Rongxing Yi

Determination of cobalt in low-alloy steels using laser-induced breakdown spectroscopy combined with laser-induced fluorescence

Cobalt element plays an important role for the properties of magnetism and thermology in steels. In this work, laser-induced breakdown spectroscopy combined with laser-induced fluorescence (LIBS-LIF) was studied to selectively enhance the intensities of Co lines. Two states of Co atoms were resonantly excited by a wavelength-tunable laser. LIBS-LIF with ground-state atom excitation (LIBS-LIFG) and LIBS-LIF with excited-state atom excitation (LIBS-LIFE) were compared. The results show that LIBS-LIFG has analytical performance with LoD of 0.82μg/g, R(2) of 0.982, RMSECV of 86μg/g, and RE of 9.27%, which are much better than conventional LIBS and LIBS-LIFE. This work provided LIBS-LIFG as a capable approach for determining trace Co element in the steel industry.

Background removal in soil analysis using laser- induced breakdown spectroscopy combined with standard addition method

The matrix effect of powder samples, especially for soil samples, is significant in laser-induced breakdown spectroscopy (LIBS), which affects the prediction accuracy of the element concentration. In order to reduce this effect of the soil samples in LIBS, the standard addition method (SAM) based on background removal by wavelet transform algorithm was investigated in this work. Five different kinds of certified reference soil samples (lead (Pb) concentrations were 110, 283, 552, 675, and 1141 ppm, respectively) were used to examine the accuracy of this method. The root mean square error of prediction (RMSEP) was more than 303 ppm by using the conventional calibration method. After adoption of SAM with background removal by wavelet transform algorithm, the RMSEP was reduced to 25.7 ppm. Therefore, the accuracy of the Pb element was improved significantly. The mechanism of background removal by wavelet transform algorithm based on SAM is discussed. Further study demonstrated that this method can also improve the predicted accuracy of the Cd element.

Sensitive determinations of Cu, Pb, Cd, and Cr elements in aqueous solutions using chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy.

In this study, chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy (CR-SENLIBS) was for the first time applied to improve the detection sensitivities of trace heavy metal elements in aqueous solutions. Utilizing chemical replacement effect, heavy metal ions in aqueous solution were enriched on the magnesium alloy surface as a solid replacement layer through reacting with the high chemical activity metallic magnesium (Mg) within 1 minute. Unitary and mixed solutions with Cu, Pb, Cd, and Cr elements were prepared to construct calibration curves, respectively. The CR-SENLIBS showed a much better detection sensitivity and accuracy for both unitary and mixed solutions. The coefficients of determination R2 of the calibration curves were above 0.96, and the LoDs were of the same order of magnitude, i.e., in the range of 0.016-0.386 μg/mL for the unitary solution, and in the range of 0.025-0.420 μg/mL for the mixed solution. These results show that CR-SENLIBS is a feasible method for improving the detection sensitivity of trace element in liquid sample, which definitely provides a way for wider application of LIBS in water quality monitoring.

Spatially selective excitation in laser-induced breakdown spectroscopy combined with laser-induced fluorescence

Spatially selective excitation was proposed to improve excitation efficiency in laser-induced breakdown spectroscopy combined with laser-induced fluorescence (LIBS-LIF). Taking chromium (Cr) and nickel (Ni) elements in steels as examples, it was discovered that the optimal excitation locations were the center of the plasmas for the matrix of the iron (Fe) element but the periphery for Cr and Ni elements. By focusing an excitation laser at the optimal locations, not only excitation efficiency but also the analytical accuracy and sensitivity of quantitative LIBS-LIF were better than those with excitation at the plasma center in conventional LIBS-LIF. This study provides an effective way to improve LIBS-LIF analytical performance.

Spectral Interference Elimination in Soil Analysis Using Laser-Induced Breakdown Spectroscopy Assisted by Laser-Induced Fluorescence

The complex and serious spectral interference makes it difficult to detect trace elements in soil using laser-induced breakdown spectroscopy (LIBS). To address it, LIBS-assisted by laser-induced fluorescence (LIBS-LIF) was applied to selectively enhance the spectral intensities of the interfered lines. Utilizing this selective enhancement effect, all the interference lines could be eliminated. As an example, the Pb I 405.78 nm line was enhanced selectively. The results showed that the determination coefficient (R2) of calibration curve (Pb concentration range = 14-94 ppm), the relative standard deviation (RSD) of spectral intensities, and the limit of detection (LOD) for Pb element were improved from 0.6235 to 0.9802, 10.18% to 4.77%, and 24 ppm to 0.6 ppm using LIBS-LIF, respectively. These demonstrate that LIBS-LIF can eliminate spectral interference effectively and improve the ability of LIBS to detect trace heavy metals in soil.

