Gegenstand der vorliegenden Dissertation ist die Untersuchung von Ca-dotierten PrMnO3 (PCMO) als Katalysator für die (photo)elektrochemische Wasseroxidation. Im Fokus der Untersuchungen stehen die folgenden elementaren Schritte des Gesamtprozesses: i) Die optische Absorption in PCMO wird zunächst als Funktion der Ca-Dotierung und der Temperatur untersucht mit dem Ziel, den Einfluß von Korrelationseffekten auf die optischen Eigenschaften zu verstehen. Die präsentierten Ergebnisse zeigen, dass die Bildung kleiner Polaronen im PCMO als Folge starker Korrelationswechselwirkungen in breites Absorptionsmaximum im Nah-Infrarot bis sichtbarem Energiebereich verursacht, welches im Rahmen eines Photonen-assistierten Polaronenhüpfprozesses und einer Anregung zwischen Jahn-Teller-aufgespaltenen Zuständen diskutiert wird. Weiterhin legt die Dotierungsabhängigkeit der Spektren nahe, dass O 2p und Mn 3d Hybridzustände die Fermienergie-nahe elektronische Struktur bestimmen, wobei der relative Anteil von O 2p mit der Ca-Dotierung variiert. ii) Der aktive Zustand von PCMO in Kontakt mit Wasser bzw. Wasserdampf wird mit Hilfe von Zyklovoltammetrie und in situ ‚environmental‘ Transmissionselektronenmikroskopie (ETEM) für verschiedene Dotierlevels untersucht. Die Ergebnisse beider Methoden ergeben, dass die katalysierte Wasseroxidation gemäß $2\text{H}_2\text{O} \rightarrow \text{O}_2 + 4 \text{H}^+$ mit einem Korrosionsprozess in Form einer Pr/Ca Verarmung und Amorphisierung der PCMO-Elektrode konkurriert. Die höchste katalytische Aktivität sowie Korrosionsstabilität werden im mittleren Dotierungsbereich gefunden. Auf Basis der in situ ETEM Ergebnisse wird außerdem gezeigt, dass durch Zufügen von Monosilan zu Wasserdampf-basierten Elektrolyten im ETEM eine Elektronenstrahl-induzierte Wasseroxidation an aktiven PCMO Oberflächen über die Sekundärreaktion $\text{SiH}_4+2\text{O}_2\rightarrow\text{SiO}_2+2\text{H}_2\text{O}$ nachgewiesen werden kann. Elektronenenergieverlustspektroskopie von PCMO vor und nach der Reaktion in Wasserdampf ergeben, dass der aktive Zustand von PCMO die Bildung und Ausheilung von Sauerstoffleerstellen im Rahmen einer Interkalation des bei der Wasseroxidation freiwerdenden Sauerstoffs beinhaltet. Die Rolle des Elektronenstrahls als Triebkraft für die Wasseroxidation im ETEM wird mithilfe von Elektronenholographie und elektrischen Experimenten sowie theoretischer Modellierung basierend auf Sekundärelektronenemissionen als ein positives Elektronenstrahl-induziertes elektrisches Potential identifiziert.

Thesis describes recent advances in the synthesis of donor-acceptor conjugated copolymers and their efficient doping via molecular p-dopants.

The diploma thesis is focused on issues of measurement and evaluation of hydraulic characteristics of soil. In the literary research, the definitions of hydraulic conductivity and retention curve of soil moisture, their measurements in laboratory and field conditions and the prediction of these characteristics by using of pedotransfer functions. In the practical part of the diploma thesis, an evaluation of the hydraulic conductivity of soil from the experimental areas near the village Bohaté Málkovice. Two-cylindrical and mini-disc infiltration meters were used for field measurements, and a constant-gradient permeameter was used in the laboratory. Physical and empirical equations were used to evaluate the hydraulic conductivity. The results were processed numerically, tabulated and then compared.

This aim of task deals with study of heat dissipation mechanisms and the description of physical phenomena, which is accompanied by non-stationary measurement of thermal characteristics by the method "hot-wire method". In particular, we observe the coefficient of thermal conductivity and its dependence on various variables such as the temperature of the measured sample, its moisture state, the volume of the sample and its porosity. The above mentioned findings are used for the invention of the measuring device of a nonstationary gauge, which is based on regular heating and is dedicated to measuring the thermal conductivity coefficient and the heat capacity by the "hot-wire method" method. In the last part of the thesis is verified functionality of the proposed measuring device, the suitability of the created algorithm for the processing of the measured data and the evaluation of the results was verified. The reproducibility of the measurements was verified and the measured results were compared with the measurement methods, which are commonly used. the influence of humidity on the coefficient of thermal conductivity.

