This master’s thesis deals with the measurement of the electrical soil resistivity. In the theoretical part there are described the methods by which the soil resistivity is measured – especially the Wenner’s method, which was used for the practical measurements. Then there is also described the one-layered and the two-layered model of this method. Furthermore, there is described the procedure for the measurement of soil resistivity using the OMICRON CPC 100 and PU 193 instruments used in the measurement. To verify the modeling of a two-layered soil model, the theoretical part of the thesis describes the soil modeling process using the program Ansys. As for the practical part of the thesis, the measurements were carried out in three localities: Brno – Královo Pole; Hrušovany nad Jevišovkou – Pravice; Hustopeče nad Bečvou – Vysoká. The measured values were processed using the Matlab’s graphical user interface (GUI) that was developed within this thesis. From these values, at least one two-layered soil model was created for each location and both meters – a total of 12 models were created. For these models, measurements were simulated in Ansys. The results of the simulations were then compared with the measured values. The aim of this thesis is to compare the measured data with the data obtained by the simulations and subsequently to describe the suitability / unsuitability of the substitution of the one-layered soil model for the two-layered one for given measurements.

Layered double hydroxides (LDHs) are clay-like minerals commonly referred to as anionic clays" with a wide range of physical and chemical properties. LDHs often find application in pharmaceuticals, as polymer additives, as additives in cosmetics, as nanomaterial's and in catalysis. This is due to having variable layer charge density, reactive interlayer space, ion exchange capabilities, a wide range of chemical compositions and rheological properties (Forano et al., 2006). Various techniques exist for the synthesis of layered double hydroxides. These include co-precipitation, the urea method, induced hydrolysis, sol-gel and hydrothermal methods. Many of these produce environmentally unfriendly effluents or by-products, are energy intensive, make use of metallic salts or require inert synthesis environments (Rives, 2001). Limitations associated with these existing processes make LDH synthesis at an industrial level expensive or difficult to achieve. The need for 'green', affordable and repeatable synthesis methods are therefore often sought after. Recently the use of mechanochemistry as an alternative synthesis technique has gained wide-spread attention. Mechanochemistry involves the breaking and forming of chemical bonds due to an induced mechanical force. Various mechanochemical techniques for the synthesis of LDH materials exist or have been explored. These include methods such as single-step, two-step and mechano-hydrothermal grinding techniques. Grinding methods can be conducted dry, wet or collectively (Qu, Zhang, et al., 2015a). Mechanochemistry has further been used in conjunction with micro-wave energy and ultrasonic irradiation. The use of mechanochemistry as a synthesis method has proven to be promising with successful and unique LDHs produced. Intercalation of unique or complex anions within the interlayer has further been proven possible. The versatility and robust nature of this synthesis method makes it ideal for industrial application. Although many studies exist it was noted that limited research has been conducted on single-step wet grinding for LDH synthesis and warrants further investigation (Qu, Zhang, et al., 2015a) (Iwasaki,Yoshii, et al., 2012). This was due to factors such as incomplete conversion, difficulties associated with grinding and morphological imperfections. Single step wet milling could be benifi cial as a synthesis procedure as it eliminates hazards associated with dry powder, contains less process steps and is therefore possibly more cost effective and can be conducted batch, semi-batch or continuously due to fluid flow. Throughout the literature research conducted it was further noted that not many different milling devices have been explored. Ball mills, mixer mills and manual grinding were the most common methods used to supply mechanical energy to a system. The study therefore aims to expand on single-step wet synthesis of LDH materials by making use of a different milling device, namely a Netzsch LME 1 horizontal bead mill. The selected mill is designed for wet grinding application and can easily be up-scaled to a commercial batch, semi-batch or continuous process. Raw materials selected were a combination of oxides, hydroxides and basic carbonates. This would eliminate hazardous salt by-products and effluent, promoting 'green' synthesis of LDH materials. It was noted that the synthesis of LDH with the use of these materials have previously proven to be challenging (Qu, Zhang, et al., 2015a). The study was divided up into two sections namely a 'parameter study' and a 'versatility study'. The 'parameter study' involved exploring the in influence of milling and experimental parameters, such as rotational speed, retention time, solids loading, bead size and jacket water temperature, on the synthesis of Mg-Al LDH. The raw materials selected were MgO and Al(OH)3 combined at a divalent to trivalent cationic ratio of 2:1. The parameters were individually investigated, with the exception of jacket water temperature as it was varied with a change in retention time and a change in rotational speed. Unless stated otherwise or under investigation, parameters were investigated at a set speed of 2000 rpm, jacket water temperature of 30 °C, solids loading of 10 %, retention time of 1 h and with 2 mm yttrium stabilised zirconia beads. Therefore when investigating a specific c parameter, the others remained as stated above. Comparatively the 'versatility' study further explores the synthesis of Mg-Al, Ca-Al, Cu-Al and Zn-Al LDH by adapting optimal synthesis conditions, derived from existing mechanochemical techniques and methods, to the selected process. These were related to the divalent to trivalent cationic ratio and selected starting materials. Ageing of the samples obtained through the 'versatility study' were further explored to determine if the potential for a two-step commercial process exists. The study was investigated at a set speed of 2000 rpm, jacket water temperature of 30 °C, solids loading of 10 %, retention time of 1 h and with 2 mm yttrium stabilised zirconia beads. Half of the sample collected was subjected to ageing at 80 °C for 24 h under atmospheric conditions. / Dissertation (MEng (Chemical Engineering))--University of Pretoria, 2020. / This research was funded by Techsparks (Pty) Ltd and the Technology and Human Resources for Industry Programme (THRIP) administered by the Department of Trade and Industry, South Africa, (grant number THRIP/133/31/03/2016) / Chemical Engineering / MEng (Chemical Engineering) / Unrestricted

