TY - CONF A1 - Gornushkin, Igor B. T1 - Calibration- and Calibration-Free LIBS: Past and Future (invited) T2 - SciX-FACSS CY - Providence, RI, USA DA - 2015-09-27 PY - 2015 AN - OPUS4-35141 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Recent Advancements in Modeling of Laser Induced Plasmas and Supporting Plasma Diagnostics (invited) T2 - EMSLIBS CY - Linz, Austria DA - 2015-09-14 PY - 2015 AN - OPUS4-35140 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Demidov, Alexandr A1 - Eschlböck-Fuchs, S. A1 - Kazakov, Alexander Ya. A1 - Gornushkin, Igor B. A1 - Kolmhofer, P. J. A1 - Pedarnig, J. D. A1 - Huber, N. A1 - Heitz, J. A1 - Schmid, Thomas A1 - Rössler, R. A1 - Panne, Ulrich T1 - Monte Carlo standardless approach for laser induced breakdown spectroscopy based on massive parallel graphic processing unit computing N2 - The improved Monte-Carlo (MC) method for standard-less analysis in laser induced breakdown spectroscopy (LIBS) is presented. Concentrations in MC LIBS are found by fitting model-generated synthetic spectra to experimental spectra. The current version of MC LIBS is based on the graphic processing unit (GPU) computation and reduces the analysis time down to several seconds per spectrum/sample. The previous version of MC LIBS which was based on the central processing unit (CPU) computation requested unacceptably long analysis times of 10's minutes per spectrum/sample. The reduction of the computational time is achieved through the massively parallel computing on the GPU which embeds thousands of co-processors. It is shown that the number of iterations on the GPU exceeds that on the CPU by a factor > 1000 for the 5-dimentional parameter space and yet requires > 10-fold shorter computational time. The improved GPU-MC LIBS outperforms the CPU-MS LIBS in terms of accuracy, precision, and analysis time. The performance is tested on LIBS-spectra obtained from pelletized powders of metal oxides consisting of CaO, Fe2O3, MgO, and TiO2 that simulated by-products of steel industry, steel slags. It is demonstrated that GPU-based MC LIBS is capable of rapid multi-element analysis with relative error between 1 and 10's percent that is sufficient for industrial applications (e.g. steel slag analysis). The results of the improved GPU-based MC LIBS are positively compared to that of the CPU-based MC LIBS as well as to the results of the standard calibration-free (CF) LIBS based on the Boltzmann plot method. KW - Monte Carlo simulation KW - Parallel computing KW - Calibration-free laser-induced breakdown spectroscopy KW - Post-breakdown laser induced plasma KW - Quaternary oxides PY - 2016 DO - https://doi.org/10.1016/j.sab.2016.09.016 VL - 125 SP - 97 EP - 102 PB - Elsevier B.V. AN - OPUS4-38489 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scheuschner, Nils A1 - Altenburg, Simon A1 - Pignatelli, Giuseppe A1 - Maierhofer, Christiane A1 - Straße, Anne A1 - Gornushkin, Igor B. A1 - Gumenyuk, Andrey T1 - Vergleich der Messungen der Schmelzbadtemperatur bei der Additiven Fertigung von Metallen mittels IR-Spektroskopie und Thermografie T1 - Comparison of measurements of the melt pool temperature during the additive production of metals by means of IR spectroscopy and thermography N2 - Im Rahmen des Themenfeldprojektes „Process Monitoring of AM“ (ProMoAM) evaluiert die Bundesanstalt für Materialforschung und -Prüfung (BAM) gegenwärtig die Anwendbarkeit verschiedenster ZfP-Verfahren zur in-situ Prozessüberwachung in der additiven Fertigung (AM) von Metallen in Hinblick auf die Qualitätssicherung. Einige der wichtigsten Messgrößen sind hierbei die Temperatur des Schmelzbades und die Abkühlrate, welche starken Einfluss auf das Gefüge und die Eigenspannung haben. Aufgrund der Zugänglichkeit zum Werkstück während des Bauprozesses bieten sich optische Verfahren zu Temperaturbestimmung an. Hierbei stellen jedoch u. a. die hohe Bandbreite der zu messenden Temperaturen, die Bestimmung der Emissivität und ihre Änderung bei Phasenübergängen der verwendeten Legierung große experimentelle Herausforderungen dar. Eine weitere Herausforderung stellt für die IR-Spektroskopie die Absorption durch das Schutzgas und weitere optische Elemente dar. Um diese auch in einem industriellen Umfeld kompensieren zu können, wurde eine Methode entwickelt, die das gemessene Spektrum bei der Verfestigung des Werkstoffes als Referenz nutzt. In diesem Beitrag wird die Anwendung dieser Methode für die IR-Spektrometrie als auch Thermografische Messungen beim Laser-Pulver-Auftragschweißen von 316L gezeigt, wobei beide Methoden weiterhin in Hinblick auf ihre individuellen Vor- und Nachteile miteinander verglichen werden. N2 - Within the topic area project “Process Monitoring of AM” (ProMoAM) the Federal Institute for Materials Research and Testing is currently evaluating the applicability of various NDT methods for in-situ process Monitoring in the additive manufacturing (AM) of metals with regard to quality assurance. Two of the most important variables to measure are the temperature of the molten pool and the cooling rate, which have a strong influence on the microstructure and the residual stress. Due to the accessibility of the workpiece during the construction process, optical methods for temperature determination are suitable. However, the wide range of temperatures to be measured, the determination of emissivity and its change during phase transitions of the alloy pose great experimental challenges. Another challenge for IR spectroscopy is the absorption by the inert gas and other optical elements. In order to be able to compensate for this in an industrial environment, a method was developed which uses the measured spectrum as a reference when the material is solidified. This paper shows the application of this method for IR spectrometry as well as thermographic measurements during laser powder cladding of 316L. Furthermore both methods are compared with respect to their individual Advantages and disadvantages. KW - Laser-Pulver-Auftragschweißen KW - Thermografie KW - Direct Energy Deposition KW - IR-Spektroskopie KW - Additive Fertigung KW - Laser metal deposition KW - Thermography KW - IR-spectroscopy KW - Additive manufacturing PY - 2021 DO - https://doi.org/10.1515/teme-2021-0056 VL - 88 IS - 10 SP - 626 EP - 632 PB - De Gruyter CY - Oldenburg AN - OPUS4-52987 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Shcheglov, Pavel A1 - Gumenyuk, Andrey A1 - Gornushkin, Igor B. A1 - Rethmeier, Michael T1 - Experimental investigation of the laser-plume interaction during high power fiber laser welding N2 - The effect of the well-known plasma absorption and refraction in CO2-laser metal welding plumes is in case of high power solid state laser welding negligibly small. By contrast, the diffraction effects