TY - JOUR A1 - Galbacs, G. A1 - Keri, A. A1 - Kalomista, I. A1 - Kovacs-Szeles, E. A1 - Gornushkin, Igor B. T1 - Deuterium analysis by inductively coupled plasma mass spectrometry using polyatomic species: An experimental study supported by plasma chemistry modeling N2 - based on the use of the signal from hydrogen-containing polyatomic ions formed in the inductively coupled plasma. Prior to analytical experiments, a theoretical study was performed to assess the concentration of polyatomic species present in an equilibrium Ar-O-D-H plasma, as a function of temperature and stoichiometric composition. It was established that the highest sensitivity and linearity measurement of D concentration in a wide range can be achieved by monitoring the ions of D2 and ArD, at masses 4 and 42, respectively. Results of the calculations are in good agreement with the experiments. Signal stability, spectral interferences, as well as the effect of plasma parameters were also assessed. Under optimized conditions, the limit of detection (LOD) was found to be 3 ppm atom fraction for deuterium when measured as ArD (in calcium and potassium free water), or 78 ppm when measured as D2. The achieved LOD values and the 4 to 5 orders of magnitude dynamic range easily allow the measurement of deuterium concentrations at around or above the natural level, up to nearly 100% (or 1 Mio ppm) in a standard quadrupole ICP-MS instrument. An even better performance is expected from the method in high resolution ICP-MS instruments equipped with low dead volume sample introduction systems KW - ICP MS KW - Deuterium KW - Deuterium enriched water PY - 2020 DO - https://doi.org/10.1016/j.aca.2020.01.011 VL - 1104 SP - 28 EP - 37 PB - Elsevier B.V. AN - OPUS4-50777 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gaft, M. A1 - Nagli, L. A1 - Gornushkin, Igor B. T1 - Laser-induced breakdown spectroscopy of Zr in short ultraviolet wavelength range N2 - Emission and absorption spectra of a laser-induced zirconium plasma are studied at early times after plasma formation in the short UV spectral range from 190 to 240 nm. Many lines from highly ionized Zr ions, such as Zr IV at 216.4 and 228.7 nm and Zr III at 194.1, 194.7, 193.1, 196.3, 196.6, 197.5, 199.0, 200.3, 200.8, 202.8, 203.6, 205.7, 206.1, 207.1, 208.6, 210.2, 211.4, 217.6, and 219.1 nm have been found in the plasma under ambient and vacuum conditions. These lines could be detected in both single-pulse and double-pulse ablation modes. Several of the detected lines, namely those observed at 195.0, 198.2, 199.7, 229.4, 231.6, 232.4 and 233.0 nm, could not be attributed to Zr after inspecting known spectral data bases. From the temporal persistence behavior of these lines, it is concluded that they most likely belong to Zr I and Zr II emission lines that have not previously been reported. KW - Laser-induced breakdown spectroscopy KW - Zirconium KW - Triple ionization KW - Double ionization KW - Unknown lines PY - 2013 DO - https://doi.org/10.1016/j.sab.2013.04.006 SN - 0584-8547 SN - 0038-6987 VL - 85 SP - 93 EP - 99 PB - Elsevier CY - Amsterdam AN - OPUS4-30435 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nagli, L. A1 - Gaft, M. A1 - Gornushkin, Igor B. A1 - Glaus, Reto T1 - Stimulated emission and lasing in laser-induced plasma plume N2 - The lasing effect is demonstrated in laser plasmas induced on various metal targets and pumped by a laser tuned in resonance with a strong optical transition of a metal. The intense, polarized and lowdivergent radiation is emitted from a longitudinally pumped plasma plume in forward and backward directions with respect to the pump beam. Lasing occurs only within duration of the pumping pulse. The effect is found for elements of 13th and 14th groups and for Ca, Ti, Zr, Fe and Ni. The Einstein coefficients for spontaneous emission of all lasing transitions are higher than 10⁷ s⁻¹. For some elements like Al and In, a three-level lasing scheme is realized. For others, like Tl, both three- and four-level lasing schemes are realized. It is found that the longitudinal pump geometry is more efficient than the transversal one. KW - Optically pumped plasma lasers KW - Laser Induced Breakdown Spectroscopy (LIBS) KW - Laser Induced Fluorescence (LIF) PY - 2016 DO - https://doi.org/10.1016/j.optcom.2016.05.071 SN - 0030-4018 VL - 378 SP - 41 EP - 48 PB - Elsevier CY - Amsterdam, Netherlands AN - OPUS4-36320 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Shabanov, Sergej V. A1 - Gornushkin, Igor B. T1 - Modeling chemical reactions in laser-induced plasmas N2 - Under the assumption of local thermal equilibrium, a numerical algorithm is proposed to find the equation of state for laser-induced plasmas (LIPs) in which chemical reactions are permitted in addition to ionization processes. The Coulomb interaction in plasma is accounted for by the Debye–Hückel method. The algorithm is used to calculate the equation of state for LIPs containing carbon, silicon, nitrogen, and argon. The equilibrium reaction constants are calculated using the latest experimental and ab initio data of spectroscopic constants for the molecules N2 ,C2 ,Si2 ,CN,SiN,SiC and their ions. The algorithm is incorporated into a fluid dynamic numerical model based on the Navier–Stokes equations describing an expansion of LIP plumes into an ambient gas. The dynamics of LIP plumes obtained by the ablation of SiC, solid silicon, or solid carbon in an ambient gas containing N2 and Ar is simulated to study formation of molecules and molecular ions. KW - Laser-induzierte Plasmaspektroskopie KW - Numerische Simulation KW - Chemische Reaktion KW - Elektronische Spektren PY - 2015 DO - https://doi.org/10.1007/s00339-015-9445-0 SN - 0947-8396 VL - 121 IS - 3 SP - 1087 EP - 1107 PB - Springer CY - Berlin AN - OPUS4-35225 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Glaus, Reto A1 - Riedel, Jens A1 - Gornushkin, Igor B. T1 - Insight into the formation of molecular species in laser-induced plasma of isotopically labeled organic samples N2 - Recently, the detection of molecular species in laser-induced breakdown spectroscopy (LIBS) has gained increasing interest, particularly for isotopic analysis. In LIBS of organic materials, it is predominantly CN and C2 species that are formed, and multiple mechanisms may contribute to their formation. To gain deeper insight into the formation of these species, laser-induced plasma of 13C and 15N labeled organic materials was investigated in a temporally and spatially resolved manner. LIBS on fumaric acid with a 13C labeled double bond allowed the formation mechanism of C2 to be investigated by analyzing relative signal intensities of 12C2, 12C13C, and 13C2 molecules. In the early plasma (<5 µs), the majority of C2 originates from association of completely atomized target molecules, whereas in the late plasma, the increased concentration of 13C2 is due to incomplete dissociation of the carbon double bond. The degree of this fragmentation was found to be up to 80% and to depend on the type of the atmospheric gas. Spatial distributions of C2 revealed distinct differences for plasma generated in nitrogen and argon. A study of the interaction of ablated organics with ambient nitrogen showed that the ambient nitrogen contributed mainly to CN formation. The pronounced anisotropy of the C15N to C14N ratio across the diameter of the plasma was observed in the early plasma, indicating poor initial mixing of the plasma with the ambient gas. Overall, for accurate isotope analysis of organics, LIBS in argon with relatively short integration times (<10 µs) provides the most robust results. On the other hand, if information about the original molecular structure is of interest, then experiments in nitrogen (or air) with long integration times appear to be the most promising. KW - Laser-induzierte Plasmaspektroskopie KW - Ablation KW - Emission KW - Isotopenmarkierung PY - 2015 DO - https://doi.org/10.1021/acs.analchem.5b02926 SN - 0003-2700 SN - 1520-6882 VL - 87 IS - 19 SP - 10131 EP - 10137 PB - American Chemical Society CY - Washington, DC AN - OPUS4-35226 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Improving Limits of Detection of Chlorine and Sulfur in Cement with Double Pulse LIBS and Electric Spark Reheating T2 - EMSLIBS CY - Linz, Austria DA - 2015-09-14 PY - 2015 AN - OPUS4-35147 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Detection of CaCl in cement by LIBS T2 - EMSLIBS CY - Linz, Austria DA - 2015-09-14 PY - 2015 AN - OPUS4-35148 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Tomography of laser-induced plasma using Radon transform technique for temporally and spatially resolved plasma diagnostics T2 - ANAKON 2015 CY - Graz, Österreich DA - 2015-03-23 PY - 2015 AN - OPUS4-35152 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - CN and C2 formation in laser induced plasmas of isotopic labeled target substances T2 - EMSLIBS CY - Linz, Austria DA - 2015-09-14 PY - 2015 AN - OPUS4-35145 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - High speed sorting of scrap metal based on meta-modeling T2 - EMSLIBS CY - Linz, Austria DA - 2015-09-14 PY - 2015 AN - OPUS4-35146 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sennikov, P. A1 - Gornushkin, Igor B. A1 - Kornev, R. A1 - Nazarov, V. A1 - Polyakov, V. A1 - Shkrunin, V. T1 - Hydrogen Reduction of MoF6 and Molybdenum Carbide Formation in RF Inductively Coupled Low‑Pressure Discharge: Experiment and Equilibrium Thermodynamics Consideration N2 - The physical plasma parameters, temperature and electron number density, are studied in the RF-IC (RF inductively coupled) discharge at a reduced pressure of 3 Torr in mixtures of MoF6 with Ar, H2 and CH4. The emission spectra of mixtures are investigated. It is shown that in the presence of argon, the concentration of free electrons in plasma and dissociation rate of MoF6 increase. A main role of molecular hydrogen is the generation of atomic hydrogen that binds atomic fuorine and leads to the formation of gaseous and solid products. Exhaust gas mixtures exiting the reactor are analyzed by mass spectrometry. It is shown that for all cases, the conversion of MoF6 into reaction products is close to 100%. A thermodynamic analysis of the equilibrium composition of MoF6 systems with Ar, H2 and CH4 was carried out and the obtained results are in good agreement with experimentally observed composition of the solid and gas phases. Analysis of solid deposits from mixture MoF6/H2/Ar revealed the presence of molybdenum powder and large amount of amorphous MoFx. The deposit obtained from mixtures with methane, MoF6/H2/Ar/CH4, contained crystalline molybdenum carbide, Mo3C2. KW - Molybdenum carbide KW - RF ICP discharge KW - Reduction of MoF6 KW - Thermodynamic KW - Molybdenum PY - 2020 DO - https://doi.org/10.1007/s11090-020-10138-3 SN - 0272-4324 VL - 41 IS - 2 SP - 673 EP - 690 PB - Springer AN - OPUS4-51569 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gaft, M. A1 - Nagli, L. A1 - Gornushkin, Igor B. A1 - Raichlin, Y. T1 - Review on recent advances in analytical applications of molecular emission and modelling N2 - The review mainly deals with two topics that became important in applications of laser-induced breakdown spectroscopy (LIBS) in recent years: the emission of halogen- and rare-earth-containing molecules and selective excitation of molecules by molecular laser-induced fluorescence (MLIF). The first topic is related to the emission of alkaline-earth diatomic halides MX, M = Ca, Mg, Ba, Sr and X = F, Cl, Br, and I and rare-earth element (REE) oxides LaO, YO, and ScO. These molecules form in laser-induced plasma (LIP) soon after its ignition and persist for a long time, emitting broad bands in a visible part of the spectrum. They are best detected after relatively long delay times when emission from interfering plasma species (atoms and ions) has already been quenched. Such behavior of molecular spectra allows of using, for their detection, inexpensive CCD detectors equipped with simple electronic or mechanical shutters and low-resolution spectrometers. A main target for analysis by molecular spectroscopy is halogens; these elements are difficult to detect by atomic spectroscopy because their most intense atomic lines lie in the vacuum UV. Therefore, in many situations, emission from CaF and CaCl may provide a substantially more sensitive detection of F and Cl than emission from elemental F and Cl and their ions. This proved to be important in mining and concrete industries and even Mars exploration. A similar situation is observed for REEs; their detection by atomic spectroscopy sometimes fails even despite the abundance of atomic and ionic REEs' lines in the UV-VIS. For example, in minerals and rocks with low concentrations of REEs, emission from major and minor mineral elements hinders the weak emission from REEs. Many REEs do not form molecules that show strong emission bands in LIP but can still be detected with the aid of LIP. All REEs except La, Y, and Sc exhibit long-lived luminescence in solid matrices that is easily excited by LIP. The luminescence can be detected simultaneously with molecular emission of species in LIP within the same time and spectral window. The second topic is related to the combination of MLIF and LIBS, which is a technique that was proved to be efficient for analysis of isotopic molecules in LIP. For example, the characteristic spectral signals from isotopic molecules containing 10B and 11B are easier to detect with MLIF-LIBS than with laser ablation molecular isotopic spectrometry (LAMIS) because MLIF provides strong resonance excitation of only targeted isotopes. The technique is also very efficient in detection of halogen molecules although it requires an additional tunable laser that makes the experimental setup bulky and more expensive. KW - Plasma induced luminescence KW - Molecular emission KW - Laser induced plasma KW - Plasma modeling KW - Molecular analysis KW - LIBS PY - 2020 DO - https://doi.org/10.1016/j.sab.2020.105989 VL - 173 SP - 105989 PB - Elsevier B. V. AN - OPUS4-51420 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -