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In this work, the potential of laser-induced breakdown spectroscopy (LIBS) for discrimination and analysis of geological materials was examined. The research was focused on classification of mineral ores using their LIBS spectra prior to quantitative determination of copper. Quantitative analysis is not a trivial task in LIBS measurement because intensities of emission lines in laser-induced plasmas (LIP) are strongly affected by the sample matrix (matrix effect). To circumvent this effect, typically matrix-matched standards are used to obtain matrix-dependent calibration curves. If the sample set consists of a mixture of different matrices, even in this approach, the corresponding matrix has to be known prior to the downstream data analysis. For this categorization, the multielemental character of LIBS spectra can be of help. In this contribution, a principal component analysis (PCA) was employed on the measured data set to discriminate individual rocks as individual matrices against each other according to their overall elemental composition. Twenty-seven igneous rock samples were analyzed in the form of fine dust, classified and subsequently quantitatively analyzed. Two different LIBS setups in two laboratories were used to prove the reproducibility of classification and quantification. A superposition of partial calibration plots constructed from the individual clustered data displayed a large improvement in precision and accuracy compared to the calibration plot constructed from all ore samples. The classification of mineral samples with complex matrices can thus be recommended prior to LIBS system calibration and quantitative analysis.
A spatial heterodyne spectrometer (SHS) is tested for the first time in combination with laser-induced breakdown spectroscopy (LIBS). The spectrometer is a modified version of the Michelson interferometer in which mirrors are replaced by diffraction gratings. The SHS contains no moving parts and the gratings are fixed at equal distances from the beam splitter. The main advantage is high throughput, about 200 times higher than that of dispersive spectrometers used in LIBS. This makes LIBS-SHS a promising technique for low-light standoff applications. The output signal of the SHS is an interferogram that is Fourier-transformed to retrieve the original plasma spectrum. In this proof-of-principle study, we investigate the potential of LIBS-SHS for material classification and quantitative analysis. Brass standards with broadly varying concentrations of Cu and Zn were tested. Classification via principal component analysis (PCA) shows distinct groupings of materials according to their origin. The quantification via partial least squares regression (PLS) shows good precision (relative standard deviation , 10%) and accuracy (within 6 5% of nominal concentrations). It is possible that LIBS-SHS can be developed into a portable, inexpensive, rugged instrument for field applications.
Cracks are always present in reinforced concrete structures. In the presented research, influence of mechanical cracks on chloride ingress is studied. A compact reinforced concrete specimen was designed, mimicking the cracking behaviour of beam elements. Cracks of different widths were induced by means of mechanical loading. These cracked specimens were then subjected to weekly cycles of wetting and drying with NaCl solution. After the exposure, the specimens were cut, and chloride distributions were determined using Laser Induced Breakdown Spectroscopy (LIBS), an innovative technique which enables simultaneous determination of different elements with high spatial resolution and minimal specimen preparation. By combining element distributions of different elements, it is possible to discriminate between coarse aggregate particles, and the mortar matrix. It was found that the wider the crack is, the higher the ingress of chloride ions. This was, however, different for two tested concrete mixes. Due to highly inhomogeneous chloride distribution around the cracks, use of fine-scale experimental techniques for chloride mapping is advised, based on the presented study.
New developments in spectroscopic techniques for process control are, in general, driven by shortcomings of existing technology, for example, when sensitivity, selectivity, robustness, and so forth do not meet the demands. The perfect process analytical method would be based on a robust and easy to handle customized technique operating in real time, come without any need for calibration, that is, be an absolute method, have a professional support, and be compliant to increasing regulatory requirements. However, there are at least trends toward such an all-in-one device suitable for every purpose.
Small, low-field NMR systems equipped with permanent magnet technology have been developed and allow for quantitative analysis as on-line instruments in a production environment. Quantitative high-resolution on-line NMR spectroscopy contributes to process understanding in pilot plant and research environments.
Laser spectroscopy is a promising field in process analysis owing to its sensitivity and selectivity. Laser-induced breakdown spectroscopy LIBS is a promising field for direct in situ analysis and remote sensing. Applications of quantum-cascade lasers for process analytical applications are a promising technique. Techniques such as cavity ring-down spectroscopy (CRDS), tunable diode laser absorption spectroscopy (TDLAS), and photothermal techniques are briefly introduced.
Recent developments of new detectors have improved X-ray fluorescence analysis (XRF) for qualitative and quantitative on-line evaluation of the elementary composition of liquid or solid samples, regardless of whether compact or bulk material.
The chapter also introduces miscellaneous techniques such as ion mobility spectroscopy (IMS), microwave and dielectric spectroscopy, terahertz spectroscopy, ultrasonic acoustic spectroscopy, and other methods.
