Simplified LIBS-based intensity-ratio approach for concentration estimation (SLICE): an approach for elemental analysis using laser induced breakdown spectroscopy.

We propose what we believe to be a new approach for elemental analysis using laser induced breakdown spectroscopy (LIBS). This method offers enhanced convenience and simplicity for elemental analysis as it eliminates the necessity of Boltzmann/ Saha-Boltzmann plot. It is an intensity-ratio based approach that provides several notable advantages. One of the key benefits is its ability to perform comprehensive elemental analysis using only a few spectral lines; specifically, only n + 1 emission lines are sufficient for a sample containing n elemental species. This offers a great flexibility in the choice of emission lines which do not suffer from self-absorption. Further, high accuracy can be obtained as many repeated estimations from a single measurement are possible. We demonstrate the theory and working procedure of this technique by experimentally recording the data of two samples (binary and ternary copper alloys). A nanosecond Nd:YAG pulsed laser of ∼7 ns pulse duration and 532 nm incident wavelength is used. The results are in good agreement with CF-LIBS and Energy-dispersive X-ray spectroscopy (EDS).

Effect of mineral elements on the formation of gallbladder stones using spectroscopic techniques.

Long-standing gallbladder stones have been recognized as one of the highest risk factors for gallbladder cancer. However, the growth and progression of gallbladder stones are still not well-known, and their uncovering requires accurate information on the formation/nucleation and complex compositional information of gallstones. Multiple and single gallstones are analyzed using laser-induced breakdown spectroscopy (LIBS), photoacoustic spectroscopy (PAS), and Fourier transform infrared spectroscopy (FTIR). Spectral signatures as well as spatial variation in the spectral intensities of different elements are observed in the LIBS spectra of the gallstones. In the multiple-type gallstones, the concentration of inorganic content increases from core to periphery, whereas a single gallstone shows the opposite trend from the point of nucleation/core. It is suggested that the concentration of inorganic elements (Mg, Ca, K, and Na) plays an important role in the nucleation and growth of gallstones; thus, accordingly, multiple- and single-type gallstones are found in the gallbladder. The presence of different electronic bands of molecules, such as CH, C2, CN, and NH, is confirmed by LIBS and FTIR. PAS has identified molecules, such as cholesterol, calcium carbonate, and calcium phosphate, in different gallstone samples. These results show that PAS combined with LIBS is a promising candidate for the compositional analysis of gallstones. Furthermore, principal component analysis (PCA) is used to discriminate different layers present in the gallstones.

Time-Dependent Intensity Ratio-Based Approach for Estimating the Temperature of Laser Produced Plasma.

Reported here is a rapid and simplified approach for modeling the temporal evolution of the plasma temperature. The use of only two emission lines makes this technique simple, accurate, and fast. Usually, multiple emission lines are required for estimating plasma temperature using Boltzmann/Saha-Boltzmann plots. But, in several cases, either multiple emission lines are not available for every element and/or sufficient lines are not free from self-absorption effect. The proposed method greatly increases the possibility of plasma temperature estimation as it requires only two lines. A brass target was used to generate the plasma, using a conventional single-pulse nanosecond laser of ∼7 ns pulse duration at an excitation wavelength of 532 nm. The initial temperature of plasma and the radiation decay constant were estimated using a proposed intensity ratio model. The results were estimated using various combinations of emission lines, which show an excellent agreement with the values obtained using the previously reported method.

Spatio-temporal characterization of ablative Cu plasma produced by femtosecond filaments.

We present the spatial and temporal characterization of the copper (Cu) plasma produced by the femtosecond laser filaments. The filaments of various lengths and intensities were generated with the aid of three different focusing lenses. Further, the filamentation induced breakdown spectroscopy (FIBS) measurements were carried out for each filament at three different positions along the length of the filament. The filaments were spatially characterized by estimating the plasma temperature and electron density. Our investigation has demonstrated that the centre of the filament is the best to obtain a maximum signal. Both the spectral line intensity and their persistence time are highest for the center of the filament. The enhanced persistence and the scalability of the spectral line intensity tested across different focusing geometries can boost the application of this technique in various fields.