of shorter wavelength laser radiation are considerable. According to the results of preliminary studies, the fine condensed metal particles in the welding plume can lead to essential worsening of the laser beam quality. This work is devoted to the investigation of the lasermatter interaction during up to 20 kW ytterbium fiber laser welding of thick mild steel plates. The plume attenuation of a probe 1.3 µm wavelength diode laser beam as well as of continuous radiation in 250-600 nm wavelength range was measured during welding with and without Ar shielding gas supply. The measured results allow it to calculate average size and concentration of fine condensed metal particles in different plume areas using the multi-wavelength method and the Mie scattering theory. The plume temperature, which determines the condensation conditions, was measured by means of Fe I atom spectral line emission registration. The obtained results can be also of interest for remote metal treatment with high-power fiber or disc lasers. T2 - 30th ICALEO - International congress on applications of lasers & electro-optics CY - Orlando, FL, USA DA - 2011-10-23 PY - 2011 SN - 978-0-912035-94-9 SP - Paper 1606, 637 EP - 645 AN - OPUS4-24921 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Shcheglov, Pavel A1 - Gumenyuk, Andrey A1 - Gornushkin, Igor B. A1 - Rethmeier, Michael A1 - Petrovskiy, V.N. T1 - Vapor-plasma plume investigation during high-power fiber laser welding N2 - This work is devoted to the investigation of the laser–matter interaction during up to 20 kW ytterbium fiber laser welding of thick mild steel plates. The plume attenuation of a probe 1.3 µm wavelength diode laser beam as well as of continuous radiation in the 250–600 nm wavelength range was measured during welding with and without Ar shielding gas supply. The measured results allow the calculation of the average size and concentration of fine condensed metal particles in different plume areas using the multi-wavelength method and the Mie scattering theory. The plume temperature, which determines the condensation conditions, was measured by means of Fe I atom spectral line emission registration. The spatial distribution of the extinction coefficient in the welding plume was measured and the plume attenuation of the high-power fiber laser beam during the welding process was estimated. PY - 2013 DO - https://doi.org/10.1088/1054-660X/23/1/016001 SN - 1054-660X SN - 1531-8494 VL - 23 IS - 016001 SP - 1 EP - 7 PB - MAIK Nauka/Interperiodica Publ. CY - Moscow AN - OPUS4-27280 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Straße, Anne A1 - Gumenyuk, Andrey A1 - Scheuschner, Nils A1 - Altenburg, Simon A1 - Pignatelli, Giuseppe A1 - Gornushkin, Igor B. A1 - Baensch, Franziska A1 - Rethmeier, Michael T1 - In-situ Prozessüberwachung beim Laser-Pulver-Auftragschweißen (LPA) mittels Thermografie, optischer Emissionsspektroskopie (OES) und Schallemissionsanalyse (SEA) N2 - Vor allem in den letzten Jahren ist das Interesse der Industrie an der additiven Fertigung deutlich gestiegen. Die Vorteile dieser Verfahren sind zahlreich und ermöglichen eine ressourcenschonende, kundenorientierte Fertigung von Bauteilen, welche zur stetigen Entwicklung neue Anwendungsbereiche und Werkstoffe führen. Aufgrund der steigenden Anwendungsfälle, nimmt auch der Wunsch nach Betriebssicherheit unabhängig von anschließenden kostenintensiven zerstörenden und zerstörungsfreien Prüfverfahren zu. Zu diesem Zweck werden im Rahmen des von der BAM durchgeführten Themenfeldprojektes „Prozessmonitoring in Additive Manufacturing“ verschiedenste Verfahren auf ihre Tauglichkeit für den in-situ Einsatz bei der Prozessüberwachung in der additiven Fertigung untersucht. Hier werden drei dieser in-situ Verfahren, die Thermografie, die optische Emissionsspektroskopie und die Schallmissionsanalyse für den Einsatz beim Laser-Pulver-Auftragschweißen betrachtet. T2 - 41. Assistentenseminar der Füge- und Schweißtechnik CY - Magdeburg, Germany DA - 02.09.2020 KW - Laser-Pulver-Auftragschweißen (LPA) KW - Thermographie KW - Optische Emissionsspektroskopie (OES) KW - Schallemissionsanalyse (SEA) PY - 2021 SN - 978-3-96144-141-9 VL - 370 SP - 132 EP - 140 PB - DVS MEdia CY - Düsseldorf AN - OPUS4-53967 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - LIBS as an Analytical Method 2.0 T2 - EMSLIBS CY - Rome, Italy DA - 2009-09-28 PY - 2009 AN - OPUS4-19840 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Matiaske, Anna-Maria A1 - Gornushkin, Igor B. A1 - Panne, Ulrich T1 - Double-pulse laser-induced breakdown spectroscopy for analysis of molten glass N2 - A mobile double-pulse laser-induced breakdown spectroscopy system for industrial environments is presented. Its capabilities as a process analytical technique for the recovery of metals from molten inorganic wastes are investigated. Using low-melting glass doped with different amounts of additives as a model system for recycling slags, the optimum number of shots, laser inter-pulse and acquisition delay times are optimized for solid and liquid (1200 °C) glass. Limits of detection from 7 ppm (Mn) to 194 ppm (Zn) are achieved working at a distance of 75 cm from the sample. To simplify the quantification of molten samples in an industrial furnace, the possibility is examined of using solid standards for analysis of molten material. KW - Laser-induced breakdown spectroscopy KW - LIBS KW - Double-pulse LIBS KW - Molten glass KW - Recycling PY - 2011 DO - https://doi.org/10.1007/s00216-011-5165-2 SN - 1618-2642 SN - 1618-2650 VL - 402 IS - 8 SP - 2597 EP - 2606 PB - Springer CY - Berlin AN - OPUS4-23950 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gornushkin, Igor B. A1 - Panne, Ulrich T1 - Radiative models of laser-induced plasma and pump-probe diagnostics relevant to laser-induced breakdown spectroscopy N2 - The paper describes past and present efforts in modeling of laser-induced plasma and overviews plasma diagnostics carried out by pump-probe techniques. Besides general information on existing plasma models, the emphasis is given to models relevant to spectrochemical analysis, i.e. models of radiating plasma. Special attention is paid to collisional-radiative (CR) and collisional-dominated (CD) plasma models where radiative processes play an important role. Also, calibration-free (CF) models are considered which may endow with the possibility for standardless spectroscopic analysis. In the diagnostic part, only methods based on the use of additional diagnostic tools (auxiliary lasers, optics, and probes) are described omitting those based on plasma own radiation. A short review is provided on image-based diagnostics (shadowgraphy, schlieren, and interferometry), absorption and fluorescence, Langmuir probe, and less frequently