Multivariate data analysis (MVDA) is getting popular across the spectroscopic community. To assess accurate results, the obtained data should be preprocessed prior to utilization of any MVDA algorithm. The process of data normalization or “internal standardization” is widely used across a broad range of applications. In this manuscript we investigate the utilization of Laser-Induced Breakdown Spectroscopy (LIBS) coupled with MVDA. However, many articles regarding the use of MVDA on data from LIBS do not provide any information about the data pretreatment. This work describes the impact of LIBS data normalization approaches on MVDA classification accuracy. Also, the impact of classical data preprocessing (mean centering and scaling) exploiting the prior utilization of MVDA was studied. This issue was investigated exploiting simple soft independent modelling of class analogies algorithm. The findings were generalized for three sample matrices (steel, Al alloys, and sedimentary ores). Furthermore, the selection of an appropriate normalization algorithm is not trivial since the spectrum of each sample matrix is composed of a different number of elements and corresponding elemental lines.

SPECTRUM STANDARDIZATION; QUANTITATIVE-ANALYSIS; LIBS; NORMALIZATION; SIGNAL; MODEL

The uncertainty of collected spectral data is one of the most important issues for the application of laser-induced breakdown spectroscopy (LIBS) quantitative analysis. The fluctuation of the target surface simultaneously affects both the focus depth of the laser beam and the relative collection position, either of which may lead to severe fluctuation of the spectral signal. Thus, in this study, for detecting and reducing the fluctuation, an imaging system was deployed to monitor the plasma, and a mathematical model was also built based on both spectral signal and positional information. An ICCD camera was used to record the image of the plasma so as to detect the plasma and acquire positional information. Furthermore, the relationship between plasma position and specific spectral line intensity was obtained by the fitting function. Five aluminium alloy samples were employed to validate the reliability of the proposed method. As a result, the average RSDs of the samples (with a position fluctuation range of about 2 mm) in different spectral lines (Si 288.15 nm, Fe 273.95 nm, Cu 324.75 nm, Mn 259.37 nm and Mg 280.27 nm) were reduced from 34.57%, 38.86%, 31.05%, 39.74%, and 36.91% (without normalization) to 4.63%, 6.84%, 5.64%, 7.64%, and 4.83% (with the combination method presented in this paper), respectively; the determination coefficients (R-2) reached 0.996, 0.999, 0.989, 0.999, and 0.9999, respectively. These results prove that the proposed method can both improve measurement reliability and guarantee measurement accuracy.

LIBS quantitative analysis; reduction of matrix effect; internal standard calibration; normalization; correction of self-absorption;PART II; SAMPLES; PARAMETERS

A procedure for matrix effect reduction is proposed to enhance the precision of quantitative analysis of metal alloys using laser-induced breakdownspectroscopy (LIBS). This procedure is based on a number of successive steps in order to correct the signal fluctuations caused by plasma interaction and the matrix effect. The first step is the selection of optimum parameter settings of the detection system, such as laser power, delay time, and focal distance. The second step is the estimation of the absolute or relative values of impurities on the basis of the internal standard calibration. The third step is the analysis of the metal basis of the alloy used as an internal standard, which requires spectrum averaging, whole integral spectrum normalization, and self-absorption correction. Three sets of metal-based alloys (aluminum, steel, and copper) are used in this investigation as reference standards for calibration and validation. Successive improvements of the quality of calibration curves are observed during the proposed procedure.

Laser induced plasma; Spectral line profile; Continuum intensity; Full width at half maximum (FWHM); Spectral line shift;INDUCED BREAKDOWN SPECTROSCOPY; INDUCED PLASMA DYNAMICS; ABLATION