Thesis describes recent advances in the synthesis of donor-acceptor conjugated copolymers and their efficient doping via molecular p-dopants.:Chapter I Preface Motivation and Goals Outline 7 Chapter II 8 State of the Art & Characterization Techniques 8 2.1. General Introduction 8 2.1.1. Concept of Conjugated Polymers 9 2.1.2. Electronic Conduction and Necessity of Doping in Conjugated Polymers 11 2.1.3. Solubility and Processing. 14 2.2. Doping 17 2.2.1. Concept of Doping in Conjugated Polymers 17 2.2.2. Morphological Changes of the Material upon Doping. Conductivity. 20 2.2.3. State-of-the-art p-dopants. 23 2.3. Synthetic Strategies for the Design of (Semi)conducting Polymers 28 2.3.1. A Concise Review: from Polyacetylene till Modern DA Polymers 28 2.3.2. Synthetic Routes to Conjugated Polymers 31 2.3.3. Step-growth vs Chain-growth 34 2.3.4. Benchmark solution-processable Polymers 38 2.4. Characterization techniques 41 2.4.1. Conductivity Measurements 41 2.4.2. Electrochemical Voltammetry 42 2.4.3. Uv-vis-near-infrared 44 2.4.4. Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy. 44 2.4.5. Morphological studies. 45 2.4.6. Electron Spin Resonance Spectroscopy. 46 Chapter III 48 Results & Discussion 48 3.1. Diketopyrrolopyrrole-Based Copolymers 50 3.1.1. Motivation 50 3.1.2. Results and Discussion 51 3.1.4. Summary 89 3.2. Naphthalene Diimide-based Copolymer 90 3.2.1. Motivation 90 3.2.2. Results and Discussion 92 3.2.4. Summary 105 3.3. Isoindigo-Based Copolymers 107 3.3.1. Motivation 107 3.3.2. Results and Discussion 108 3.3.4. Summary 119 Summary & Conclusions 120 Outlook 123 Chapter IV 125 Experimental Part 125 4.1. General Methods and Instrumentation 125 4.2. Synthesis 129 4.2.1. Synthesis of diketopyrrolopyrrole copolymer. 129 4.2.2. Synthesis of electron-conducting polymer (PNDIT2) 132 4.2.3. Synthesis of polyisoIndigo 132 4.2.3. Synthesis of Dopants 135 4.3. Cyclic voltammetry measurements 136 4.4. GIWAX data. 143 4.5. Films preparation 145 References 147 Table of Abbreviations 159 List of Publications 161 Acknowledgements 162 Appendix 163

В данной работе твердофазным методом синтезированы образцы составов Ba3Sc2MO8 (где M=Ti4+, Zr4+). Растворным методом синтезирован оксифторид Ba1.9K0.1In2O4.9F0.1. Проведена рентгенофазовая аттестация образцов. Исследованы электрические свойства образцов методом электрохимического импеданса при варьировании термодинамических параметров внешней среды (Т, рО2, pH2O). Установлено влияние влажности на электропроводность образцов. Проведена дифференциация общей электропроводности на кислородно-ионный, электронный и протонный вклады. Выявлены условия доминирования протонного переноса. / In this work samples Ba3Sc2MO8 (where M=Ti4+, Zr4+) are synthesized by solid state reaction. Oxyfluoride with formula Ba1.9K0.1In2O4.9F0.1 is synthesized by solution method. Phase composition of the samples is certificated by X-ray diffraction. Electric properties of the samples are investigated by electrochemical impedance method at a variation of thermodynamic parameters of environment (T, pO2, pH2O). An influence of humidity on the conductivity of the samples is established. The total conductivity is differentiated on oxygen-ionic, electronic and protonic contributions. Conditions of domination of proton transfer are revealed.