The work was focused on the preparation of layered ceramic materials and their characterizations. The direct measurment of weight deposite for enhanced description of one component system was studied within this work. The kinetics of electrophoretic deposition obtained from theoretical calculation and from experimental values were confronted. It was prepared a lot of depositions for described kinetic of electrophoretic deposition with applied constant currents. The relative density and porosity were determined on the annealled and sintered bodies. The hardness measurments were performed on sintered bodies and then resulted values were confronted with the used currents. A ceramic composite based on Al2O3 and ZrO2 was prepared by using of precision describtion of electrophoretic deposition kinetic.

Thermoelectric materials can convert waste heat into electric power and thus provide a way to reduce the dependence on fossil fuels. Our aim is to model the underlying materials properties and, in particular, the transport as controlled by electrons and lattice vibrations. The goal is to develop an understanding of the thermoelectric properties of selected materials at a fundamental level. The structural, electronic, optical, and phononic properties are studied in order to tune the transport, focusing on KxRhO2, NaxRhO2, PtSb2 and Bi2Se3. The investigations are based on density functional theory as implemented in the all electron linearized augmented plane wave plus local orbitals WIEN2k and pseudo potential Quantum-ESPRESSO codes. The thermoelectric properties are derived from Boltzmann transport theory under the constant relaxation time approximation, using the BoltzTraP code. We will discuss first the changes in the electronic band structure under variation of the cation concentration in layered KxRhO2 in the 2H phase and NaxRhO2 in the 3R phase. We will also study the hydrated phase. The deformations of the RhO6 octahedra turn out to govern the thermoelectric properties, where the high Seebeck coefficient results from ”pudding mold" bands. We investigate the thermoelectric properties of electron and hole doped PtSb2, which is not a layered material but shares “pudding mold" bands. PtSb2 has a high Seebeck coefficient at room temperature, which increases significantly under As alloying by bandgap opening and reduction of the lattice thermal conductivity. Bi2Se3 (bulk and thin film) has a larger bandgap then the well-known thermoelectric material Bi2Te3, which is important at high temperature. The structural stability, electronic structure, and transport properties of one to six quintuple layers of Bi2Se3 will be discussed. We also address the effect of strain on a single quintuple layer by phonon band structures. We will analyze the electronic and transport properties of Tl-doped Bi2Se3 under strain, focusing on the giant Rashba spin splitting (Tl doping breaks the inversion symmetry in Bi2Se3) and its dependence on biaxial tensile and compressive strain.

1 Abstract The structure of layered zinc hydroxide intercalated with dodecyl sulfate (LZH-DS) anions was studied in detail. LZH-DS was prepared by direct precipitation in water and formed different phases. The following phases of LZH-DS were prepared - "extended" phase (ex) by direct precipitation in water, "shrunk" (s) and "super-shrunk" (ss) phases via treatment of LZH-DS(ex) phase in methanol. The studies of the thermal behavior of LZH-DS(ex) revealed interstratification of intercalated DS anions. It is the first example of interstratification in layered hydroxides that are intercalated with long aliphatic alkyl chain anions. The experimental results were used for molecular dynamic modelling of the structures. Nanometric thin films were prepared by dip-coating and inkjet printing of ZnO nanosheets on glass plates. The side-by-side alignment of the ZnO nanosheets on the substrate resulted in thin, transparent, oriented ZnO surfaces with the high-energy {001} facets exposed. The method of nanosheet deposition affected the film morphology; the dip-coated films were smooth and nonporous, while the inkjet-printed films were rough and had a surface area in the range of approximately 100-160 m2 g-1 . The first-order rate constants for the photocatalytic degradation of 4-chlorophenol on the nanosheet-based films...

