Titan, the largest moon of Saturn, is the only known moon with a fully developed nitrogen-rich atmosphere, its ionosphere is detectable as high as 2200 km above its surface and hosts complex organic chemistry. Titan’s atmosphere and ionosphere has striking similarities to current theories of these regions around Earth 3.5 billion years ago. The Cassini spacecraft has been in orbit around Saturn since 2004 and carries a wide range of instruments for investigating Titan’s ionosphere, among them the Langmuir probe, a “space weather station”, manufactured and operated by the Swedish Institute of Space Physics, Uppsala. This thesis presents studies of positive ions, negative ions and negatively charged dust grains (also called aerosols) in Titan’s ionosphere using the in-situ measurements by the Cassini Langmuir probe, supplemented by the data from particle mass spectrometers. One of the main results is the detection of significant (up to about 4000 cm-3) charge densities of heavy (up to about 13800 amu/charge) negative ions and dust grains in Titan’s ionosphere below 1400 km altitude. The dust is found to be the main negative charge carrier below about 1100 km on the nightside/terminator ionosphere, forming a dusty plasma (also called “ion-ion” plasma). A new analysis method is developed using a combination of simultaneous observations by multiple instruments for a case study of four flybys of Titan’s ionosphere, further constraining the ionospheric plasma charge densities. This allows to predict a dusty plasma in the dayside ionosphere below 900 km altitude (thus declaring it a global phenomenon), as well as to empirically estimate the average charge of the negative ions and dust grains to between -2.5 and -1.5 elementary charges. The complete Cassini dataset spans just above 13 years, allowing to study effects of the solar activity on Titan’s ionosphere. From solar minimum to maximum, the increase in the solar EUV flux increases the densities by a factor of ~2 in the dayside ionosphere and, surprisingly, decreases by a factor of ~3-4 in the nightside ionosphere. The latter is proposed to be an effect of the ionospheric photochemistry modified by higher solar EUV flux. Modelling photoionization also reveals an EUV trend (as well as solar zenith angle and corotational plasma ram dependencies) in the loss rate coefficient.

This thesis was focused on the possibility of secondary utilization of waste material from the wine industry to remove heavy metals from wastewater. In the theoretical part, there were discussed mainly the problems of heavy metals pollution including methods of their removal and ICP-OES detection. Furthermore, the waste material from the wine production and the possibilities of its further processing were discussed there. The primary objective of the experimental part was to characterize the material by IR analysis, optimization of adsorption conditions, isotherms construction and determination of maximum adsorption capacities of white, red and chemically modified marc for Cd, Cr, Cu, Ni and Pb. From the parameters influencing the adsorption efficiency, the adsorbent load was optimized (m/V ratio = 0,02); pH values found were 5 for Cd, Cu, Ni, Pb and 3 for Cr and the contact time to reach the equilibrium was 15 minutes for Cd, Ni, Pb and 30 minutes for Cr and Cu. Maximum adsorption capacity for heavy metals were calculated from adsorption isotherms by applying the Langmuir model and found to be 18,829 7 mg/g for Cd; 10,664 7 mg/g for Ni; 35,602 0 mg/g for Pb (modified marc with 1M NaOH); 4,678 4 mg/g for Cu and 9,629 0 mg/g for Cr. The results of the work confirm the good adsorption potential of heavy metals on marc and the positive effect of chemical modification of natural biosorbents to improve their adsorption capacity.

Sorption of quaternary metal ions (Pb2+, Cu2+, Cd2+ and Zn2+) was carried out on lignite from the South Moravia. Following experiments were tested: kinetic sorption, dependence of sorption on pH, initial concentration, temperature, effect of electrolytes (KNO3 and NaCl) and desorption in deionized water. Sorption studies was carried out in quaternary mixtures and in the case of inicial concentration effect additional in a single-component solution. The batch sorption experiments was used. Sorption time was 24 hour, although concentration of ions was a near equilibrium after two hour. As the optimal pH was determined pH 5. The order of affinity by lignite was obtained Pb >> Cd > Zn > Cu for the sorption of metals in the single-component solution and the order was Pb > Cu > Zn > Cd for the sorption of mixture of metals. The maximum adsorptium capacities from single solutions were for Pb 97,82 mg/g, Cd 60,34 mg/g, Zn 49,88 mg/g and Cu 30,28 mg/g and in the case of ones from mixture solutions were for Pb 39,03 mg/g, Cu 25,94 mg/g, Zn 15,21 mg/g and Cd 5,18 mg/g. Experimental data have been analysed using Langmuir and Freundlich model. Thermodynamic values H°, S° and G° were calculated. Desorption test showed that desorption efficiency is 0–3 %. NaCl had the greatest influence on sorption from electrolytes. On the basis obtained results we can say that metals are binding to lignite in particular due to chemical interactions. Lignite is s suitable as a sorption material for metal ions especially in the field of low concentrations.

