquired by
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Figure 8. (a) Internal calibration curves of carbon in steels meas-ured by LIBS with atomic lines 193.1 nm
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Figure 8(b) internal calibration curves of carbon in steels measured by LIBS-LIRF in nitrogen gas (red
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