used cavity ringdown and Thomson scattering methods. KW - Laser ablation KW - Modeling KW - Plasma diagnostics KW - Laser-induced breakdown spectroscopy PY - 2010 DO - https://doi.org/10.1016/j.sab.2010.03.021 SN - 0584-8547 SN - 0038-6987 VL - 65 IS - 5 SP - 345 EP - 359 PB - Elsevier CY - Amsterdam AN - OPUS4-24003 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Novel low cost compact Echelle spectrograph for laser induced breakdown spectroscopy with a diode pumped solid state laser T2 - Colloquium Spectroscopicum Internationale XXXVII CY - Rio de Janeiro, Brazil DA - 2011-08-28 PY - 2011 AN - OPUS4-24633 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Laser Induced Breakdown and Raman Spectroscopy with Diode Pumped Solid State (DPSS) Lasers T2 - ANAKON 2011 CY - Zurich, Switzerland DA - 2011-03-22 PY - 2011 AN - OPUS4-24881 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Laser Induced Breakdown Spectroscopy (LIBS) and Raman Spectroscopy for Material Analysis T2 - 16. Tagung Festkörperanalytik CY - Vienna, Austria DA - 2011-07-04 PY - 2011 AN - OPUS4-24885 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hoehse, M. A1 - Paul, Andrea A1 - Gornushkin, Igor B. A1 - Panne, Ulrich T1 - Multivariate classification of pigments and inks using combined Raman spectroscopy and LIBS N2 - The authenticity of objects and artifacts is often the focus of forensic analytic chemistry. In document fraud cases, the most important objective is to determine the origin of a particular ink. Here, we introduce a new approach which utilizes the combination of two analytical methods, namely Raman spectroscopy and laser-induced breakdown spectroscopy (LIBS). The methods provide complementary information on both molecular and elemen tal composition of samples. The potential of this Hyphen ation of spectroscopic methods is demonstrated for ten blue and black ink samples on white paper. LIBS and Raman spectra from different inks were fused into a single data matrix, and the number of different groups of inks was determined through multivariate analysis, i.e., principal component analysis, soft independent modelling of class analogy, partial least-squares discriminant analysis, and support vector machine. In all cases, the results obtained with the combined LIBS and Raman spectra were found to be superior to those obtained with the individual Raman or LIBS data sets. KW - Pigments KW - Raman KW - LIBS KW - Chemometrics PY - 2012 DO - https://doi.org/10.1007/s00216-011-5287-6 SN - 1618-2642 SN - 1618-2650 VL - 402 IS - 4 SP - 1443 EP - 1450 PB - Springer CY - Berlin AN - OPUS4-25440 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gornushkin, Igor B. A1 - Shabanov, Sergej V. A1 - Panne, Ulrich T1 - Abel inversion applied to a transient laser induced plasma: implications from plasma modeling N2 - We test the effects of non-uniformity, non-transparency, and non-stationarity of a laser-induced plasma on the results obtained by the Abel inversion method. The method is commonly used for obtaining spatially resolved emissivity of axially symmetric non-homogeneous radiating objects. Besides the axial symmetry, the plasma is assumed to be optically thin. As the method addresses a certain plasma state, the plasma is required to be stationary during measurements. It is difficult to satisfy the aforementioned conditions for transient laser induced plasmas. As such the plasmas are not stationary; they have steep gradients of thermodynamic parameters that rapidly vary during the plasma evolution. Therefore, any conclusion based on time-integrated measurements and the corresponding data processing should account for these effects. In this work, we use the collision-dominated plasma model to generate time- and spatially resolved synthetic spectra. The spectra are processed by executing the Abel inversion using two numerical algorithms. Thus obtained spatially resolved plasma parameters (emissivity, temperature, and number density) are compared with the exact parameters used to set up the model. In doing so, the accuracy of the Abel inversion method is assessed. Special attention is paid to the dynamic aspect of the expanding plasma and possible errors which result from time-integrated measurements. PY - 2011 DO - https://doi.org/10.1039/c1ja10044k SN - 0267-9477 SN - 1364-5544 VL - 26 IS - 7 SP - 1457 EP - 1465 PB - Royal Society of Chemistry CY - London AN - OPUS4-25824 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Diagnostic and Modeling of Laser Induced Breakdown Spectroscopy Based on Optical Tomography T2 - SCIX (FACSS) CY - Kansas City, MO, USA DA - 2012-09-30 PY - 2012 AN - OPUS4-27325 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Modeling and diagnostics of laser induced plasma for needs of spectrochemical analysis N2 - Two topics will be addressed: (1) calibration-free LIBS based on Monte Carlo spectral optimization and (2) insight into the possibility of simultaneous elemental and molecular analysis by LIBS. Both topics heavily rely on modeling of laser induced plasma and are closely connected to experiment. In Monte Carlo LIBS (MC LIBS), concentrations are found by fitting model-generated synthetic spectra to experimental spectra. The model of a static uniform isothermal plasma in local thermodynamic equilibrium is employed. Many configurations of plasma parameters and their corresponding spectra are simultaneously generated using a graphic processing unit (GPU). Using the GPU allows for the reduction of computational time down to several minutes for one experimental spectrum that presents the significant progress in comparison with earlier versions of MC LIBS. The method is tested by analyzing industrial oxides containing various concentrations of CaO, Fe2O3, MgO, and TiO2. The agreement within several percent between found and certified concentrations is achieved. Next, a newly developed collisional-dominated model of a laser induced plasma is introduced. The model includes the coupled Navier-Stokes, state, radiative transfer, and material transport equations and incorporates plasma chemistry through the equilibrium approach based on the use of atomic and molecular partition functions. Simple chemical systems are modeled including ablation of Si and C in N2 and Ar atmospheres.The model is used to study evolution of number densities of atomic and molecular species in the expanding plasma plume. The distribution is compared to experimental observations obtained by optical imaging and tomography. To further verify the model, dynamic plasma T2 - FLAMN 2016 CY - St. Petersburg, Russia DA - 27.06.2016 KW - Plasma diagnostics KW - Laser induced plasma KW - LIBS KW - Plasma modeling PY - 2016 AN - OPUS4-38775 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Modeling and