This work is devoted to studying of electric properties, chemical stability and features of disordering in a crystal structure of the phases La28-xW4+xO54+1,5x[VО]2-1,5x (x=0,85; 1,01; 1,17; 1,33) and Pr28-xW4+xO54+1,5x[VО]2-1,5x (x = 0,92; 1,12; 1,33; 1,55) with cubic structure of defective double fluorite with an incomplete oxygen sublattice. Phases are received by solid-state ceramic technology. Using X-ray difractiion method phase composition is established, structural parameters and presumable phase composition taking into account shift of parameters are determined. Measurements of temperature dependence of conductivity are taken by method of impedance spectroscopy at a variation of temperature, partial pressure of oxygen pO2 and water vapors pH2O. Activation energy calculated of mixed hole, oxygen-ion conductivity and proton conductivity is calculated. Dependences of total ionic transport numbers t (ion) on pO2 for La28-хW4+хO54+1,5х[VO]2-1,5х are calculated from experimental isotherms of conductivity. Ion transport number t (ion) for Pr28-xW4+xO54+1,5x[VО]2-1,5x are measured by the EMF method, the type of the dominating charge carriers is defined. Chemical stability of ceramics La28-хW4+хO54+1,5х[VO]2-1,5х to hydrolytic decomposition and its interactions with acid gases were estimated increasing of grain boundary resistance after the cycle "hydration/dehydration", and also by results of X-ray phase analysis, thermogravimetric analysis and research of surfaces of the samples by of the optical and scanning electronic microscopy methods. Water uptake XH2O and extent of filling of structural vacancies of the phases La28-хW4+хO54+1,5х[VO]2-1,5х are defined by the thermogravimetric analysis the 2-1,5kh and, hydration enthalpies ΔНгидр are calculated. An influence of pO2 and pH2O on loss of weight of Pr28-xW4+xO54+1,5x[VО]2-1,5x samples testifies to susceptibility of the phases to oxidation. / Данная работа посвящена изучению электрических свойств, химической устойчивости и особенностей разупорядочения в кристаллической решетке фаз La28-xW4+xO54+1,5x[VО]2-1,5x (х=0,85; 1,01; 1,17; 1,33) и Pr28-xW4+xO54+1,5x[VО]2-1,5x (х = 0,92; 1,12; 1,33; 1,55), обладающих кубической структурой дефектного двойного флюорита с некомплектной кислородной подрешеткой. Фазы получены твердофазным синтезом по керамической технологии, методом РФА установлен фазовый состав, определены параметры кристаллической решетки и предположительный фазовый состав с учетом сдвига параметров. Проведены измерения температурной зависимости проводимости методом импедансной спектроскопии при вариации температуры, парциального давления кислорода Ро2 и паров воды Рн2о. Рассчитаны энергии активации смешанной дырочно-кислородной проводимости и протонной проводимости. Из экспериментальных изотерм проводимости La28-хW4+хO54+1,5х[VO]2-1,5х рассчитаны зависимости суммарных ионных чисел переноса t(ион) от Ро2. Для Pr28-xW4+xO54+1,5x[VО]2-1,5x t(ион) измерены методом ЭДС, определен тип доминирующих переносчиков заряда. Проведена оценка устойчивости керамики La28-хW4+хO54+1,5х[VO]2-1,5х к гидролизному разложению и взаимодействию с кислотными газами по приросту зернограничного сопротивления после цикла «гидратация/дегидратация», а также по результатам рентгенофазового анализа, термогравиметрического анализа и исследованием поверхностей образцов методами оптической и сканирующей электронной микроскопии. С помощью термогравиметрического анализа определена степень гидратации Хн2о фаз La28-хW4+хO54+1,5х[VO]2-1,5х и степень заполнения структурных вакансий, рассчитаны энтальпии гидратации ΔНгидр. Влияние Ро2 и Рн2о на потерю массы образцами Pr28-xW4+xO54+1,5x[VО]2-1,5x свидетельствует о подверженности фаз окислению.