Investigation of the self-absorption effect using spatially resolved laser-induced breakdown spectroscopy

The self-absorption effect will seriously influence the accuracy of quantitative analyses using laser-induced breakdown spectroscopy (LIBS). To reduce the self-absorption effect, elements Na and K (major elements) and Pb and Cu (minor elements) in soil plasmas have been studied by spatially resolved LIBS (SRLIBS). The 2-dimensional distributions of line intensities and self-absorption coefficients of lines in the plasmas were investigated and the influence parameters of the self-absorption effect were also studied. Results have shown that the self-absorption effect could be reduced greatly and the accuracy of quantitative LIBS could be improved obviously by selecting the collecting zones of the plasmas carefully. Meanwhile, a high laser energy and a short delay time could be useful to expand the region which is influenced slightly by the self-absorption effect.

Quantitative analysis of steel samples using laser-induced breakdown spectroscopy with an artificial neural network incorporating a genetic algorithm

In this work, a genetic algorithm (GA) was employed to select the intensity ratios of the spectral lines belonging to the target and domain matrix elements, then these selected line-intensity ratios were taken as inputs to construct an analysis model based on an artificial neural network (ANN) to analyze the elements copper (Cu) and vanadium (V) in steel samples. The results revealed that the root mean square errors of prediction (RMSEPs) for the elements Cu and V can reach 0.0040 wt. % and 0.0039 wt. %, respectively. Compared to 0.0190 wt. % and 0.0201 wt. % of the conventional internal calibration approach, the reduction rates of the RMSEP values reached 78.9% and 80.6%, respectively. These results indicate that the GA combining ANN can excellently execute the quantitative analysis in laser-induced breakdown spectroscopy for steel samples and further improve analytical accuracy.

Simultaneous determination of La, Ce, Pr, and Nd elements in aqueous solution using surface-enhanced laser-induced breakdown spectroscopy

Determination of rare earth elements (REEs) plays an important role in the extraction process. In this work, surface-enhanced laser-induced breakdown spectroscopy (SENLIBS) was introduced to detect REEs (lanthanum, cerium，praseodymium，and neodymium elements) in an aqueous solution. The emission lines of La II 394.91nm, Ce II 418.66nm, Pr II 422.29nm, and Nd II 406.10nm were selected for quantitative analysis by drying the analytical samples on a Zn metal substrate surface and optimizing the experimental parameters. The results showed that the limits of detection (LoDs) for determining La, Ce, Pr, and Nd elements can reach to 0.85, 4.07, 2.97, and 10.98μgmL-1, respectively, which proved that SENLIBS is a feasible method for determining REEs.

Laser-induced breakdown spectroscopy of liquid solutions: A comparative study on the forms of liquid surface and liquid aerosol

Liquid surface and liquid aerosol as the traditional liquid forms for laser-induced breakdown spectroscopy (LIBS) and inductively coupled plasma (ICP), respectively, have been used to analyze chromium (Cr) and cadmium (Cd) elements using LIBS in a liquid solution. The spectral differences, the effects of laser energy and laser frequency, the accumulated number of laser pulses, gate delay time, and the quantitative analyses for a liquid surface and a liquid aerosol were compared. The results showed that the liquid surface demonstrated a lower plasma threshold, higher optical emission intensity, and higher single-to-noise ratio. Moreover, the relative standard deviations (RSDs) of the intensities of the liquid aerosol are better than those of the liquid surface. Furthermore, the results of the quantitative analyses of Cr I 357.86 nm and Cd I 361.05 nm of the liquid surface are close to those of the liquid aerosol. The limit of detections of Cr and Cd of the liquid surface were 2.764 and 86.869  μg/mL, which were close to those of liquid aerosol, 2.847  μg/mL of Cr and 97.635  μg/mL of Cd. For both the liquid surface and liquid aerosol, the coefficient of determination R2 of the calibration curve for Cr and Cd were above 0.99, and the average RSDs of Cr and Cd of the liquid surface were 0.027 and 0.054, which were similar to the 0.020 of Cr and 0.042 of Cd of the liquid aerosol. These results suggest that both the liquid surface and aerosol have similar detection abilities for water quality monitoring.

Determination of Carbon Content in Steels Using Laser-Induced Breakdown Spectroscopy Assisted with Laser-Induced Radical Fluorescence

Carbon is a key element for steel properties but hard to be determined by laser-induced breakdown spectroscopy (LIBS). Utilizing the combination of carbon in analytes and nitrogen in ambient gas to generate carbon-nitrogen (CN) radicals, LIBS assisted with laser-induced radical fluorescence (LIBS-LIRF) was proposed to resonantly excite radicals instead of atoms in plasmas. The CN radicals in the B2Σ-A2Π band were stimulated by a 421.60 nm laser wavelength and emitted 388.34 nm fluorescence. The results show that the spectral intensity of the CN radicals was enhanced by 2 orders of magnitude using LIBS-LIRF. 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 wt % in air and nitrogen gas, respectively. This work demonstrated the feasibility of LIBS to realize reliable carbon determination in steel industry.