diagnostics of molecules in laser induced plasmasmodeling and diagnostics of molecules in laser induced plasmas N2 - A collisional-dominated model of a laser induced plasma will be presented which includes the coupled Navier-Stokes, state, radiative transfer, and material transport equations and incorporates plasma chemistry through the equilibrium approach based on the use of atomic and molecular partition functions. Simple chemical systems are modeled including ablation of Si, C, SiC, CaCl2 in N2 or Ar atmospheres with the formation of molecules N2, C2, Si2, CN, Cl2, SiN, SiC, CaCl, CaCl2 and their corresponding positive and negative ions1,2. The initial conditions are specially chosen to emulate the plasma state on the onset of expansion just after the laser pulse had ended. The model is used to study evolution of number densities of atomic and molecular species in the expanding plasma plume. The distribution is compared to experimental observations obtained by optical imaging and tomography. The model and experiment serve to elucidate mechanisms of molecular formation in LIPs, the topic which has recently received much attention in the LIBS community. T2 - LIBS 2016 CY - Chamonix, France DA - 12.09.2016 KW - Plasma diagnostics KW - Plasma physics PY - 2016 AN - OPUS4-38776 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Modeling and diagnostics of molecules in laser induced plasmasmodeling and diagnostics of molecules in laser induced plasmas N2 - A collisional-dominated model of a laser induced plasma will be presented which includes the coupled Navier-Stokes, state, radiative transfer, and material transport equations and incorporates plasma chemistry through the equilibrium approach based on the use of atomic and molecular partition functions. Simple chemical systems are modeled including ablation of Si, C, SiC, CaCl2 in N2 or Ar atmospheres with the formation of molecules N2, C2, Si2, CN, Cl2, SiN, SiC, CaCl, CaCl2 and their corresponding positive and negative ions. The model is used to study evolution of number densities of atomic and molecular species in the expanding plasma plume. The distribution is compared to experimental observations obtained by optical imaging and tomography. The model and experiment serve to elucidate mechanisms of molecular formation in LIPs, the topic which has recently received much attention in the LIBS community. T2 - SCIX 2016 CY - Minneapolis, USA DA - 18.09.2016 KW - Plasma diagnostics KW - Plasma physics PY - 2016 AN - OPUS4-38777 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Eschlböck-Fuchs, S. A1 - Huber, N. A1 - Ahamer, C. M. A1 - Hechenberger, J. G. A1 - Kolmhofer, P. J. A1 - Heitz, J. A1 - Rössler, R. A1 - Demidov, Alexander A1 - Schmid, Thomas A1 - Gornushkin, Igor B. A1 - Panne, Ulrich A1 - Pedarnig, J. D. T1 - Application of laser-induced breakdown spectroscopy for the analysis of slags in industrial steel production N2 - Laser-induced breakdown spectroscopy (LIBS) is a fast and versatile technique for (semi) quantitative element analysis of solids, liquids, gases, and particulate matter. The LIBS method is used for optical sensing in various branches of industrial production. In the contribution we review some of our recent results on LIBS analysis of slags from secondary metallurgy in industrial steel making. Major oxides in steel slags are measured at-line and after homogenization using a calibration-free (CF) method. Two approaches for CF analysis based on the Boltzmann plot method and on the calculation of synthetic spectra are compared for the analysis of quaternary oxides. We also present the research in cooperation with our industrial partners in the process-analytical chemistry network PAC. T2 - 11. Kolloquium Arbeitskreis Prozessanalytik CY - Vienna, Austria DA - 30.11.2015 KW - Laser-induced breakdown spectroscopy (LIBS) KW - Process analytical technology KW - Steel slag PY - 2015 PB - Plandruck+ Gesellschaft m.b.H. CY - Wien AN - OPUS4-39005 LA - eng 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 - FKA, Festkörperanalytik CY - Wien, Österreich DA - 2015-06-07 PY - 2015 AN - OPUS4-35151 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Tomography of laser-induced plasma for temporally, spectrally and spatially resolved plasma diagnostics using Radon transform technique T2 - EMSLIBS CY - Linz, Austria DA - 2015-09-14 PY - 2015 AN - OPUS4-35149 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bierstedt, Andreas A1 - Kersten, H. A1 - Glaus, Reto A1 - Gornushkin, Igor B. A1 - Panne, Ulrich A1 - Riedel, Jens T1 - Characterization of an airborne laser-spark ion source for ambient mass spectrometry N2 - An airborne laser plasma is suggested as an ambient ion source for mass spectrometry. Its fundamental physical properties, such as an excellent spatial and temporal definition, high electron and ion densities and a high effective cross section in maintaining the plasma, make it a promising candidate for future applications. For deeper insights into the plasma properties, the optical plasma emission is examined and compared to mass spectra. The results show a seemingly contradictory behavior, since the emitted light reports the plasma to almost entirely consist of hot elemental ions, while the corresponding mass spectra exhibit the formation of intact molecular species. Further experiments, including time- resolved shadowgraphy, spatially resolved mass spectrometry, as well as flow-dependent emission spectroscopy and mass spectrometry, suggest the analyte molecules to be formed in the cold plasma vicinity upon interaction with reactive species formed inside the hot plasma center. Spatial separation is maintained by concentrically expanding pressure waves, inducing a strong unidirectional diffusion. The accompanying rarefaction inside the plasma center can be compensated by a gas stream application. This replenishing results in a strong increase in emission brightness, in local reactive species concentration, and eventually in direct mass spectrometric sensitivity. To determine the analytical performance of the new technique, a comparison with an atmospheric pressure chemical ionization (APCI) source was conducted. Two kitchen herbs, namely, spearmint and basil, were analyzed without any sample pretreatment. The presented results demonstrate a considerably higher sensitivity of the presented laser-spark ionization technique. KW - Laser-spark KW - Laser induced plasma KW - Ambient mass spectrometry KW - Optical emission spectroscopy KW - Ionization PY - 2017 DO - https://doi.org/10.1021/acs.analchem.6b04178 SN - 0003-2700 SN - 1520-6882 VL - 89 IS - 6 SP - 3437 EP - 3444 PB - American Chemical Society CY - Washington, DC, USA AN - OPUS4-39474 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Model