One interesting approach is the development of conductive polymer composite fibers for innovative textile applications such as in sensors, actuators and electrostatic discharge. In this study, conductive polymer composite fibers were prepared using several different blends containing conductive components: a conjugated polymer (polyaniline-complex) and/or carbon nanotubes. Different factors such as processing parameters, the morphology of the initial blends and the final fibers, fiber draw ratio and material selection were studied separately to characterize their effects on the fiber properties. In binary blends of PP/polyaniline-complex, the processing conditions, the matrix viscosity and the fiber draw ratio had substantial effects on the electrical conductivity of the fibers and linearity of resistance-voltage dependence. These factors were associated with each other to create conductive pathways through maintaining an appropriate balance of fibril formation and breakage along the fiber. The blend morphology was defined as the initial size of the dispersed conductive phase (polyaniline-phase), which depended on the melt blending conditions as well as the PP matrix viscosity. Depending on the initial droplet phase size, an optimum draw ratio was necessary to obtain maximum conductivity by promoting fibril formation (sufficient stress) and preventing fibril breakage (no excess stress) to create continuous pathways of conductive phase. Ternary blend fibers of PP/PA6/polyaniline-complex illustrated at least three-phase morphology with matrix/core-shell dispersed phase style. When ternary fibers were compared to binary fibers, the former could combine better mechanical and electrical properties only at a specific draw ratio; this showed that draw ratio was a more determinant factor for the ternary fibers, as both conductivity and tensile strength depended on the formation of fibrils from the core-shell droplets of the PA6/polyaniline-complex through the polypropylene matrix. The achieved maximum conductivity so far was in the range of 10 S/cm to 10 S/cm, which for different samples were observed at different fiber draw ratios depending on the mixing conditions, the matrix viscosity or whether the fiber was a binary or ternary blend. To improve the properties, PP/polyaniline-complex blends were filled with CNTs. The CNTs and the polyaniline-complex both had an increasing effect on the crystallization temperature and the thermal stability of PP. Furthermore, the maximum conductivity was observed in samples containing both CNTs and polyaniline-complex rather than the PP with either one of the fillers. Although increasing the content of CNTs improved the conductivity in PP/CNT fibers, the ease of melt spinning, diameter uniformity and mechanical properties of fibers were adversely affected. Diameter variation of PP/CNT as-spun fibers was shown to be an indication of hidden melt-drawings that had occurred during the fiber extrusion; this could lead to variations in morphology such as increases in the insulating microcracks and the distance between the conductive agglomerates in the drawn parts of the fiber. Variations in morphology result in variations in the electrical conductivity; consequently, the conductivity of such inhomogeneous fiber is no longer its physical property, as this varies with varying size. / Thesis to be defended in public on Friday, May 20, 2011 at 10.00 at KC-salen, Kemigården 4, Göteborg, for the degree of Doctor of Philosophy.

Thesis (MScEng)-- Stellenbosch University, 2013. / ENGLISH ABSTRACT: The coating thermal conductivity, the effective coated-tube thermal conductivity and the coating factor of three artificial protective coatings (APCs) applied to condenser tubes are experimentally evaluated. This testing broadens the limited available knowledge of these coatings, which is necessary for effective condenser refurbishment and operation. The coatings are applied to 25.4 mm brass tubes at thicknesses of 44, 46, 50, and 130 μm. Steady state heat transfer tests are performed on these tubes fitted in a double-pipe counter-flow heat exchanger, with heated water in the annulus and coolingwater inside the tube. The experimentally determined thermal conductivities of the coatings range from 0.5 to 2.3 W/m·K. The effective coated-tube conductivity and the coating factor depend on the tube material and size, as well as the coating thickness. A one-dimensional condenser model is used to parametrically investigate the relative overall effect on condenser performance. From these results, coating guidelines for Admiralty brass tubes are proposed in terms of the minimum and maximum coating conductivity and thickness. The effect of the coating on the thermal performance is equivalent to a Heat Exchange Institute (HEI) cleanliness factor of at least 0.85, when adhering to these guidelines. APCs provide a layer of protection against corrosion, erosion and fouling and can preferentially fill tube-wall pits. They can therefore be used to extend the condenser life-span effectively, but, to ensure minimal impact on the overall condenser performance, the coating thickness and conductivity must be carefully controlled and verified experimentally. / AFRIKAANSE OPSOMMING: Die termiese geleidingsvermoë, die effektiewe termiese geleidingsvermoë van bedekte buise en die bedekkingsfaktor van drie kunsmatige beskermingsbedekkingslae wat op kondensorbuise aangewend word, word eksperimenteel geëvalueer. Hierdie evaluering verbreed die beperkte beskikbare kennis oor sodanige bedekkingslae, wat nodig is vir effektiewe kondensor herinrigting en bedryf. Die lae word teen diktes van 44, 46, 50 en 130 μm in 25.4 mm geelkoperbuise aangewend. Warmteoordragstoetse by gestadigde toestande word gedoen op hierdie buise in ’n dubbelpyp-teenvloeiwarmteoordraer, met verhitte water in die annulus en verkoelingswater binne-in die buis. Die eksperimenteel bepaalde termiese geleidingkoëffisiënte wissel tussen 0.5 tot 2.3 W/m·K. Die effektiewe geleidingsvermoë en bedekkingsfaktor hang af van sowel die buis se materiaal en grootte sowel as die dikte van die bedekkings. ’n Eendimensionele kondensormodel word gebruik om die algehele effek van hierdie beskermingsbedekkingslae op kondensorwerkverrigting parametries te ondersoek. Riglyne ten opsigte van aanwending van beskermingslae vir buise van “Admiralty” geelkoper word verskaf in terme van die minimum en maksimum geleidingsvermoë en dikte van bedekkingslae. Met behulp van hierdie riglyne word ’n “Heat Exchange Institue” (HEI) ekwivalente skoonheidsfaktor van minstens 0.85 op ’n nuwe buis behaal. Hierdie kunsmatige bedekkingslaeslae bied beskerming teen korrosie, erosie en bevuiling en kan klein kuile in die buiswand vul. Hulle kan dus gebruik word om die lewensduur van die kondensator te verleng, maar hul dikte en geleidingsvermoë moet noukeurig beheer word en moet eksperimenteel geverifieer word.