Laser induced breakdown spectroscopy (LIBS) - visualization of ion transport processes in concrete
(2014)
Laser induced breakdown spectroscopy (LIBS) is a combination of laser ablation and optical emission spectroscopy. Due to the possibility of direct measurements on the sample surface and a minimum of sample preparation investigations of building materials can be conducted quite fast. In combination with a scanning technique (translation stage or scanning mirrors head) the element distributions are evaluated with mm resolution. Thus the heterogeneity of the material may be considered. This is a significant advantage compared to standard procedures. LIBS measurements are also time and cost saving in comparison to standard methods. The automated measurement procedures minimize the liability for errors. All elements are detectable. Results can be quantified after calibration. At BAM LIBS has been successfully applied for the investigation of distribution and transport of different ions in building materials. Quantitative measurements are performed for chlorine, sodium, potassium, sulfur, lithium and hydrogen. In addition the identification of substances and the evaluation of quantitative ratios by means of an integrated marker are possible. An overview about the principle and the possibilities of LIBS investigations of building materials is presented and typical applications are shown. The LIBS technique is close to practical application on-site.
Laser Induced Breakdown Spectroscopy (LIBS) is a combination of laser ablation, plasma formation and optical emission spectroscopy. The possibility of direct measurements on the sample surface, the minimum of necessary sample preparation and the automated setup allows for fast investigations of building materials. In combination with a scanning technique (translation stage or scanning mirrors head) the element distribution can be evaluated in consideration of the material's heterogeneity. LIBS measurements are also time-and cost-saving. The ingress profile of chlorine on a 50mm diameter concrete core up to a depth of 50mm can be measured and evaluated in less than 10 minutes. The results are normally referred to the evaporated mass, which is approximately the cement mass of the specific concrete. As a completion to micro XRF measurements also light elements like sodium or hydrogen can be detected. The spatial resolution of the measurement may reach 50 ìm at a maximum measurement frequency of up to 100 Hz. On the basis of calibration curves, results can be quantified.
High repetition rate laser-induced breakdown spectroscopy using acousto-optically gated detection
(2014)
This contribution introduces a new type of setup for fast sample analysis using laser-induced breakdown spectroscopy (LIBS). The novel design combines a high repetition rate laser (up to 50 kHz) as excitation source and an acousto-optical modulator (AOM) as a fast switch for temporally gating the detection of the emitted light. The plasma radiation is led through the active medium of the AOM where it is diffracted on the transient ultrasonic Bragg grid. The diffracted radiation is detected by a compact Czerny-Turner spectrometer equipped with a CCD line detector. Utilizing the new combination of high repetition rate lasers and AOM gated detection, rapid measurements with total integration times of only 10 ms resulted in a limit of detection (LOD) of 0.13 wt.% for magnesium in aluminum alloys. This short integration time corresponds to 100 analyses/s. Temporal gating of LIP radiation results in improved LODs and consecutively higher sensitivity of the LIBS setup. Therefore, an AOM could be beneficially utilized to temporally detect plasmas induced by high repetition rate lasers. The AOM in combination with miniaturized Czerny-Turner spectrometers equipped with CCD line detectors and small footprint diode pumped solid state lasers results in temporally gateable compact LIBS setups.
The laser induced breakdown spectroscopy (LIBS) is a combination of laser ablation and optical emission spectroscopy. Due to the possibility of direct measurements on the sample surface and a minimum of required sample preparation investigations of building materials can be conducted quite fast. In combination with a scanning technique (translation stage or scanning mirrors head) the element distributions are evaluated taking in to account the heterogeneity of the material. This is a significant advantage compared to standard procedures. LIBS measurements are also time and cost saving in comparison to standard methods. The automated measurement procedures minimise the liability for errors. All elements are detectable and after calibration results can be quantified. At BAM LIBS has been successfully applied for the investigation of distribution and transport of different ions in building materials. Quantitative measurements are performed for chlorine, sodium, potassium, sulphur, lithium and hydrogen. Beside this the identification of substances and the evaluation of quantitative ratios by means of an integrated marker are possible. An overview about the principle and the possibilities of LIBS investigations of building materials is presented and typical applications are shown. The LIBS technique is on the step from laboratory application to on-site analyses.
Cracks are always present in reinforced concrete structures. In the presented research, influence of mechanical cracks on chloride ingress is studied. A compact reinforced concrete specimen was designed, mimicking the cracking behaviour of beam elements. Cracks of different widths were induced by means of mechanical loading. These cracked specimens were then subjected to weekly cycles of wetting and drying with NaCl solution. After the exposure, the specimens were cut, and chloride distributions were determined using Laser Induced Breakdown Spectroscopy (LIBS), an innovative technique which enables simultaneous determination of different elements with high spatial resolution and minimal specimen preparation. By combining element distributions of different elements, it is possible to discriminate between coarse aggregate particles, and the mortar matrix. It was found that the wider the crack is, the higher the ingress of chloride ions. This was, however, different for two tested concrete mixes. Due to highly inhomogeneous chloride distribution around the cracks, use of fine-scale experimental techniques for chloride mapping is advised, based on the presented study.