Charles University Faculty of Science Study programme: Inorganic Chemistry Mgr. Barbora Hyklová Layered Transition Metal Hydroxides: Delamination and Properties Extended abstract Supervisor: Ing. Kamil Lang CSc., DSc. Supervisor-Consultant: RNDr. Jan Demel PhD. Prague, 2017 Layered transition-metal hydroxides have attracted increasing attention as promising active electrode materials for electrochemical energy storage and conversion device due to facile preparation and modification, good tunability, high capacitance capability, fast reversible redox reactions, and cost effectiveness. Many reported hierarchical architectures based on nickel and cobalt hydroxides are composed of bulky nanoplatelet-like aggregates; however, the nanomorphology and behavior of the separated hydroxide nanosheets is much less known. Figure 1. Scheme of layered nickel or cobalt hydroxide delamination and subsequent restacking on conductive HOPG support. In this respect, the dissertation thesis reports characterization and electrochemical performance of nickel, nickel-cobalt, and cobalt hydroxide nanosheets, synthesized by an economical and environmentally friendly method based on delamination of corresponding layered hydroxides in water (Figure 1). For this purpose, lactate and nitrate layered hydroxides were prepared by two...

Ein fundiertes Verständnis der Mechanismen der Gummi-Vulkanisation von Dien-Kautschuken ist noch immer eine der größten Herausforderungen in der Chemie und Technologie der Elastomere. Die Schwefelvulkanisation von Elastomerwerkstoffen ist ein seit langem verwendeter, aber dennoch sehr anspruchsvoller Prozess, mit dessen Hilfe moderne Reifen hergestellt werden. Bei dieser chemischen Reaktion spielt Zinkoxid, zusammen mit den anderen Hilfsstoffen der Schwefelvulkanisation eine entscheidende Rolle. Um die Produkteigenschaften von mit Schwefel vulkanisierten Elastomermaterialien zu verbessern, sollten die Mechanismen der chemischen Vernetzung - und insbesondere auch die Rolle von Zink enthaltenden Verbindungen bei der Vulkanisationsreaktion besser verstanden werden. Zum Beispiel könnte das Eigenschaftsprofil von Reifen durch die Ausbildung von geeigneten Netzwerken aus Schwefel oder anderen Netzknoten optimiert werden. Nitrilkautschke aus der Klasse der Spezialelastomere und die meisten nicht-Tire- Kautschuk in der ganzen Welt eingesetzt, wecken ein großes Interesse der Forschung wegen ihrer einzigartigen Vulkanisationschemie bei der Vernetzung mittels Zinkverbindungen und wegen der besonderen Eigenschaften der dadurch erzeugten Elastomerwerkstoffe. In dieser Arbeit wurde besonderes Augenmerk darauf gelegt, die Rolle von verschiedenen Zinkverbindungen in der Schwefelvulkanisation von carboxylierten Nitrilkautschuken zu verstehen. In der vorliegenden umfangreichen und eingehenden Untersuchung konnte die Ausbildung einer weiteren Polymerphase im Elastomer nachgewiesen werden. Durch dieses Ergebnis kann nun das dynamische mechanische Verhalten von solchen Polymerwerkstoffen besser verstanden werden. Teile dieser Arbeit beschäftigen sich mit der Erforschung der Rolle von Zinkchlorid bei der Vernetzung von Nitrilkautschuken. Hierzu wurde festgestellt, dass Zinkchlorid einen besonderen Einfluss auf die chemische Vernetzung des NBR aufweist, auch in Abwesenheit anderer Vernetzungs- oder Vulkanisationsadditive. Die so vernetzten Elastomere weisen ein stark hydrophiles Verhalten auf, im Gegensatz zu den allgemeinen Eigenschaften solcher Elastomerwerkstoffe. Eine detaillierte Analyse dieser neuartigen Netzwerkstruktur, gebildet durch eine Koordinationsbindung zwischen dem Zinkatom des Zinkchlorids und dem Nitrilkautschuk, wurde durchgeführt. Carboxylierter Nitrilkautschuk (XNBR) wurde ebenfalls eingesetzt, um funktionale Kautschukmischungen mit neuartigen flammhemmenden Eigenschaften zu entwickeln. Zu dieser Thematik wurden Zink enthaltende Doppelhydroxide (Layered Doube Hydroxides, LDH) als multifunktionale Füllstoffe in XNBR-Kautschuk eingesetzt. Neben dem Flammschutzverhalten zeigt LDH einzigartige Eigenschaften als verstärkenden Füllstoff und gleichzeitig als aktivierendes Additiv für die Schwefelvulkanisation. Eine weitere Zink enthaltenden Verbindung, Zinkstearat, wurde eingesetzt um mechanoadaptive elastomere Materialien durch gezieltes Einstellen des kristallinen bzw. amorphen Charakters dieser Verbindung zu entwickeln. Dies könnte einen wichtigen Beitrag zur Entwicklung zukünftiger Reifenmaterialien mit intrinsisch adaptiven Eigenschaften liefern.

