Laser-induced breakdown spectroscopy; Proximate analysis of coal; Spectral fitting; Support vector machine;LIBS; SYSTEM

Online accurate proximate analysis of coal is vitally important to the optimization of industrial production and reduction in coal consumption. However, due to the ""matrix effect"" caused by the complex and diverse coal species in China, the measurement accuracy needs to be improved by using laser-inducedbreakdown spectroscopy (LIBS). In our experiment, both the spectral pretreatment method and the calibration model for the conversion of laser induced coal plasma spectra to the coal proximate analysis results were optimized. Experimental results showed that, compared with the traditional method, the proposed single or multiple-peak Lorentzian spectral fitting for spectral line intensity calculation reduced the mean RSD from 12. 1% to 9. 7%. For kernel function parameters optimization, the mean absolute error (MAE) of the particle swarm optimization (PSO) was smaller than that of the grid parameter (Grid) and the genetic algorithm (GA). The root mean square error (RMSEP) of support vector machine (SVM) regression model based on PSO parameter optimization was less than that of partial least squares regression (PLS). By combining the single- or multiple-peak Lorentzian spectral fitting method with the PSO based SVM for regression modeling, the average absolute errors (AAE) of predicted proximate analysis results were certified to be: 1. 37% for coal ash content of 16%similar to 30%, 1. 77% for coal ash content of 30% or more, 0. 65 MJ . kg(-1) for calorific value of 9 similar to 24 MJ . kg(-1), 1. 09% for volatile matter of 20% or less, and 1. 02% for volatile matter of 20% or more.

Laser-induced breakdown spectroscopy (LIBS); laser ablation; stability; monitoring;NEUTRON-ACTIVATION ANALYSIS; SPECTROMETRY; SULFUR; LIBS; ENVIRONMENT; FLUORINE; AEROSOLS; CHLORINE; CONCRETE; COAL

Mastering the change of cement raw materials composition in real time has important significance to timely adjusting the proportion of raw materials and improving the quality of cement products. As a result, a greater need for online chemical sensors is evolving. Laser-induced breakdown spectroscopy (LIBS) possesses many of the characteristics required for such online chemical sensing, and is a promising technique for field measurements in harsh industrial environments. In this work, we developed a LIBS device for online cement raw materials quality monitoring in the way of ejecting gas-powder mixture, and enhanced the measurement stability through approaches including powder concentration of the ejected gas-powder stream stabilization, pulsed laser power stabilization, and optical efficiency enhancement.

Time-of-flight mass spectroscopy; Laser induced breakdown spectroscopy; Tungsten plasma; Multi-charged ions; Dynamic plasma sheath;INDUCED-BREAKDOWN-SPECTROSCOPY; ABLATION; SPECTROMETRY; LIBS

In this work, the plasma was produced by irradiating a tungsten target with an 8 ns pulsed Nd:YAG (lambda = 1064 nm) laser in a vacuum chamber under the pressure of 4 x 10(-4) Pa. The optical and particle emissions were systematically investigated using laser induced breakdown spectroscopy and time-of-flight mass spectroscopy respectively. The results showed that not only there were neutral and single ionized atoms in the laser induced plasma, but also quite a number of multi-charged ions were observed. The ion charge state was even up to 6 at the laser power density of similar to 11 GW/cm(2). Time and space resolved optical spectroscopy was investigated by using a bundle of lined fibers. Meanwhile, the time-resolved mass spectrometric study of laser produced tungsten plasma was carried out. The variation in intensities of the different species with time showed that higher charged ions reached their peak intensities earlier. This demonstrated that the higher charged ions had higher velocities and the different charged ions were separated during the expansion process. The kinetic energy corresponding to the velocity of the ions was found to increase exponentially with ionic charge state which was related to the acceleration of the dynamic plasma sheath. (C) 2017 Elsevier B.V. All rights reserved.

EMISSION-LINES; ALUMINUM; PLASMAS; COAL

A novel self-absorption-free laser-induced breakdown spectroscopy (SAF-LIBS) technique is proposed to directly capture the optically thin spectral line by matching the measured doublet atomic lines intensity ratios with the theoretical one. To realize the experimental SAF-LIBS, the integration time, the fiber collection angle, and the delay time are optimized. The optically thin conditions are validated by comparing the linearity of Boltzmann plots with the traditional self-absorption (SA) correction method and evaluating the SA coefficients. The applicability and limitation of SAF-LIBS on element concentration and laserenergy are also discussed. Univariate quantitative analysis results show that, compared with ordinary LIBS, the average absolute error of aluminum concentration has been reduced by an order of magnitude, which proves that this SAF-LIBS technique is qualified to realize accurate chemical composition measurements. (C) 2017 Optical Society of America

QUANTITATIVE-ANALYSIS; PARAMETERS; SAMPLES; LIBS

A calibration method based on homogeneous material for correcting laser-induced breakdown spectroscopy (LIBS) measurement-error bias in the case of dust pollution under laboratory conditions is proposed. The measured plasma spectra of the sample can be corrected by measuring the spectral integral of the homogeneous material. Thus, we can effectively minimize the dust pollution effect on LIBS and guarantee its precision. Results show that the mean absolute errors of CaO, MgO, Fe2O3, Al2O3, and SiO2 in cement samples are decreased notably from 1.02%, 0.06%, 0.15%, 0.57%, and 0.80% to 0.41%, 0.02%, 0.04%, 0.35%, and 0.39%, respectively. Combination of this calibration method with the traditional optical dustproof methods will significantly extend the LIBS equipment maintenance cycle and make preliminary preparations for the next practical industrial application. (C) 2017 Optical Society of America

INDUCED BREAKDOWN SPECTROSCOPY; SELF-ABSORPTION; EMISSION-LINES

The temporal evolution of doublet lines intensity ratio, plasma temperature (T) and electron density (N-e) of different radial parts of aluminum plasma as well as the relationship between optically thin condition and plasma characteristics are investigated. With respect to doublet lines intensity ratio, the optimal delay time (t(ot)) when the plasma is optically thin is determined by comparing the experimental intensity ratio of doublet Al(I) lines with the theoretical value. The optimal integration time, fiber collection angle, and delay time corresponding to the optically thin condition are 400 ns, 45 degrees, and 500 ns, respectively, in which case the linearity of the calibration curve reaches 0.98, enabling more accurate composition measurements. The maximum temperature values are reached within 300 ns at 10 degrees, 30 degrees, 45 degrees, and 80 degrees, but after 900 ns at 55 degrees, 60 degrees, and 70 degrees. Combined with the morphologic image of the plasma, we infer that the time at which a radial part of plasma reaches the highest temperature is related to the extent of its expansion. It is generally understood that the faster the radial part of plasma expands, the sooner the temperature reaches its maximum. The radial part of plasma may not be optically thin when the corresponding temperature reaches its maximum. If the highest temperature is obtained earlier, the optically thin condition is likely to appear in the descending stage of the temporal evolution curve of temperature. Otherwise, it may appear in the ascending stage. There seems to be no simple positive correlation between electron density and optically thin condition.