Investigation On Prediction Of Temperature And Electron Density From Emission Spectra Of Laser Induced Plasma T2 - 2010 Winter Conference on Plasma Spectrochemistry Fort Myers CY - Fort Myers, FL, USA DA - 2010-01-04 PY - 2010 AN - OPUS4-22910 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Test for validity of the Boltzmann Plot Method: Implications from Plasma Modeling T2 - FACSS 2010 CY - Raleigh, NC, USA DA - 2010-10-17 PY - 2010 AN - OPUS4-22911 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gornushkin, Igor B. A1 - Shabanov, Sergej V. A1 - Merk, Sven A1 - Tognoni, E. A1 - Panne, Ulrich T1 - Effects of non-uniformity of laser induced plasma on plasma temperature and concentrations determined by the Boltzmann plot method: implications from plasma modeling PY - 2010 DO - https://doi.org/10.1039/C0JA00016G SN - 0267-9477 SN - 1364-5544 VL - 25 SP - 1643 EP - 1653 PB - Royal Society of Chemistry CY - London AN - OPUS4-22942 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Boltzmann Plot and Abel Inversion Methods for Plasma Diagnostics: Implications from Plasma Modeling T2 - LIBS 2010 CY - Memphis, TN, USA DA - 2010-09-13 PY - 2010 AN - OPUS4-22912 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Höhse, Marek A1 - Gornushkin, Igor B. A1 - Merk, Sven A1 - Panne, Ulrich T1 - Assessment of suitability of diode pumped solid state lasers for laser induced breakdown and Raman spectroscopy N2 - The potential of a diode pumped solid state (DPSS) laser for laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy was investigated. The DPSS laser operating at repetition rates of 1 Hz–200 kHz, pulse energy of ~1 mJ, and pulse duration of ~20 ns was added to a conventional LIBS system equipped with the flashlamp-pumped Nd:YAG laser (10 Hz, 400 mJ, 6 ns) to directly compare the two laser systems. Despite the lower mass ablated per laser pulse (~several nanograms) and a weaker plasma, the total mass ablated per measurement interval (~1 s) and total emission signal were significantly higher than those obtained with the flashlamp pumped Nd:YAG laser. This resulted in the improved signal-to-noise ratio and better limits of detection (LOD). The best LODs were obtained for Cu, Cr and Ni in ultrapure standard iron samples, 0.7 ppm, 1 ppm and 5 ppm, correspondingly. The plasma from the DPSS laser was characterized in terms of its radiative properties, temperature, and shockwave propagation speed. The suitability of this laser for LIBS-Raman was demonstrated by mapping the elemental and molecular composition of a mineral sample. The results strongly imply that DPSS lasers are the promising source for LIBS, Raman, or combined LIBS-Raman spectroscopy. PY - 2011 DO - https://doi.org/10.1039/c0ja00038h SN - 0267-9477 SN - 1364-5544 VL - 26 IS - 2 SP - 414 EP - 424 PB - Royal Society of Chemistry CY - London AN - OPUS4-22943 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Höhse, Marek A1 - Mory, D. A1 - Florek, S. A1 - Weritz, Friederike A1 - Gornushkin, Igor B. A1 - Panne, Ulrich T1 - A combined laser-induced breakdown and Raman spectroscopy Echelle system for elemental and molecular microanalysis N2 - Raman and laser-induced breakdown spectroscopy is integrated into a single system for molecular and elemental microanalyses. Both analyses are performed on the same ~ 0.002 mm² sample spot allowing the assessment of sample heterogeneity on a micrometric scale through mapping and scanning. The core of the spectrometer system is a novel high resolution dual arm Echelle spectrograph utilized for both techniques. In contrast to scanning Raman spectroscopy systems, the Echelle-Raman spectrograph provides a high resolution spectrum in a broad spectral range of 200-6000 cm- 1 without moving the dispersive element. The system displays comparable or better sensitivity and spectral resolution in comparison to a state-of-the-art scanning Raman microscope and allows short analysis times for both Raman and laser induced breakdown spectroscopy. The laser-induced breakdown spectroscopy performance of the system is characterized by ppm detection limits, high spectral resolving power (15,000), and broad spectral range (290-945 nm). The capability of the system is demonstrated with the mapping of heterogeneous mineral samples and layer by layer analysis of pigments revealing the advantages of combining the techniques in a single unified set-up. KW - LIBS KW - Raman KW - Echelle KW - Laser-induced breakdown spectroscopy KW - Hyphenated technique PY - 2009 DO - https://doi.org/10.1016/j.sab.2009.09.004 SN - 0584-8547 SN - 0038-6987 VL - 64 IS - 11-12 SP - 1219 EP - 1227 PB - Elsevier CY - Amsterdam AN - OPUS4-20493 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gornushkin, Igor B. A1 - Panne, Ulrich A1 - Winefordner, J. D. T1 - Linear correlation for identification of materials by laser induced breakdown spectroscopy: Improvement via spectral filtering and masking N2 - The purpose of this work is to improve the performance of a linear correlation method used for material identification in laser induced breakdown spectroscopy. The improved correlation procedure is proposed based on the selection and use of only essential spectral information and ignoring empty spectral fragments. The method is tested on glass samples of forensic interest. The 100% identification capability of the new method is demonstrated in contrast to the traditional approach where the identification rate falls below 100% for many samples. KW - Correlation analysis KW - Linear correlation KW - Material identification KW - Laser induced plasma KW - LIBS PY - 2009 DO - https://doi.org/10.1016/j.sab.2009.07.038 SN - 0584-8547 SN - 0038-6987 VL - 64 IS - 10 SP - 1040 EP - 1047 PB - Elsevier CY - Amsterdam AN - OPUS4-20621 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Tomography of laser-induced plasma homogenized in double pulse mode or by pulsed arc discharge T2 - LIBS 2014 CY - Beijing, China DA - 2014-09-09 PY - 2014 AN - OPUS4-32130 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Promising novel instrumental and theoretical approaches to diagnostics and spectrochemical analysis of laser induced plasma (invited) T2 - SciX 2014 CY - Reno, USA DA - 2014-03-10 PY - 2014 AN - OPUS4-32123 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Theoretical and instrumental tools for study, diagnostics and applications of laser included plasma T2 - LIBS 2014 CY - Beijing, China DA - 2014-09-09 PY - 2014 AN - OPUS4-32126 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Spectrochemical Analysis and Diagnostics via Modeling of Laser Included Plasma T2 - Winter Plasma Conference 2014 CY - Amelia Island, USA DA - 2014-03-01 PY - 2014 AN - OPUS4-32122 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - LIBS as an analytical method-facts, figures and high hopes T2 - Winter Plasma Conference 2014 CY - Amelia Island, USA DA - 2014-03-01 PY - 2014 AN - OPUS4-32125 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Data processing and modeling T2 - LIBS 2014 CY - Beijing, China DA - 2014-09-09 PY - 2014 AN - OPUS4-32128 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Standardless analysis of steel slags via plasma modeling T2 - LIBS 2014 CY - Beijing, China DA - 2014-09-06 PY - 2014 AN - OPUS4-32131 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Porizka, Pavel A1 - Demidov, Alexandr A1 - Kaiser, J. A1 - Keivanian, J. A1 - Gornushkin, Igor B. A1 - Panne, Ulrich A1 - Riedel, Jens T1 - Laser-induced breakdown spectroscopy for in situ qualitative and quantitative analysis of mineral ores N2 - 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. KW - Laser-induced breakdown spectroscopy KW - LIBS KW - Chemometrics KW - Principal component analysis KW - Geochemical analysis PY - 2014 DO - https://doi.org/10.1016/j.sab.2014.08.027 SN - 0584-8547 SN - 0038-6987 VL - 101 SP - 155 EP - 163 PB - Elsevier CY - Amsterdam AN - OPUS4-32588 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Eschlböck-Fuchs, S. A1 - Demidov, Alexander A1 - Gornushkin, Igor B. A1 - Schmid, Thomas A1 - Rössler, R. A1 - Huber, N. A1 - Panne, Ulrich A1 - Pedarnig, J. D. T1 - Tomography of homogenized laser-induced plasma by Radon transform technique N2 - Tomography of a laser-induced plasma in air is performed by inverse Radon transform of angle-resolved plasma images. Plasmas were induced by single laser pulses (SP), double pulses (DP) in collinear geometry, and by a combination of single laser pulses with pulsed arc discharges (SP-AD). Images of plasmas on metallurgical steel slags were taken at delay times suitable for calibration-free laser-induced breakdown spectroscopy (CFLIBS). Delays ranged from few microseconds for SP and DP up to tens of microseconds for SP-AD excitation. The white-light and the spectrally resolved emissivity ε(x,y,z) was reconstructed for the three plasma excitation schemes. The electron number density Ne(x,y,z) and plasma temperature Te(x,y,z) were determined from Mg and Mn emission lines in reconstructed spectra employing the Saha-Boltzmann plot method. The SP plasma revealed strongly inhomogeneous emissivity and plasma temperature. Re-excitation of plasma by a second laser pulse (DP) and by an arc discharge (SP-AD) homogenized the plasma and reduced the spatial variation of ε and Te. The homogenization of a plasma is a promising approach to increase the accuracy of calibration-free LIBS analysis of complex materials. KW - Plasma tomography KW - Laser induced plasma KW - Radon transform technique KW - Laser induced breakdown spectroscopy (LIBS) KW - Steel slag KW - Calibration-free analysis PY - 2016 DO - https://doi.org/10.1016/j.sab.2016.07.007 VL - 123 SP - 59 EP - 67 PB - Elsevier B.V. AN - OPUS4-37452 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Shabanov, Sergej V. A1 - Gornushkin, Igor B. T1 - Absorption tomography of laser induced plasmas N2 - An emission tomography of laser-induced plasmas employed in the laser induced breakdown spectroscopy (LIBS) requires signal integration times in a microsecond range during which the LIBS plasma cannot be considered stationary. Consequently, the use of the data for reconstructing the plasma properties under the assumption that the latter does not change significantly during the integration time leads to inaccurate results. To reduce the integration time, it is proposed to measure a plasma absorption in parallel rays using a scanning rectangular aperture whose dimension Δ along the scanning direction is about a characteristic size of plasma plumes (Δ ~ 1 cm) and the other dimension Δp is of the order of a uniformity length of plasma parameters (Δp ~ 10 µm). The aperture is moved step by step along the scanning direction and the total energy of photons coming through the aperture is measured during time T at each position of the aperture. Owing to the large size of the aperture, the integration time T is reduced by a factor ~ Δp/Δ. A numerical data processing is proposed to restore the spatial resolution of the plasma absorption along the scanning direction. It is determined by the scanning step Δs ≤ Δp. Another advantage of the proposed procedure is that inexpensive linear CCD or non-discrete (PMT, photodiode) detectors can be used instead of costly 2-dimensional detectors. KW - Plasma tomography KW - Laser induced plasma PY - 2012 DO - https://doi.org/10.1016/j.jqsrt.2011.12.016 SN - 0022-4073 VL - 113 IS - 7 SP - 518 EP - 523 PB - Pergamon Press CY - Oxford [u.a.] AN - OPUS4-25823 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xue, Boyang A1 - You, Yi A1 - Gornushkin, Igor B. A1 - Zheng, R. A1 - Riedel, Jens T1 - High-throughput underwater elemental analysis by μJ-laser-induced breakdown spectroscopy at kHz repetition rates: part I, ultrasound-enhanced optical emission spectroscopy towards application perspectives N2 - In recent years, laser-induced breakdown spectroscopy (LIBS) has gained significant attention as a means for simple elemental analyses. The suitability of LIBS for contactless analysis allows it to be a perfect candidate for underwater applications. While the majority of LIBS systems still rely upon sub-kHz pulsed lasers, this contribution introduces 10s-kHz low pulse-energy lasers into underwater LIBS to improve the throughput and statistical validity. Interestingly, the spectral component significantly changed above a critical laser repetition-rate threshold. Spectral lines of atomic hydrogen and oxygen stemming from water become visible beyond a ∼10 kHz repetition rate. This observation suggests a different plasma dynamic compared to low repetition rates. When the pulse-to-pulse interval becomes sufficiently short, a cumulative effect begins to be significant. Apparently, the new phenomena occur on a timescale corresponding to a threshold rate of ∼10 kHz, i.e. ∼100 μs. Analytically, the high repetition rates result in improved statistical validity and throughput. More plasma events per unit time allowed the use of low efficiency Echelle spectrometers without compromising on the analytical performance. Meanwhile, the presence of H I and O I out of the water (as the matrix) also offers internal standardization in underwater elemental analysis. Since the laser fluence was on the lower edge of the plasma threshold, an additional ultrasound source was introduced to induce external perturbation, which significantly improved the plasma formation stability. A huge advantage of LIBS is the possibility of detecting almost all elements within a sample simultaneously. Throughout the periodic table, chlorine is one of the most challenging elements. Consequently, Ca2+ and Na+ were used as samples to demonstrate the capability of this high repetition-rate LIBS platform. As an ambitious benchmark for our system, chlorine detection in water was also discussed. KW - High repetition rate KW - Laser-induced breakdown spectroscopy PY - 2020 DO - https://doi.org/10.1039/D0JA00290A VL - 35 IS - 12 SP - 2901 EP - 2911 PB - The Royal Society of Chemistry AN - OPUS4-51564 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gottlieb, Cassian A1 - Gojani, Ardian A1 - Völker, Tobias A1 - Günther, Tobias A1 - Gornushkin, Igor B. A1 - Wilsch, Gerd A1 - Günster, Jens T1 - Investigation of grain sizes in cement-based materials and their influence on laser-induced plasmas by shadowgraphy and plasma imaging N2 - The effect of particle grain sizes in different cement-based mixtures on the laser-induced plasma evolution is studied using two experimental methods: (i) temporal and spatial evolution of the laser-induced shock wave is investigated using shadowgraphy and two-dimensional plasma imaging, and (ii) temporal and spatial distribution of elements in the plasma is investigated using two-dimensional spectral imaging. This study is motivated by the interest in applying laser-induced breakdown spectroscopy (LIBS) for chemical analysis of concrete, and subsequently obtain information related to damage assessment of structures like bridges and parking decks. The distribution of grain sizes is of major interest in civil engineering as for making concrete different aggregate grain sizes defined by a sieving curve (64mm to 0.125 mm) are needed. Aggregates up to a size of 180 μm can be excluded from the data set, therefore only the amount of small aggregates with a grain size below 180 μm must be considered with LIBS. All components of the concrete with a grain size smaller than 0.125mm are related to the flour grain content. Tested samples consisted of dry and hardened cement paste (water-cement ratio w/z=0.5), which served as a reference. Aggregate mixtures were made by adding flour grains (size 40 μm) and silica fume (size 0.1 μm) in different ratios to cement: 10%, 30%, 50% and 60%, all combined to the remaining percentage of dry or hydrated cement. The visualization results show that a dependance in the evolution of the plasma as a function of sample grain size can be detected only in the initial stages of the plasma formation, that is, at the initial 3 μs of the plasma life. Spectral information reveals the elemental distribution of the silicon and calcium in plasma, in both neutral and ionized form. Here also, a significant effect is observed in the first 1 μs of the plasma lifetime. KW - LIBS KW - Cement-based materials KW - Particle size KW - Shadowgraphy KW - Plasma imaging PY - 2020 DO - https://doi.org/10.1016/j.sab.2020.105772 VL - 165 SP - 105772 PB - Elsevier B.V. AN - OPUS4-50319 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gornushkin, Igor B. A1 - Shabanov, Sergej V. A1 - Sennikov, P. G. T1 - Equilibrium Chemistry in BCl3–H2–Ar Plasma N2 - The approach, which was developed earlier for modeling chemical reactions in laser induced plasmas, is applied to radio-frequency discharge plasmas. The model is based on the assumption that all ionization processes and chemical reactions are at local thermodynamic equilibrium. A chemical composition of an argon-hydrogen plasma with an Addition of boron trichloride is studied as a function of plasma temperature and mole ratio H2∕BCl3. It is established that more than twenty simple and composite molecules and ions can be formed in the course of chemical reactions. The results are compared with those obtained earlier by means of another equilibrium model that uses ab-initio quantum chemical computations of thermochemical and kinetic data and a 0D thermochemical quilibrium solver. KW - Modeling chemical reactions KW - Plasma physics KW - Plasma enhanced chemical vapor deposition PY - 2019 DO - https://doi.org/10.1007/s11090-019-09985-6 VL - 39 IS - 4 SP - 1087 EP - 1102 PB - Springer AN - OPUS4-47817 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Laser induced plasma as a chemical reactor: how feasible? N2 - A goal of this work is to apply 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. Also, chemical reactions in laser induced plasmas (LIPs) created on calcium hydrate and calcium carbonate targets in argon are modeled. The results are compared with those obtained by means of the equilibrium model based on the minimization of Gibbs free energy. T2 - 1st workshop on Tandem LIBS/LA-ICP-MS CY - BAM, Berlin, Adlershof DA - 18.11.2019 KW - LIBS KW - Laser induced plasma KW - Plasma modeling KW - Plasma chemical reactor PY - 2019 AN - OPUS4-49776 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Molecule formation in calcium carbonate and calcium hydroxide libs plasmas: model and experiment N2 - Analysis of calcium hydrate and calcium carbonate samples and their mixtures is important for archeology, anthropology, and geology. Laser-induced plasma spectroscopy (LIBS) is a suitable tool for such the analysis as it allows for in- and on-line real time chemical assays. LIBS is inherently a technique for atomic analysis; however, since recently, it is also used for molecular analysis. The information attained by the latter is mainly related to “secondary” chemistry that deals with re-association of atoms and ions into molecules at long delay times (≥10 μs) after the initial breakdown. Even though the direct information about the initial molecular content in the target may be lost, the molecular analysis by LIBS can still be useful to assess the composition of samples. In this work, chemical reactions in laser induced plasmas (LIPs) created on calcium hydrate and calcium carbonate targets in argon are modeled and compared to experiment. The model is based on the assumption that all ionization processes and chemical reactions are at local thermodynamic equilibrium. A chemical composition of argon-calcium-oxygen and argon-calcium-hydrogen plasmas is studied as a function of plasma temperature and pressure. It is established that more than twenty simple and composite molecules and ions can be formed in the course of chemical reactions. The results are compared with those obtained by means of the equilibrium model based on the minimization of Gibbs free energy. T2 - SciX 2019 CY - Palm Springs, USA DA - 13.10.2019 KW - Plasma diagnostics KW - LIBS KW - Laser induced plasma KW - Plasma modeling PY - 2019 AN - OPUS4-49775 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Modeling equilibrium chemistry in laser induced plasmas and plasma chemical reactors N2 - A goal of this work is to apply 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. Also, chemical reactions in