Masters of Science / The redistribution patterns of trace elements related to ore mineralisation in the secondary environment are the foundation of regolith exploration geochemistry. Understanding the controls of these element patterns is important for the detection of underlying ore deposits, especially in areas where bedrock is concealed by extensive regolith. The study area, which hosts PGE and gold deposits within the Stella Layered Intrusion is one such area. A major aim of this study was to use major element data to characterise the regolith materials enclosing the PGE mineralisation in the Stella Layered Intrusion to ascertain the degree of weathering that has occurred. Furthermore, the study aimed to relate the weathering patterns in regolith to the distribution of pathfinder elements of PGEs and gold in areas proximal and distal to the mineralised zones. The study was conducted using XRF data, which included major oxide and trace element data. These data were used to characterise regolith materials (scatter plots, K/Al versus Mg/Al plots) and calculating indices that determine the degree of weathering such as CIA and ICV indices as well as A-CN-K and A-CN-FM diagrams. Signatures of pathfinder/ trace elements were enhanced by hydroxylamine hydrochloride partial selective leach technique. The distribution patterns of the partial leach data were compared to the intensity of weathering and weathering products, e.g. manganese oxides, carbonates in areas proximal and distal to the ore zone. In the Serpens North Prospect, the major horizons that were identified include saprolith, stone line and aeolian sands. Incipient calcrete formation occurs in some parts of the Sirius Prospect, while in some parts, well developed, thick calcrete layers are found interlayered with the saprolith and aeolian sand.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23216号 / 工博第4860号 / 新制||工||1759(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 阿部 竜, 教授 陰山 洋, 教授 藤田 晃司 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Le développement de céramiques légères à hautes performances mécaniques et à bas coût à base de silico-alumineux, suscite un intérêt grandissant dans divers domaines d’application tels que la protection balistique. Dans ce contexte, l’objectif de ce travail a été de développer un matériau innovant susceptible de rivaliser avec les protections balistiques en alumine ou en carbure. Plusieurs voies ont été explorées. Une étude approfondie des compositions de silico-alumineux a permis d’obtenir des matériaux présentant un meilleur compromis masse volumique / module d’Young, et dont le principal avantage est d’utiliser des procédés d’élaboration conventionnels (pressage, coulage sous pression) ainsi que les fours dédiés à la cuisson de la porcelaine par frittage naturel. Afin de renforcer la dureté de surface, des dépôts de carbures ont été réalisés à l’aide d’un protocole qui a permis une bonne accroche du carbure sur le substrat tout en conservant un traitement thermique conventionnel de consolidation. Enfin, des architectures lamellaires ont également été élaborées afin de maximiser les phénomènes de dissipation d’énergie. En bénéficiant d’un différentiel d’expansion thermique entre deux compositions de silico-alumineux, l’apparition de contraintes thermiques résiduelles au refroidissement de l’étape de frittage a permis d’augmenter la valeur de contrainte à la rupture des matériaux à architectures lamellaires de plus de 60%. / The development of lightweight alumino-silicate based ceramics exhibiting high mechanical performances and low cost, shows a growing interest in various application areas such as ballistic protection. In this context, the aims of this study is the development of innovative materials corresponding to competitive ballistic protection comparing to carbide or alumina materials. Several ways were explored. A thorough study of alumino-silicate compositions has allowed to obtain materials with a best compromise density / Young's modulus, the main advantage is the ability to use conventional methods of preparation (pressing, die-casting) and conventional kilns used for the firing of porcelain. To improve the surface hardness, carbide coatings were performed. The original protocol developed leads to carbide coating with good adhesion on the substrate using a traditional thermal treatment method. Finally, lamellar architectures of materials were developed to increase the energy dissipation of failure. Thanks to a differential thermal expansion between the two compositions of alumino-silicates, the occurrence of residual thermal stresses in lamellar materials has increased the average stress of failure values of more than 60%.