A low-cost LIBS detection system combined with chemometrics for rapid identification of plastic waste.

We present, rapid and efficient identification of ten different types of post-consumer plastics obtained from a local recycling unit by deploying a low cost, compact CCD spectrometer in laser-induced breakdown spectroscopy (LIBS) technique. For this investigation, spectral emissions were collected by an Echelle spectrograph equipped with an intensified charge-coupled device (ES-ICCD) as well as a non-gated Czerny Turner CCD spectrometer (NCT-CCD). The performance is evaluated by interrogating the samples in a single-shot as well as accumulation mode (ten consecutive laser shots). The results from principal component analysis (PCA) have shown excellent discrimination. Further, the artificial neural network (ANN) analysis has demonstrated that individual identification accuracies/rates up to ~99 % can be achieved. The data acquired with ES-ICCD in the accumulation of ten shots have shown average identification accuracies ~97 %. Nevertheless, similar performance is achieved with the NCT-CCD spectrometer even in a single shot acquisition which reduces the overall analysis time by a factor of ~15 times compared to the ES-ICCD. Furthermore, the detector/collection system size, weight, and cost also can be reduced by ~10 times by employing a NCT-CCD spectrometer. The results have the potential in realizing a compact and low-cost LIBS system for the rapid identification of plastics with higher accuracies for the real-time application.

Real-time fingerprinting of structural isomers using laser induced breakdown spectroscopy.

Laser induced breakdown spectroscopy (LIBS) has surfaced as an attractive alternative to mass spectrometry and wet chemistry methods for chemical identification, driven by its real-time, label-free nature. Rapid analysis needs, especially in high-energy materials and pharmaceutical compounds, have further fueled an increasing number of refinements in LIBS. Yet, isomers are seldom identifiable by LIBS as they generate nearly identical spectra. Here we employ a suite of chemometric approaches to exploit the subtle, but reproducible, differences in LIBS spectra acquired from structural isomers, a set of pyrazoles, to develop a sensitive and reliable segmentation method. We also investigate the possible mechanistic principles (causation) behind such spectral variations and confirm their statistically significant nature that empowers the excellent classification performance.

Non-gated laser induced breakdown spectroscopy provides a powerful segmentation tool on concomitant treatment of characteristic and continuum emission.

We demonstrate the application of non-gated laser induced breakdown spectroscopy (LIBS) for characterization and classification of organic materials with similar chemical composition. While use of such a system introduces substantive continuum background in the spectral dataset, we show that appropriate treatment of the continuum and characteristic emission results in accurate discrimination of pharmaceutical formulations of similar stoichiometry. Specifically, our results suggest that near-perfect classification can be obtained by employing suitable multivariate analysis on the acquired spectra, without prior removal of the continuum background. Indeed, we conjecture that pre-processing in the form of background removal may introduce spurious features in the signal. Our findings in this report significantly advance the prior results in time-integrated LIBS application and suggest the possibility of a portable, non-gated LIBS system as a process analytical tool, given its simple instrumentation needs, real-time capability and lack of sample preparation requirements.

Dynamical and statistical behavior of discrete combustion waves: a theoretical and numerical study.

We present a detailed theoretical and numerical study of combustion waves in a discrete one-dimensional disordered system. The distances between neighboring reaction cells were modeled with a gamma distribution. The results show that the random structure of the microheterogeneous system plays a crucial role in the dynamical and statistical behavior of the system. This is a consequence of the nonlinear interaction of the random structure of the system with the thermal wave. An analysis of the experimental data on the combustion of a gasless system (Ti + xSi) and a wide range of thermite systems was performed in view of the developed model. We have shown that the burning rate of the powder system sensitively depends on its internal structure. The present model allows for reproducing theoretically the experimental data for a wide range of pyrotechnic mixtures. We show that Arrhenius' macrokinetics at combustion of disperse systems can take place even in the absence of Arrhenius' microkinetics; it can have a purely thermal nature and be related to their heterogeneity and to the existence of threshold temperature. It is also observed that the combustion of disperse systems always occurs in the microheterogeneous mode according to the relay-race mechanism.