laser induced plasmas (LIPs) created on calcium hydrate and calcium carbonate targets in argon are modeled. The results are compared with those obtained by means of the equilibrium model based on the minimization of Gibbs free energy. T2 - SciX 2019 CY - Palm Springs, USA DA - 13.10.2019 KW - LIBS KW - Laser induced plasma KW - Plasma modeling PY - 2019 AN - OPUS4-49774 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gornushkin, Igor B. A1 - Dell’Aglio, M. A1 - Motto-Ros, V. A1 - Pelascini, F. A1 - De Giacomo, A. T1 - Investigation on the material in the plasma phase by high temporally and spectrally resolved emission imaging during Pulsed Laser Ablation (PLAL) in Liquid for NPs production and consequent considerations on NPs formation N2 - In this paper experimental temperature and density maps of the laser induced plasma in water during Pulsed Laser ablation in Liquid (PLAL) for the production of metallic nanoparticles (NPs) has been determined. A detection system based on the simultaneous acquisition of two emission images at 515 and 410 nm has been constructed and the obtained images have been processed simultaneously by imaging software. The results of the data analysis show a variation of the temperature between 4000 and 7000 K over the plasma volume. Moreover, by the study of the temperature distribution and of the number densities along the plasma expansion axis it is possible to observe the condensation zone of the plasma where NPs can be formed. Finally, the time associated to the electron processes is estimated and the plasma charging effect on NPs is demonstrated. The set of observations retrieved from these experiments suggests the importance of the plasma phase for the growth of NPs and the necessity of considering the spatial distribution of plasma parameters for the understanding of one of the most important issues of the PLAL process, that is the source of solid material in the plasma phase. KW - LIBS KW - Laser induced plasma KW - Plasma modeling KW - Plasma diagnostics KW - Nanoparticle formation PY - 2019 DO - https://doi.org/10.1088/1361-6595/ab369b VL - 28 IS - 8 SP - Article Number: 085017 PB - IOP Publishing AN - OPUS4-48753 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Optimization and detailed spectroscopic characterization of an improved SH-LIBS setup N2 - The spatial heterodyne detection principle has a great potential in spectroscopy. It has an optical setup similar to that of a Michelson interferometer, with the mirrors replaced by diffraction gratings positioned at fixed, equal distances from the beamsplitter and are slightly tilted. The resulting interference pattern is recorded by a digital camera and the spectrum is recovered by using Fourier transformation. Although SHS was initially developed for astronomical and satellite-based atmospheric measurements, but in recent years it has been started to be applied in other branches of spectroscopy too. Recently the area of laser-induced breakdown spectroscopy (LIBS) has also discovered the potential of SHS. The main appeal of SHS detection in LIBS includes the compactness and robustness of the setup (in view of field applications) and the flexibility to optimize the setup for either high sensitivity or for high resolution, which can be benficially exploited in applications like stand-off measurements, quantitative analysis with isotope resolution, etc. In the present work, we have improved and further optimized our initial LIBS-SHS setup described in a previous conference. By using optical simulations, we have modelled the light transmission efficiency, instrumental function and imaging properties of the system. We significantly improved and automated the spectral and image data processing sequence. The optimizations carried out resulted in an improved spectral resolution and repeatability, a lower spectral background and the elimination of the central line artifact originating from the Fourier transformation procedure. A detailed characterization of the LIBS spectroscopy performance (e.g. resolution, spectral coverage, tuning range, linearity, etc.), including a comparison with that of a LIBS setup based on a conventional dispersion CCD spectrometer was also performed. T2 - European Winter Conference on Plasma Spectrochemistry (EWSPS-2019) CY - Pau, France DA - 03.02.2019 KW - SHS KW - Laser induced plasma KW - LIBS KW - Plasma modeling KW - Spatial heterodyne spectrometer PY - 2019 AN - OPUS4-48047 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Laser induced Plasma: Modeling and diagnostics N2 - Laser-induced plasmas are widely used in many areas of science and technology; examples include spectrochemical analysis, thin film deposition, material processing, and even jet propulsion. Several topics will be addressed. First, general phenomenology of laser-induced plasmas will be discussed. Then, a chemical model will be presented based on a coupled solution of Navier-Stokes, state, radiative transfer, material transport, and chemical (Guldberg-Waage) equations. Results of computer simulations for several chemical systems will be shown and compared to experimental observations obtained by optical imaging, spectroscopy, and tomography. The latter diagnostic tools will also be briefly discussed. T2 - Lecture at the Dept of Chemistry of Czeged University (Hungary) on 31.05.2019 CY - Czeged, Hungary DA - 31.05.2019 KW - Plasma KW - LIBS KW - Plasma modeling PY - 2019 AN - OPUS4-48188 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Several approaches to calibration-free LIBS: Advantages and pitfalls N2 - An overview of calibration-free laser induced breakdown spectroscopy (CF LIBS) methods is presented. Advantages and pitfalls of these methods are critically discussed. T2 - Workshop of the Spectrochemical Working Committee (SWC) of the Hungarian Academy of Sciences CY - Budapest, Hungary DA - 05.06.2019 KW - Calibration-free LIBS KW - CF LIBS algorithms PY - 2019 AN - OPUS4-48189 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Equilibrium chemistry of boron halides in plasma chemical reactors N2 - 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. T2 - European Winter Conference on Plasma Spectrochemistry (EWSPS-2019) CY - Pau, France DA - 03.02.2019 KW - Chemical reactors KW - Laser induced plasma KW - LIBS KW - Plasma modeling KW - Plasma diagnostics PY - 2019 AN - OPUS4-47541 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gornushkin, Igor B. T1 - Modeling chemistry in laser-induced and other types of plasmas N2 - 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. T2 - Workshop on Laser and Plasmas Applications CY - Bari, Italy DA - 04.03.2019 KW - Plasma KW - LIBS KW - Plasma modeling PY - 2019 AN - OPUS4-47545 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -