Chemische Charakterisierung und Spurenanalytik
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Eingeladener Vortrag
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Society for Applied Spectroscopy (SAS) Atomic Section Student Award.
Magnesium is a major element in the hydrosphere and biosphere and plays important roles in (bio-) geochemical and physiological cycles. Mg has three stable isotopes, 24Mg, 25Mg and 26Mg. It is due to their relatively large mass difference (~8% between) that isotope fractionation leads to slight variations of isotope amount ratios in biological, environmental and geological samples. Traditionally, isotope ratios are measured by mass spectrometric methods. Their drawbacks include the high costs for instruments and their operation, experienced operators and elaborate time-consuming chromatographic sample preparation.
Recently, optical spectrometric methods have been proposed as faster and low-cost alternative for the analysis of isotope ratios of selected elements by means of high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS), and laser ablation molecular isotopic spectrometry (LAMIS).
For the determination of Mg isotope ratios in selected rock reference materials, the molecular spectrum of the in-situ generated MgF and MgO molecules were studied and their results compared with MC-ICP-MS. By HR-CS-MAS, samples were dissolved by acid digestion and Mg isotopes analyzed with and without matrix. The absorption spectrum was recorded for MgF for the electronic transitions X 2Σ → A 2 Πi, and X 2Σ → B 2Σ+. In the case of LAMIS, we investigated the MgF molecule for the electronic transition A 2Πi → X 2Σ, as well as direct analysis by the MgO molecule for the electronic transition A 1Π+ → X 1Σ. The MgF and MgO spectra are described as the linear combination of their isotopic components or isotopologues: 24MgF, 25MgF, and 26MgF for the MgF and 24MgO, 25MgO, and 26MgO for the MgO. The isotope analysis was done by deconvolution of the MgF spectrum by partial least square regression (PLS) calibrated with enriched isotope spikes. Results were accurate with precisions ranging between 0.2 ‰ and 0.8 ‰ (2 SD, n= 10) for HR-CS-GFMAS. No statistically significant differences were observed for samples w/o matrix extraction. On the other hand, LAMIS allows the direct analysis of solid samples with the extended possibility of direct analysis, however the precision is lower due the lack of solid isotopic calibration standards.
Analyse des Tausalzeintrages in Fahrbahndeckenbetone im Kontext der Alkali-Kieselsäure-Reaktion
(2018)
In den letzten Jahren sind im deutschen Bundesautobahnnetz (BAB-Netz) vermehrt AKR-Schäden an Betonfahrbahndecken aufgetreten, die zum Teil zu einer Halbierung ihrer geplanten Nutzungsdauer von 30 Jahren führte. Ursächlich hierfür ist die Verwendung alkaliempfindlicher Gesteinskörnung, die bei gleichzeitiger Anwesenheit von Wasser infolge der Exposition der Fahrbahndecke und dem alkalischen Milieu durch den Einsatz alkalireicher Portlandzemente bei der Betonherstellung zu einer Alkali-Kieselsäure-Reaktion (AKR) führt. Zusätzlich wird der AKR-Schädigungsprozess in Betonfahrbahndecken durch den externen Tausalzeintrag (primär NaCl) im Winter begünstigt. Vor diesem Hintergrund kommt der Ermittlung des Tausalzeintrags in den Fahrbahndeckenbeton eine große Bedeutung zu. Die Analyse des Tausalzeintrags erfolgte bisher ausschließlich nasschemisch an gemahlenen Bohrkernsegmenten. Nachteilig ist hierbei die fehlende differenzierte Betrachtung des Natriumgehaltes im Zementstein und in der Gesteinskörnung. Der alternative Einsatz von LIBS (Laser-induced breakdown spectroscopy) eröffnet in diesem Kontext neue Möglichkeiten. So wird in diesem Beitrag an Hand von Bohrkernen aus einem AKR-geschädigten BAB-Abschnitt exemplarisch die Vorgehensweise bei der LIBS-Analyse zur Ermittlung der Na- und interagierenden Cl-Verteilung an vertikalen Schnittflächen des Bohrkerns aufgezeigt. Da der Tausalzeintrag primär über den Zementstein erfolgt, wurde der verfälschende Na-Grundgehalt der Gesteinskörnung mittels Zementsteinkriteriums (Nutzung unterschiedlichen Ca-Gehalts in Zementstein und Gesteinskörnung) eliminiert. Vergleichend durchgeführte Cl-Mappings mit Mikroröntgenfluoreszenzanalyse (MRFA) belegen die Güte der durchgeführten LIBS-Messungen.
