The first part of the master thesis is focused on theoretical analysis of the problems of diagnostics of an electric arc physical properties. In the thesis there is shown identification of spectral lines in experimentally measured electric arc spectra. The thesis deals also with energy balance of the arc. Next part of thesis is aimed to theoretical analysis of effects of electric arc on construction materials of low voltage electric apparatuses. The main part of thesis is devoted to experimental measurement of arc radial temperature changes, measurement of cathode temperature and research of electrical arc effect on selected construction materials of low voltage apparatuses.

The aim of this thesis is diagnose post-discharge nitrogen plasma with optical emission spectroscopy. There is long interest of investigated of nitrogen post-discharge plasma and study how to use it in theory as well as in practice. All results were measured with method of optical emission spectroscopy of post-discharge plasma. Discharge was generated by direct-current voltage generator with flowing regime. In this thesis was used for different series of experiments. First experiment was performed with adding water vapour into argon plasma. Measuring was processed at constant current 140 mA, voltage 1.5 V and pressure 1 000 Pa. It was changed flow rate and for each individual flow rate was measured in range 1–25 cm from end of active discharge. Second experiment was with adding nitrogen into argon plasma. Measuring was processed at constant current 140 mA, voltage 1.5 V and pressure 1 000 Pa. We were changing flow rate of nitrogen (0,2 sccm, 0,4 sccm and 0,8 sccm). For each individual flow rate was same experiment with changing distance from active discharge. Third experiment was about adding mercury vapour into nitrogen post-discharge. Measuring was processed at constant current 120 mA, voltage 3.5 V and pressure 1 000 Pa. Measuring was performed with two configuration: with diaphragm and without it. Last experiment was about adding air into argon plasma. Measuring was processed at constant current 140 mA, voltage 1.0 V and pressure 1 000 Pa. Temperature of outer face of tube was measured by thermocouple and infrared thermometer, was measured for last two experiments (argon – air and nitrogen). During experiments with pure nitrogen was visible phenomenon called pink afterglow which is manifested by noticeable increase pink coloration. Optical emission spectrums post-discharge was take at various range of wavelength. At argon with water vapour was 280–600 nm and at adding nitrogen into argon was at range 320–500 nm. At added mercury vapour into nitrogen was 320–600 nm. For experiment argon – air was wavelength range 320–600 nm. From results of experiments were designed dependencies of calculated intensity from measured spectra on distance from active discharge. Also were constructed dependencies of measured temperature on distance from active discharge.

Abstract In this thesis, different spectroscopic methods are used for studying metals. Electron spectroscopy is applied for the study of binding energy shifts between atomic vapor and solid metals. Photoionization and Auger decay of high temperature aluminum vapors are investigated. Ionization of atomic chromium metal vapor by light absorption is studied with synchrotron radiation and time-of-flight ion mass spectroscopy. Optical spectroscopy is used for studying light emission from electric arc furnace plasma in experimental apparatuses developed during this work. Experimental techniques and sample preparation methods are presented. / Original papers The original publications are not included in the electronic version of the dissertation. Huttula, M., Jänkälä, K., Mäkinen, A., Aksela, H., & Aksela, S. (2008). Core shell electron spectroscopy on high temperature vapors: 2s photoionization and Auger decay of atomic aluminium. New Journal of Physics, 10(1), 13009. https://doi.org/10.1088/1367-2630/10/1/013009 Huttula, M., Partanen, L., Mäkinen, A., Kantia, T., Aksela, H., & Aksela, S. (2009). KLL Auger decay in free aluminum atoms. Physical Review A, 79(2). https://doi.org/10.1103/physreva.79.023412 Aksela, S., Kantia, T., Patanen, M., Mäkinen, A., Urpelainen, S., & Aksela, H. (2012). Accurate free atom–solid binding energy shifts for Au and Ag. Journal of Electron Spectroscopy and Related Phenomena, 185(8–9), 273–277. https://doi.org/10.1016/j.elspec.2012.05.007 Mäkinen, A., Patanen, M., Aksela, S., & Aksela, H. (2012). Atom-solid 3p level binding energy shift of transition metals Cr, Mn, Fe, Co, and Ni. Journal of Electron Spectroscopy and Related Phenomena, 185(12), 573–577. https://doi.org/10.1016/j.elspec.2012.12.006 Mäkinen, A., Niskanen, J., & Aksela, H. (2012). Relative photoionization cross section of Cr atoms in the valence region. Physical Review A, 85(5). https://doi.org/10.1103/physreva.85.053411 Mäkinen, A., Niskanen, J., Tikkala, H., & Aksela, H. (2013). Optical emission from a small scale model electric arc furnace in 250–600 nm region. Review of Scientific Instruments, 84(4), 43111. https://doi.org/10.1063/1.4802833

Interest in rare-earth-doped crystalline materials, e.g., M(RE)F4 (M – alkali metal, RE – rare-earth metal), featuring unique optical properties such as light upconversion and downshifting is experiencing a surge due to the broad spectrum of applications that these photonic systems are facilitating. The development of reliable synthetic methods that grant rapid access to these materials is therefore of great importance. Microwave-assisted synthesis is appealing in this regard, because microwave radiation enables rapid and uniform heating of the reaction mixture and allows for rigid control of the reaction conditions, factors that facilitate the production of high-quality materials within minutes. Surprisingly, the investigation around microwave-assisted synthesis of M(RE)F4 materials featuring upconversion and downshifting luminescence is limited. Methods that have already been developed predominately target Na-based systems, despite the evidence that the Li-based analogues also display excellent optical properties. In fact, only a single microwave-assisted approach toward a nanoscale Li-based system has been reported to date, while to my knowledge, no report of a microwave-assisted synthesis of a microscale Li-based system existed prior to the commencement of the work presented in this thesis. The challenge lies in the fact that access to Li(RE)F4 is not easily achieved through a simple substitution of the alkali metal source in the established protocols that yield Na(RE)F4; rather, a complete re-optimization of the synthesis method is required. This particular challenge was successfully addressed in this work. Presented and discussed in Chapter 3 of this thesis is a rapid microwave-assisted solvothermal synthesis approach toward both upconverting and downshifting LiYF4:RE3+ microparticle systems. More specifically, it is detailed how the rigorous optimization of the reaction temperature/duration profile, initial reaction mixture pH, and ratio of the metal precursors was necessary in gaining control over the crystalline phase, morphology, and size of the microparticles under microwave-induced solvothermal conditions. Importantly, a materials growth mechanism involving the depletion of a Li-free crystal phase, followed by a particle ripening process is also proposed. Moreover, the versatility of the developed method is highlighted by showcasing how it can be extended toward the synthesis of other relevant Li- and Na-based M(RE)F4 nano- and microscale materials (i.e., LiYbF4, NaYF4, and NaGdF4) featuring upconversion luminescence. Lastly, potential challenges associated with microwave-assisted synthesis are discussed, and appropriate solutions are proposed. The upconversion and downshifting luminescence of the M(RE)F4 materials attained via the developed synthesis approach is investigated in Chapter 4. The first part of the chapter provides a general assessment of the characteristic luminescence generated by the M(RE)F4 materials featuring various RE3+ dopant systems. The second part of the chapter is devoted to a much more thorough single-particle investigation of the anisotropic luminescence behaviour exhibited by the LiYF4:RE3+ microparticles via hyperspectral imaging, polarized emission spectroscopy, and optical trapping. It is my hope that you, the reader, will find the work presented in this thesis stimulating from two vantage points – from the development of the most rapid microwave-assisted solvothermal synthesis of upconverting and downshifting M(RE)F4 nano/microscale materials reported to date, as well as from the utilization of specialized luminescence characterization techniques to provide fundamental insight into a seldom-considered luminescence property of crystalline materials such as LiYF4.

Mercury is an environmental contaminant that preferentially accumulates in the kidney. It has been previously shown using proton-induced X-ray emission analysis that mercury (HgCl2) accumulated in precision-cut rabbit renal cortical slices. In this study, the efficacy of seven chelating agents for the removal of Hg from renal dices has been examined. Rabbits were injected with HgCl2 (10 mg/kg) and 3 h later kidneys were sliced, or renal slices were exposed in vitro to a mildly toxic concentration of HgCl2 (5 x 10-5 M, 4 h). The slices were then treated in vitro with 10 mM concentrations of EDTA, lipoic acid (LA), penicillamine (PA), glutathione (GSH), 1,4-dithiothreitol (DTT), DMSA, or DMPS. DMPS proved to be the most effective in mobilizing Hg from in vivo or in vitro HgCl2-exposed renal tissue (>85% of control after 3 h incubation). Relative efficacies for the seven agents were DMPS > DMSA, PA > DTT, GSH > LA, EDTA. The use of renal slices appears to be a useful in vitro tool for assessing the efficacy of chelating agents on mobilizing accumulated Hg from renal tissue.

The aim of this master thesis is to study the influence of metallic atoms on nitrogen post-discharge. Pure nitrogen post-discharge is a subject study of many works dealing with kinetic processes in plasma. Unfortunately, there are only a few published works that present influence of various traces on nitrogen post-discharge kinetics. This master thesis deals with problems of nitrogen post-discharge containing mercury traces. All experimental data were obtained using optical emission spectroscopy of a DC discharge in a flowing mode, which can achieve appropriate temporal resolution in the order of milliseconds. Spectra emitted during the post-discharge were recorded in the range of 320-780 nm and the following molecular spectral systems were identified: • 1. positive system of nitrogen: N2(B) -> N2(A), • 2. positive system of nitrogen: N2(C) -> N2(B), • 1. negative system of nitrogen: N2+(C) -> N2+(X), • NO-beta system: NO(B) -> NO(X). Besides them we were able to record the mercury line at 254 nm, only (in the spectrum of the first as well as in the second order); no other mercury lines were observed. The mercury vapor was introduced into the system at selected post-discharge time. Dependence of selected molecular band head intensities as well as mercury line intensity on experimental conditions (pressure, discharge power, wall temperature, time of mercury vapor introduction) were observed in time evaluation. The data obtained in pure nitrogen were used as a reference. The obtained results showed very high sensitivity of kinetic processes on mercury atoms presence. If mercury was introduced into the post-discharge the mercury line was observable around the site where mercury vapor was introduced into the discharge. The experimental data showed that mercury line intensity was directly proportional to the mercury atoms concentration and saturation effect could be observed. The energy level diagram demonstrates that the observed mercury line can be excited by collisions with nitrogen ground state molecule excited to vibrational level 18. Thus the mercury can be used for the monitoring of population at this vibrational level. Finally we obtained the population profile at this nitrogen metastable level during the post-discharge. The presented work demonstrates possibility of mercury atoms application for the monitoring of one nitrogen metastable state. Unfortunately, the contemporary data are not sufficient for the measurement of metastable absolute concentration. However, complex understanding of nitrogen post-discharge kinetics is still an open problem. Therefore a lot of future work should be done although the presented work brings a good fundament for such research.

Nonthermal plasma-assisted combustion (PAC) has been demonstrated to be a promising potential method to enhance combustion performance and reduce the pollutant emissions. To better understand the mechanism in PAC, we have conducted a series of studies on the combustion enhancement by plasma using a home-developed PAC platform which employs a nonthermal microwave argon plasma and a suit of optical diagnostic tools including optical imaging, optical emission spectroscopy, and cavity ringdown spectroscopy. A new PAC system in which a continuous atmospheric argon microwave plasma jet is employed to enhance combustion of methane/air mixtures was reported. Reactive species in PAC were characterized in a state-resolved manner including the simultaneously measurements of OH(A) and OH(X) radicals in the PAC flames. Roles of the state-resolved OH(A) and OH(X) radicals in microwave PAC of premixed methane/air mixture were explored. It was concluded that if both OH(A) and OH(X) radicals assisted the ignition and flame stabilization processes, then we may hypothesize that the role of OH(A) was more dominant in the ignition enhancement but the role of OH(X) was more dominant in the flame stabilization. The effect of fuel injection configurations was investigated in the comparative study between PAC of the premixed and nonpremixed methane/air mixtures. It was found that emissions from the CH (A-X) and C2 Swan systems only exist in the nonpremixed PAC which suggest that the reaction pathways are different between premixed and nonpremixed PAC. The PAC of premixed methane/oxygen/argon mixtures was investigated. A U-shaped dual-layer curve of fuel ignition/flame stabilization limit showing the effects of the plasma power on the fuel ignition and flame stabilization was observed and reported. A parametric study of the microwave PAC of the premixed ethylene/air mixtures was conducted. Behavior of the OH, CH, and C2 radicals and their dependence on plasma power, argon flow rate, and total ethylene/air mixture flow rate were also studied.

The application of emission spectroscopy to monitor combustion products of solid rocket propellant combustion can potentially yield valuable data about reactions occurring within the volatile environment of a strand burner. This information can be applied in the solid rocket propellant industry. The current study details the implementation of a compact spectrometer and fiber optic cable to investigate the visible emission generated from three variations of solid propellants. The grating was blazed for a wavelength range from 200 to 800 nm, and the spectrometer system provides time resolutions on the order of 1 millisecond. One propellant formula contained a fine aluminum powder, acting as a fuel, mixed with ammonium perchlorate (AP), an oxidizer. The powders were held together with Hydroxyl-Terminated-Polybutadiene (HTPB), a hydrocarbon polymer that is solidified using a curative after all components are homogeneously mixed. The other two propellants did not contain aluminum, but rather relied on the HTPB as a fuel source. The propellants without aluminum differed in that one contained a bimodal mix of AP. Utilizing smaller particle sizes within solid propellants yields greater surface area contact between oxidizer and fuel, which ultimately promotes faster burning. Each propellant was combusted in a controlled, non-reactive environment at a range of pressures between 250 and 2000 psi. The data allow for accurate burning rate calculations as well as an opportunity to analyze the combustion region through the emission spectroscopy diagnostic. It is shown that the new diagnostic identifies the differences between the aluminized and non-aluminized propellants through the appearance of aluminum oxide emission bands. Anomalies during a burn are also verified through the optical emission spectral data collected.

The method of optical emission spectroscopy has been used with Fe-Ni and other complex alloys to investigate in-situ compositional control for additive manufacturing. Although additive manufacturing of metallic alloys is an emerging technology, compositional control will be a challenge that needs to be addressed for a multitude of industries going forward for next-gen applications. This current scope of work includes analysis of ionized species generated from laser and metal powder interaction that is inherent to the laser engineered net shaping (LENS) process of additive manufacturing. By quantifying the amount of a given element's presence in the electromagnetic (EM) spectrum, this amount can be compared to the actual amount present in the sample via post-processing and elemental dispersive x-ray (EDX) data analysis. For this work a commercially available linear silicon CCD camera captured metallic ion peaks found within the ultraviolet (UV) region to avoid background contamination from blackbody radiation. Although the additive manufacturing environment can prove difficult to measure in-situ due to time dependent phenomena, extreme temperatures, and defect generation, OEM was able to capture multiple data points over a time series that showed a positive correlation between an element's peak intensity and the amount of that element found in the final deposit.

<p>In this work a flow stabilized corona torch plasma was used for periodic domain inversion of MgO-doped lithium niobate with 19 .1 μm periodic gratings. The effective non-linear coefficient (derr) achieved through corona discharge poling was 17.5 pm/V, which agrees well with theoretical value of 16~19 pm/V. By analysing the second harmonic generation (SHG) tuning curves, the grating uniformity over the 10 mm grating was investigated. The 0.6 run bandwidth of the SHG tuning at full width half maximum (FWHM) corresponded exactly to the theoretical value. The agreement between experimental data and theoretical results imply that the obtained periodically poled lithium niobate (PPLN) has high quality. By controlling temperature in the range of 20 °C to 120 °C tunability of SHG wavelength was demonstrated between 782 run and 788 run.</p> <p>Discharge characteristics of the corona were studied using a floating potential double probe and optical emission spectroscopy. Using the double probe the distribution of ion density downstream of the corona torch was observed. The maximum ion density of 2 x 1018 (ions/cm3) was achieved 2 mm below the discharge electrode. Measurement of the optical emission spectrum was used to determine the vibrational ion temperature to be 3953 K. The observed spectrum consisted entirely of the second positive band of nitrogen.</p> <p>The applied voltage range of 9 kV to 10 kV was observed to be optimum for domain growth in periodic poling. Poling uniformity of the 12 mm grating was optimized for an electrode to crystal spacing of 13 mm. Increasing the crystal temperature during poling reduces the required coercive field for domain inversion. This reduces the required applied voltage and also reduces the required poling time by increasing the domain-switching rate. Proton exchange pretreatment of the (+z) crystal surface prior to poling has been demonstrated to control domain spreading, however future efforts are required to ensure a more reliable nucleation condition. Both high vacuum and spin coated photoresist function to increase electrical discrimination of anode grating and provide an improved nucleation condition for periodic poling of MgO-doped lithium niobate. Poling uniformity of the 12 mm grating was optimised for an electrode to crystal spacing of 13mm.</p> / Thesis / Master of Applied Science (MASc)