There are many methods to characterize plasma parameters for laser-induced plasma, optical emission spectra method is a very important one to diagnose laser-induced plasma parameters. In this paper, Nd:YAG solid state laser which output 1064 nm wavelength interact with aluminum alloy sample, the temporal evolution of spectral line profile, spectral line intensity, continuum intensity, line to background intensity ratio, spectral line broadening and spectral line shift were investigated in detail for laser induced aluminum alloy plasma. The results show that the interaction of electrons between atoms and ions are very intense, which leads to electrons production of laser induced plasma at the early stage. Stark broadening effect of spectra lines are distinct and multiple spectral lines are overlapped. With temporal evolution, the electron density and electron temperature decreased quickly, the multiple spectral lines are separated slowly, and the spectral line profile is becoming thinner and symmetric. For Mg I 285.2126 nm characteristic spectral line, the intensity increased with temporal evolution at first, the intensity reached maximum value about 100 ns, and then the intensity decreased with temporal evolution, which is due to the fact that electron and ion are dominated at early stage of laser-induced plasma, atomic spectral line is very weak, with temporal evolution, the process of recombination between electrons dominated and the atomic number density increased, when the atomic number density reached maximum value, the spectral line intensity decreased with temporal evolution because excitation temperature decreased quickly. Taking wavelength in NIST database as reference wavelength, the spectral line shift for Mg I 285.212 7 nm and Zn II 206.200 4 nm take place red shift at early stage of laser induced plasma, the continuum intensity decreased dramatically by power law with temporal evolution, on the contrary, comparing with continuum intensity and spectral line intensity, continuum intensity attenuate sharply, the line to background intensity ratio increase with temporal evolution. This early phenomenon of laser inducedaluminum alloy plasma were discussed in detail from theoretical perspective.

Laser Induced Breakdown Spectroscopy (LIBS); Transversely excited atmospheric carbondioxide (TEA CO2) laser; Aluminum alloys; Qualitative analysis; Quantitative analysis;INDUCED GAS PLASMA; SPECTROCHEMICAL ANALYSIS; QUANTITATIVE-ANALYSIS; OPTICAL-EMISSION; LIBS; SAMPLES; PULSES; SPECTROMETRY; METALS; AIR

The applicability of nanosecond infrared Transversely Excited Atmospheric (TEA) CO2 laser induced plasma for spectrochemical analysis of aluminum alloys was investigated. The plasma was generated by focusing a pulsed TEA CO2 laser that emits at 10.6 mu m on the Al target in ambient air at atmospheric pressure. The temporal profile of the laser pulse is composed of a 100 ns peak followed by a slowly decaying tail of about 2 mu s. The output pulse energy was approximately 160 mJ, thus the peak output power was estimated to be around 1.6 MW. Time-Integrated Space-Resolved Laser Induced BreakdownSpectroscopy (TISR-LIBS) was employed to obtain the emission spectra. The maximum intensity of emission, with sharp and well resolved spectral lines that were almost free of the background continuum, was obtained from plasma region 2 mm from the target surface. Linear calibration curves for Mg, Cr, Cu and Fe were obtained using aluminum alloy spectrochemical standards. The limits of detection for the investigated elements were in the 2-73 ppm range. Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) was used as a reference technique to estimate the accuracy of LIBS determination by use of control samples with known compositions. Comparison of the obtained results with those available in the literature confirms that LIBS system based on TEA CO2 laser, in combination with TISR spectral measurements, can be successfully applied to qualitative and quantitative determinations of minor elements in aluminum based alloys. (C) 2017 Elsevier B.V. All rights reserved.

INDUCED BREAKDOWN SPECTROSCOPY; TRANSFORM; IDENTIFICATION; CALIBRATION; SIGNALS; ALLOYS

Laser-induced breakdown spectroscopy (LIBS) is becoming a rapid and easy technique for quantitative elemental analysis. However, the implementation of accurate quantitative LIBS analysis is always subject to noise interference. In this work, in order to improve LIBS analysis performance for trace elements in aluminium alloys, a modified trade-off soft and hard threshold method is proposed based on the wavelet theory, where optimal parameters are deduced to eliminate noise interference. By using the modified algorithm combined with an Al I line at 308.215 nm as an internal standard, the statistical parameters including the determination coefficient (R-2), the root mean square error (RMSE) and the relative standard deviation (RSD) of magnesium (Mg), manganese (Mn) and cuprum (Cu) in aluminium alloys are all significantly improved. The most significant improvement of R-2 is 0.066 for Cu. The maximum RMSE reduction value is 0.583 for Mg, and the mean value of RMSE reduction is 0.261 for all three trace elements. And after de-noising, the value of RSD gets smaller for each trace element. Such results indicate that the optimized algorithm is valid for the effective improvement of the accuracy of quantitative LIBS analysis in the trace element determination of aluminium alloys.