Aber auch bei der Verifizierung der Übertragbarkeit der Ergebnisse der zum Ausschluss reaktiver Gesteinskörnung bei Neubau und Erneuerung im BAB-Netz eingesetzten Performanceprüfungen mit externem Alkalieintrag auf Praxisverhältnisse hat sich das LIBSVerfahren bewährt. So wurde festgestellt, dass die mit NaCl-Lösung beaufschlagten Laborprüfkörper aus einem repräsentativen Fahrbahndeckenbeton bei der Klimawechsellagerung (KWL) über ihre gesamte Höhe von 10 cm einen Eintrag von Na und Cl erfahren. Weiterhin konnte im Gegensatz zu bisherigen Annahmen erstmals mit LIBS und Nasschemie gezeigt werden, dass die Frost-Tauwechsel-Phase bei der KWL zu keinem erhöhten Tausalzeintrag führt.
Two calibration-free (CF) LIBS approaches are used for the quantitative analysis of cement samples: the CF-LIBS based on the Boltzmann plot method and the Monte Carlo (MC) LIBS based on the iterative spectrum fitting. In CF-LIBS, the inverse problem is solved, i.e. the elemental concentrations are determined by the reconstruction of plasma parameters from spectra. The MC-LIBS technique solves the direct problem by finding the highest correlation between the model-generated and experimental spectrum. The accuracy of both calibration-free LIBS methods suffers from factors such as inaccurately determined instrumental function, the deviation of experimental plasma from the mathematical model used, not taking into account the collection geometry, and from the uncertainty of spectroscopic data. The both calibration-free LIBS approaches are first applied to synthetic spectra which perfectly suit the mathematical model of the method, i.e. the model of the uniform, isothermal, and stationary plasma. This test yields the accuracy of both the approaches for the ideal case. In addition, the accuracy of both the methods is investigated for non-uniform and non-isothermal plasma, because real laser-induced plasma often has high gradients in temperature and particle number densities. Finally, both calibration-free LIBS approaches are applied to experimental spectra obtained from cement samples. The figures of merits of two approaches are compared when working with both synthetic and experimental spectra.
The equation of state for plasmas containing negative and positive ions of elements and molecules formed by these elements is modeled under the assumption that all ionization processes and chemical reactions are at local thermal equilibrium and the Coulomb interaction in the plasma is described by the Debye–Hückel theory. The hierarchy problem for constants of molecular reactions is resolved by using three different algorithms for high, medium, and low temperatures: the contraction principle, the Newton–Raphson method, and a scaled Newton–Raphson method, respectively. These algorithms are shown to have overlapping temperature ranges in which they are stable. The latter allows one to use the developed method for calculating the equation of state in combination with numerical solvers of Navier–Stokes equations to simulate laser-induced Plasmas initiated in an atmosphere and to study formation of molecules and their ions in such plasmas. The method is applicable to a general chemical network. It is illustrated with examples of Ca–Cl and C–Si–N laser-induced plasmas.
Mass spectrometric Methods MC-ICP-MS and TIMS) are without doubt the working horse of stable isotope analysis. However, drawbacks of these methods include the high costs for instruments and their operation, experienced operators and elaborate chromatographic sample preparation which are time consuming.
Optical spectrometric methods are proposed as faster and low-cost alternative for the analysis of isotope ratios of selected elements by means of high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS) and laser ablation molecular isotopic spectrometry (LAMIS). First, stable isotope amount compositions of boron (B) and magnesium (Mg) were determined based on the absorption spectra of in-situ generated heteronuclear diatomic molecules (MH or MX) in graphite furnace HR-CS-MAS. The use of a modular simultaneous echelle spectrograph (MOSES) helps to find the maximal isotope shift in the diatomic molecular spectra produced in a graphite furnace by using isotopic spike solutions. Isotopes of boron (10B and 11B) were studied via their hydrides for the electronic transition X 1Σ+ → A 1Π. The spectrum of a given sample is a linear combination of the 10BH molecule and its isotopologue 11BH. Therefore, the isotopic composition of samples can be calculated by a partial least square regression (PLS). For this, a spectral library was built by using samples and spikes with known isotope composition. Boron isotope ratios measured by HR-CS-MAS are identical with those measured by mass spectrometric methods at the 0.15 ‰ level. Similar results were obtained for a multiple isotope system like Mg (24Mg, 25Mg, and 26Mg), where isotope shifts of their isotopologues can be resolved in the MgF molecule for the electronic transition X 2Σ → A 2 Πi. Finally, the application of molecular spectrometry via emission by LAMIS is compared and discussed.
19th and 20th centuries glass paint layers consist of a colour body and a colourless lead silicate flux, in which borax or boric acid was added as further component to improve the paint ability and to reduce the firing temperature for multiple layers of paint. Model glasses were used in laboratory tests to investigate the stability of glass paints with additions of boron oxide. To determine boron in paint layers, a LIBS-system with pulsed NdYAG-laser was used.
Laser induced plasma (LIP) is a highly dynamic, short living event which presents significant difficulty for both diagnostics and modeling. The former requires precise spatially- and time-resolved measurements on a micron-nanosecond scale while the latter needs numerous descriptive parameters; many of them can only be obtained from experiment. Diagnostics and modeling should always complement each other for obtaining a truthful picture of LIP.
In this presentation, a newly developed collisional-dominated model will be presented. The model is based on the coupled Navier-Stokes, state, radiative transfer, material transport, and chemical equations. The model incorporates plasma chemistry through the equilibrium approach that relies on atomic and molecular partition functions. Several chemical systems are modeled including Si-C-Cl-N and B-H-Cl systems.
The model is used to study the equilibrium states of the systems as functions of the concentrations of plasma species and plasma temperature. The model also predicts the evolution of number densities of atomic and molecular species in the expanding plasma plume.
High purity halides of III-VI group elements, especially chloride and fluorides, are used in gas phase technologies for obtaining high purity materials and coatings. The reduction of halides in hydrogen-halide mixtures can be achieved in various discharge plasmas, e.g. inductively coupled, ark, and even laser-induced plasmas. Existing models of such plasmas are not sufficiently accurate to predict a yield of the targeted compounds and to describe the plasma processes involved in formation of these compounds. Besides, a construction of costly plasma-chemical reactors can be alleviated by the prior modeling of plasma processes that may occur in such reactors.
A goal of this work is to extend the model, which was initially developed for laser induced Plasmas, to plasmas used in chemical reactors, in particular, the inductively-coupled-RF discharge Plasma. The model predicts equilibrium chemical compositions of reaction mixtures as functions of plasma temperature and stoichiometry of reactants. The mixtures investigated are BCl3/H2/Ar and BF3/H2/Ar where Ar serves as the plasma-forming gas and H2 as a binding agent which binds the active species Cl and F and Cl- and F-containing intermediates to produce gaseous B and its condensate. An additional goal is to obtain information about intermediate reaction products for different ratios of BCl3/H2 and BF3/H2 and at different temperatures and different Ar flow rates.
It is found that the desired components B and B2 appear at appreciable concentrations of >0.1% and ~0.01% respectively only at temperatures above 3000 K. It is also established that the effect of charged species on the reaction products is miniscule for temperatures below 5000 K. The expected yield of boron as a function of the original mole fraction H2/BCl3 and H2/BF3 is calculated. The mole fractions are varied in the range 0.1-1000 and the temperature in the range 1000-10000 K. It is shown that the yield of boron increases with increasing the molar ratio H2/BCl3 and H2/BF3 up to ~100 in the temperature range 2000-5000 K. At higher temperatures, T>5000 K, the boron concentration reaches its maximum and does not depend on the concentration of hydrogen; all molecules dissociate and chemical reactions proceed only between charged particles (mostly elemental ions) and electrons. The calculated plasma parameters and composition are compared with experimental data obtained by optical emission spectroscopy. The calculated plasma temperature and electron density are shown to be in good agreement with the measured ones.
An improved algorithm for calibration-free laser induced breakdown spectroscopy (CF LIBS) will be presented which includes several novel features in comparison with previously proposed similar algorithms. In particular, it allows using spectral lines with arbitrary optical thickness for the construction of Saha-Boltzmann plots, retrieves the absorption path length (plasma diameter) directly from a spectrum, replaces the Lorentzian line profile function by the Voigt function, and allows for self-absorption correction using pre-calculated and tabulated data rather than approximating functions. The tabulated data embody the solutions of the radiative transfer equation for numerous combinations of optical thicknesses and line widths. The algorithm is thoroughly verified using synthetic spectra.
In situ chemical analysis of duplex stainless steel weld by laser induced breakdown spectroscopy
(2024)
The high corrosion resistance and good mechanical properties of duplex stainless steel (DSS) are due to its special chemical composition, which is a balanced phase ratio of ferrite (α) and austenite (γ). Many industrial applications require the integration of DSS components. For this, Gas tungsten arc welding (GTAW) is an excellent choice, as it allows an automated operation with high reproducibility. However, when the weld pool solidifies, critical ratios of α- and γ- phases can occur, which lead to solidification cracking, increased susceptibility to corrosion, and a decrease in ductility and critical strength. Previous studies have shown that these defects can be caused by the accumulation of manganese and chromium in the heat affected zone (HAZ), requiring ongoing monitoring of this accumulation. A suitable method for such monitoring is laser-induced breakdown spectroscopy (LIBS), which can be used in two operating modes: calibration using standard reference samples and calibration-free. Unlike conventional quantitative LIBS measurements, which require reference samples to generate a calibration curve, calibration-free LIBS (CF-LIBS) allows chemical compositions to be determined solely from the emission spectrum of the plasma. Numerous publications show that CF-LIBS is a fast and efficient analytical method for the quantitative analysis of metal samples. In this work, CF-LIBS is applied to spectra obtained during GTAW DSS welding and the result is compared with those obtained by PLS analysis. A good correlation was found between both types of analysis, demonstrating the suitability of the CF-LIBS method for this application. The CF-LIBS method has a significant advantage over conventional LIBS due to the rapid in situ measurement of concentrations of major alloying elements without calibration procedure. This, combined with fast feedback and appropriate adjustment of welding parameters, helps prevent welding defects.