The research presented in this thesis is a collection of many different, yet connected, parts that stemmed from the development of a new alternative material intended to be utilised as anode material in solid oxide fuel cells. The main part is the research conducted in the development and characterisation of the novel A-site deficient La₀.2₂Sr₀.₇₋ₓCaₓTiO₃. Calcium introduction resulted in reducing this perovskite unit cell volume which, at the beginning, enhanced its electrical conductivity in reducing conditions. However, the ideal cubic symmetry coud not be maintained, as in the starting material LA₀.₂Sr₀.₇TiO₃, as a result of the increased A-site ionic radius mismatch and two lower symmetries were observed at room temperature. These were the tetragonal I4/mcm for 0.1 ≤ x ≤ 0.35 and orthorhombic Pbnm for 0.4 ≤ x ≤ 0.7. Higher temperature NPD data showed that the orthorhombic samples transformed into higher symmetries with Pbnm → I4/mcm → Pm3-m phase transitions. Detailed crystallographic analysis is discussed; where the different unit cells showed changes to the tilts of the BO₆ octahedra, along with distortions to these octahedra. DC conductivity measurements showed a high electrical conductivity of 27.5 S/cm for a pre-reduced composition La₀.₂Sr₀.₂₅Ca₀.₄₅TiO₃ at 900°C and pO₂ = 10⁻¹⁹ atm. This material showed very encouraging features; which makes it a very promising anode material for SOFCs. A study was also done which explores the best renewable energy options for the United Arab Emirates given its local climate and other aspects. The reliance on seawater desalination is argued to by unsustainable for different reasons. Thus, water security should be a main element in the planning process for adopting renewable energy technologies. A system that combines different technologies; with a focus on fuel cells technology; is outlined which is thought of to be a very promising basis for a broader system that will secure power and water in a very environment friendly way. Different compositions of the system La₀.₂Sr₀.₇₋ₓCaₓTiO₃ were also studied using AC impedance spectroscopy in order to establish whether or not this system can show a ferroelectric behaviour. Results showed a variation in the dielectric constant of different samples with temperature; however, no Curie point was observed. Nonetheless, the results did show that the different compositions were very homogeneous when fully oxygenated and there were some indications of possible symmetry changes at sub-ambient temperatures. The final part of this thesis outlined the work done towards the development of a new analytical instrument. An existing TGA instrument was altered in order to provide a simultaneous thermogravimetric analysis and DC conductivity measurement for solid solutions at controlled temperature and oxygen partial pressure. Results were obtained for different samples of the system La₀.₂Sr₀.₇₋ₓCaₓTiO₃ which showed a great dependence of the electrical conductivity on the oxygen stoichiometry in these oxides. Also, a direct method is possible with this instrument to estimate the oxygen chemical diffusion coefficient using the electrical conductivity relaxation method. This new setup will be very useful for different electrochemical and thermal studies which can broaden the understanding of the different mechanisms that affect the performance of different solid state materials.