Bibliographische Beschreibung und Referat Dani, Ines "ECR-Plasmadiagnostik im System Ar-H2-N2-TMS und Charakterisierung der entstehenden SiCxNy:H-Schichten" Technische Universität Chemnitz, Institut für Physik, Dissertation, 2002 (102 Seiten, 62 Abbildungen, 17 Tabellen, 74 Literaturstellen) In den letzten Jahren wurde im Rahmen der Entwicklung neuartiger Hartstoffschichten verstärkt das System Si-C-N untersucht. Das am häufigsten zur Herstellung genutzte Verfahren ist die chemische Gasphasenabscheidung (CVD). Plasmagestützte CVD-Verfahren bieten die Möglichkeit, auch bei geringen Substrattemperaturen Schichten mit guten mechanischen Eigenschaften herzustellen. Der Abscheideprozess ist jedoch sehr komplex und bis heute nicht vollständig verstanden. Eine Optimierung erfolgt daher meist nach dem trial-and-error-Prinzip, was aber durch die Vielzahl an frei wählbaren Parametern sehr zeitaufwendig ist. Der Zusammenhang zwischen äußeren, regelbaren Parametern und inneren Entladungsparametern ist die Grundlage für ein besseres Verständnis der Plasmachemie und der Schichtwachstumsprozesse in einem molekularem Nichtgleichgewichtsplasma. Da beschichtende Plasmen besonders hohe Anforderungen an die verwendeten Diagnostikverfahren stellen, ist es in den meisten Fällen nicht möglich, die primär für die Schichtbildung interessanten Teilchen zu beobachten. Nur aus der Kombination sich ergänzender Verfahren können elementare Prozesse der Schichtbildung bestimmt werden. Aus ihrer Kenntnis ergibt sich die Möglichkeit einer gezielten Beeinflussung von Schichteigenschaften auf der Basis physikalisch relevanter Größen. In dieser Arbeit wird die Herstellung von amorphen SiCxNy:H-Schichten mit einem ECR-plasmagestützten CVD-Verfahren untersucht. Als Precursor wird dabei Tetramethylsilan (TMS) genutzt. Das vorrangig zur Bestimmung von Teilchenzahldichten eingesetzte Verfahren ist die optische Emissionsspektroskopie. Eine Weiterentwicklung der Aktinometrie ermöglicht die Bestimmung absoluter Teilchenzahldichten unter Beschichtungsbedingungen. Unter Zugrundelegung des Korona-Modells und der Nutzung publizierter Ratenkoeffizienten werden die Grundzustandsdichten von atomarem Wasserstoff, CH und Silicium berechnet. Die Überprüfung der Methode anhand von Argon zeigt eine ausgezeichnete Übereinstimmung zwischen den optisch bestimmten und den gaskinetisch berechneten Teilchenzahldichten. Die Verfälschung der berechneten Teilchenzahldichten durch dissoziative Anregung von H durch H2 ist in einem Plasma mit H2-Zugabe nicht zu vernachlässigen. Dagegen ist der Einfluss dissoziativer Anregung aus TMS auf H, CH und Si sehr gering. Die Teilchenzahldichten von Si und CH sind bei konstantem TMS-Fluss von der Elektronendichte abhängig, bei steigendem TMS-Fluss kommt es in Abhängigkeit von der jeweiligen Elektronendichte zu einer Sättigung. Die Teilchenzahldichte von atomarem Wasserstoff steigt linear mit dem TMS-Fluss. Eine Abscheidung mit hoher Rate ist nur durch Si-haltige Precursorfragmente mit kleinen Massenzahlen möglich. Als Maß für die Entstehung dieser Fragmente können die Teilchenzahldichten von Si bzw. CH genutzt werden.

Die vorliegende Arbeit widmete sich unter grundlagenorientierten und praxisrelevanten Aspekten der Entwicklung maßgeschneiderter, multifunktionalisierter Tenside mit potenziellen Sammler- und Filmbildungseigenschaften im Zusammenhang mit der mineralischen Flotation. Auf der Basis supramolekularer Konstruktionsprinzipien gelang die Synthese dendritisch verzweigter Amphiphile, die relevante Unterschiede in der Hydrophilie-Hydrophobie-Balance aufweisen und in der Flexibilität des Spacersegmentes sowie der peripheren Alkylkettenlänge im hydrophoben Molekülbereich variieren. Im Hinblick auf die Struktur-Wirkungs-Beziehungen der neuartigen Amphiphile fanden Versuche zur Ermittlung der tensidchemischen Parameter sowie Untersuchungen zu ihrem Filmbildungsverhalten statt. Des Weiteren wurden die synthetisierten Tenside im Mikroflotationsversuch auf ihre Eignung als Sammlerkomponenten am Modellmineral Fluorit getestet. Generell führt eine Erweiterung der polaren Haftgruppen zu einer wesentlich besseren Fixierung der amphiphilen Moleküle sowohl an der Phasengrenzfläche Wasser/Luft als auch an der mineralischen Fluoritoberfläche. Darüber hinaus begünstigt eine starre Geometrie die Ausbildung stabilerer monomolekularer Adsorptionsschichten. Im Flotationsprozess bewirken die präorganisierten, dendritisch verzweigten Sammlermoleküle gegenüber konventionellen Reagenzien eine deutliche Effizienzsteigerung.

In the research presented in this licentiate thesis the surface specific technique Vibrational Sum Frequency Spectroscopy, VSFS, combined with the Langmuir trough has been utilized to investigate Langmuir monolayers and Langmuir-Blodgett (LB) deposited mono- and bilayers of phospholipids. Their molecular structure, stability, and hydration were probed to gain additional understanding of important properties aiming at facilitating the use of such layers as model systems for biological membranes. VSFS was applied to in situ studies of the degradation of Langmuir monolayers of 1,2-diacyl-phosphocholines with identical C-18 chains having various degrees of unsaturation. The time-dependent change of the monolayer area at constant surface pressure as well as the sum frequency intensity of the vinyl-CH stretch at the C=C double bonds were measured to monitor the degradation. It was shown that a rapid degradation of the monolayers of unsaturated phospholipids occurred when exposed to the laboratory air compared to the fully saturated lipid, and that the degradation could be inhibited by purging the ambient air with nitrogen. The degradation was attributed to oxidation mediated by reactive species in the air. The molecular structure and order of Langmuir monolayers of 1,2-distearoyl-phosphocholine (18:0 PC) and their hydrating water were investigated at different surface pressures using VSFS. The spectroscopic data indicated a well ordered monolayer at all surface pressures with a more intense signal at higher pressures attributed to the subsequent increase of the number density and more ordered lipid molecules due to the tighter packing. Water molecules hydrating the headgroups or being in contact with the hydrophobic parts were observed and distinguished by their vibrational frequencies, and found to have different average orientations. Additionally, monolayers of 18:0 PC, its fully deuterated analogue, and 1,2-distearoyl-phosphoserine (18:0 PS) were Langmuir-Blodgett (LB) deposited on CaF2 substrates and VSFS was used to investigate the structure and order of the films as well as the hydrating water. The CH-region, water region, and lower wavenumber region containing phosphate, ester, carboxylic acid, and amine signals were probed to obtain a complete picture of the molecule. The data indicates that all deposited monolayers formed a well ordered and stable film and the average orientation of the aliphatic chains was determined using the antisymmetric methyl stretch. / I forskningen som presenteras i denna licentiatavhandling har den ytspecifika vibrationssumfrekvensspektroskopin, VSFS, använts tillsammans med Langmuirtråget för att studera Langmuir-monolager och Langmuir-Blod-gett (LB) deponerade monolager och bilager av fosfolipider. För att utvidga förståelsen av egenskaper som är viktiga för att underlätta användandet av dem som modellsystem för biologiska membran undersöktes såväl deras molekylära struktur som stabilitet och hydratisering. VSFS användes för att genomföra in situ-studier av nedbrytningen av Langmuir-monolager av 1,2-diacyl-fosfokoliner med identiska 18 kolatomer långa sidokedjor med varierande antal omättade kol-kol-bindningar. För att övervaka nedbrytningen mättes såväl den tidsberoende förändringen av monolagernas area vid konstant yttryck som sumfrekevensintensiteten från dubbelbindningarnas CH-vibration. När monolagerna bestående av omättade fosfolipider utsattes för laboratorieluften bröts de ner hastigt jämfört med det helt mättade monolagret. Denna nedbrytning som sannolikt orsakades av reaktiva ämnen i luften kunde inhiberas fullständigt genom att ersätta den omgivande luften med kvävgas. Den molekylära strukturen och ordningen hos Langmuir-monolager av 1,2-distearoyl-fosfokolin (18:0 PC) och deras hydratiseringsvatten undersöktes vid olika yttryck med VSFS. Den spektroskopiska datan visar att monolagerna är välordnade vid alla yttryck samt att sumfrekvenssignalens styrka ökar med ökande yttryck på grund av såväl det större antalet molekyler per ytenhet som den högre ordningen då molekylerna packas tätare. Vattenmolekyler som hydratiserar huvudgrupperna eller är i kontakt med hydrofoba delar och har olika medelorientering observerades och kunde identifieras genom sina vibrationsfrekvenser. Vidare deponerades monolager av 18:0 PC, dess fullt deuterade analog och 1,2-distearoyl-fofsfoserin (18:0 PS) på substrat av CaF2 och VSFS användes för att undersöka filmernas struktur och ordning såväl som hydratiseringsvattnet. CH- och vattenregionerna samt lågvågtalsområdet som innehåller fosfat-, ester-, karboxylsyra- och aminsignaler undersöktes för att få en fullständig bild av den molekylära strukturen. Data visar att alla deponerade monolager bildade en välordnad och stabil film och kolvätekedjornas medelorientering bestämdes med hjälp av signalen från den antisymmetriska metylvibrationen. / QC 20100924

Fluoride, the most abundant form of fluorine, is an ion released into the environment, mainly via anthropogenic sources and erosion of mineral rocks. Although the element is well known for its health benefits on teeth and bones, it can as well be a harmful pollutant. In some areas on earth, the population can not obtain drinking water that is below the guideline limits of fluoride, which is set to 1.5 mg/L by the world health organization (WHO). Therefore there is a relevance to develop methods that can clean the waters from excess fluoride. The potential problems when it comes to finding these types of methods is that they can be expensive. However, materials generated as residues in industrial processes may be low in cost. In this thesis, silicon reduced AOD-slag, a material generated as a by-product from the production of stainless steel, was examined by its fluoride adsorption behavior and adsorption capacity. The concentrations of fluoride were measured with ion chromatography (IC) and the concentration of metals were analyzed with microwave plasma atomic emission spectroscopy (MP-AES). Additionally pH and conductivity were measured. The functionality of the material surface was analyzed with isotherm modeling, where the Sips isotherm model was tested. Moreover, optimization of the slag was performed by heat treating the material, as well as a sorption kinetics test on both optimized and original slags. The results from the analysis indicated that the material corresponds well to the Sips isotherm. Considering this result it is suggested that at low concentrations, the surface can be characterized as heterogeneous, with different binding energies at different available sites. At higher concentrations the Sips-model explains the surface to be saturated when a monolayer of fluoride is formed. Therefore the binding on the slag surface can be described to have an inner-sphere and covalent character. The metal analysis showed that calcium ions are released from the slag when in aqueous solutions. The presence of calcium in the liquid samples are believed to result in formations of solid calcium fluoride (CaF2), precipitated on the slag surface. Lastly, the maximum fluoride removal is believed to differ between different types of AOD-slag, where there as well are possibilities to optimize the material.

The noise in the Langmuir Probe and Plasma Wave Instrument (LP-PWI) on board ESA:s future Jupiter satellite JUICE (Jupiter ICy Moons Explorer) was investigated. Thermal Johnson-Nyquist noise and shot noise, caused by fluctuations in the probe-plasma currents, were combined with the quasi-thermal noise (QTN) due to thermal fluctuations in the electric field in the plasma, using a small signal equivalent circuit model. The contributions and effects of each of the considered noise sources were examined and compared for a number of representative space plasma conditions, including the cold dense plasma of Ganymede's ionosphere and the hot tenuous plasma out in the Jovian magnetosphere. The results showed that in the cold dense plasma of Ganymede's ionosphere, the antenna was long compared to the Debye length and the quasi-thermal noise had a clearly pronounced peak and a steep high-frequency cut-off. For an antenna biased to 1 V with respect to the plasma, the shot noise due to the ambient plasma was the dominant source of noise. For a an antenna at the floating potential the photoelectron shot noise coalesced with the shot and Nyquist noises of the ambient plasma to form almost a single curve. In the hot tenuous plasma out in Jupiter's magnetosphere, the antenna was short compared to the Debye length and the QTN spectrum was much flatter, with little or no peak at the plasma frequency and a very weak high-frequency cut-off. For an antenna biased to 1 V, the shot noise due to photoelectron emission dominated at Callisto's orbital position whereas at Ganymede's and Europa's orbital positions the Nyquist and shot noises of the ambient plasma particles were the dominant noise components. For an antenna at the floating potential, the shot and Nyquist noises of the ambient plasma also dominated the output noise, except at Europa's orbital position, where the quasi-thermal noise was the largest noise component for frequencies at and above the plasma frequency. The numerical calculations were performed using MATLAB. The code was made available in a Git repository at https://github.com/eliasodelstad/irfuproj_JUICE_noise.

The functionalization of surfaces has received attention because the process allows the design and tailoring of substrate surfaces with a new or improved function. "Host-guest" thin film complexes are composed of "host" molecules attached the substrate surface, either through physisorption or covalent bonds, with cavities for the inclusion of desired "guest" molecules for the functionalization of the surface. Two methods for fabricating functional "host-guest" thin films were investigated: Langmuir-Blodgett (LB) deposition and self-assembly monolayer (SAM). Langmuir films were created at the air-water interface using octadecanesulfonic acid (C18S) as the amphiphilic "host" molecules separated by hydrophilic guanidinium (G) spacer molecules, which created a cavity allowing the inclusion of desired "guest" molecules. Surface pressure-area isotherms of the (G)C18S, with and without guests, are characterized by the lift-off molecular areas and are use to determine the proper deposition surface pressure. "Host-guest" Langmuir films are deposited onto silicon substrates using the LB deposition technique. The LB films were then subjected to stability testing using different solvents over increasing periods of time. Grazing-angle incidence X-ray diffraction (GIXD), specular X-ray reflectivity (XRR) and transfer ratio measurements were used to characterize the crystallinity, film thickness, overall film stability and film coverage. The GIXD data revealed that the crystallinity of the deposited film varies with the "guest" molecules and can be disrupted by the functional group on the "guest" molecule through hydrogen bonding. After modeling the XRR data using StochFit, it was discovered that the more polar solvent, tetrahydrofuran (THF), removed the film completely while the nonpolar solvent, hexane, compacted the thin film and increased the electron density. With transfer ratios around 0.95 to 1.05, the deposited films were homogenous. The second method used was self-assembly monolayers, which differs from Langmuir films in that they are created by a spontaneous chemical synthesis from immersing a substrate into a solution containing an active surfactant. Octadecyltrichlorosilane (OTS) was used initially as a molecule to study the self-assembled monolayer procedure. To study a "host-guest" self-assembled monolayer system, a compound is being synthesized from 9-bromoanthracene. This compound would already contain the cavity necessary for the inclusion of "guest" molecules. The solution that contained OTS was composed of a 4:1 mixture of anhydrous octadecane: chloroform. Silicon substrates with a deposited oxide layer were hydroxylated for the surfactant binding chemical reaction to occur. The OTS SAMs were exposed to the same stability tests as the LB films. Surface contact angle measurements were taken of the OTS SAMs before and after the stability tests. The contact angle prior to the stability tests was 110° (±2°). The contact angle after immersion in THF was 101° (±2°) while the contact angle resulting from immersion in hexane was 105° (±2°). From the contact angle measurements, the degradation of the OTS SAMs was less extensive than that of the (G)C18S LB films. / Master of Science

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