Clay shales are currently being assessed as possible host rock formations for the deep geological disposal of radioactive waste. However, one main concern is that the favourable long-term isolation properties of the intact rock mass could be negatively affected by the formation of an excavation damaged zone (EDZ) around the underground openings. This thesis investigated the deformation and failure process of a clay shale, namely Opalinus Clay, with particular focus on the influence of anisotropy on the short-term response of circular tunnels. To achieve this goal, a hybrid continuum-discontinuum numerical approach was used in combination with new field measurements from the Mont Terri underground research laboratory. The response of Opalinus Clay during the excavation of a full-scale emplacement (FE) test tunnel was characterized by geodetic monitoring of wall displacements, radial extensometers and longitudinal inclinometers. The deformation measurements indicated strong directionality induced by the combined effect of in situ stress field and presence of bedding planes striking parallel to the tunnel axis, with the most severe deformation occurring in the direction approximately perpendicular to the material layering. Computer simulations were conducted using a newly-extended combined finite-discrete element method (FEM/DEM), a numerical technique which allows the explicit simulation of brittle fracturing and associated seismicity. The numerical experimentation firstly focused on the laboratory-scale analysis of failure processes (e.g., acoustic activity) in brittle rocks, and on the role of strength and modulus anisotropy in the failure behaviour of Opalinus Clay in tension and compression. The fracturing behaviour of unsupported circular excavations in laminated rock masses was then analyzed under different in situ stress conditions. Lastly, the modelling methodology was applied to the aforementioned FE tunnel to obtain original insights into the possible EDZ formation process around emplacement tunnels for nuclear waste. The calibrated numerical model suggested delamination along bedding planes and subsequent extensional fracturing as key mechanisms of the damage process potentially leading to buckling and spalling phenomena. Overall, the research findings may have a potential impact on the constructability and support design of an underground repository as well as implications for its long-term safety assessment procedure.

Clay shales are currently being assessed as possible host rock formations for the deep geological disposal of radioactive waste. However, one main concern is that the favourable long-term isolation properties of the intact rock mass could be negatively affected by the formation of an excavation damaged zone (EDZ) around the underground openings. This thesis investigated the deformation and failure process of a clay shale, namely Opalinus Clay, with particular focus on the influence of anisotropy on the short-term response of circular tunnels. To achieve this goal, a hybrid continuum-discontinuum numerical approach was used in combination with new field measurements from the Mont Terri underground research laboratory. The response of Opalinus Clay during the excavation of a full-scale emplacement (FE) test tunnel was characterized by geodetic monitoring of wall displacements, radial extensometers and longitudinal inclinometers. The deformation measurements indicated strong directionality induced by the combined effect of in situ stress field and presence of bedding planes striking parallel to the tunnel axis, with the most severe deformation occurring in the direction approximately perpendicular to the material layering. Computer simulations were conducted using a newly-extended combined finite-discrete element method (FEM/DEM), a numerical technique which allows the explicit simulation of brittle fracturing and associated seismicity. The numerical experimentation firstly focused on the laboratory-scale analysis of failure processes (e.g., acoustic activity) in brittle rocks, and on the role of strength and modulus anisotropy in the failure behaviour of Opalinus Clay in tension and compression. The fracturing behaviour of unsupported circular excavations in laminated rock masses was then analyzed under different in situ stress conditions. Lastly, the modelling methodology was applied to the aforementioned FE tunnel to obtain original insights into the possible EDZ formation process around emplacement tunnels for nuclear waste. The calibrated numerical model suggested delamination along bedding planes and subsequent extensional fracturing as key mechanisms of the damage process potentially leading to buckling and spalling phenomena. Overall, the research findings may have a potential impact on the constructability and support design of an underground repository as well as implications for its long-term safety assessment procedure.

In this thesis different mechanical properties for shotcrete (sprayed concrete) such as compression strength, bond strength, bending tensile strength, elastic modulus, free and restrained shrinkage as a function of its age was investigated. One of the main issues was to investigate the difference between ordinary cast concrete and shotcrete. Reliable material data for young and hardening shotcrete is scarce which in the past have made such comparisons difficult. Also, less accurate data representative for cast concrete has often been used in numerical modelling and design analyses. The focus of the project has particularly been on the properties bond strength and restrained shrinkage for which two new testing methods has been developed and evaluated. Microstructural studies have also been performed as a complement to the bond strength testing. The bond to rock is one of the most important properties for shotcrete used as rock reinforcement. During the very first time after spraying the physical properties and the bond to the rock depend on the set accelerator and the micro structure that is formed. The investigation of early age bond strength of shotcrete is of great importance both from a production perspective and a safety perspective. The newly developed method was tested and evaluated and proved that it can be used for bond strength testing already from a couple of hours after shotcreting. The bond, or adhesion, depends on several factors such as texture of the rock, the type of accelerator, application technique, etc. In this work the development of the microstructure in the interfacial transition zone (ITZ) and strength of the bond was investigated. The results show that the bond strength is related to the hydration process, i.e. the strength gain of the shotcrete. The early development of the ITZ was here studied using a scanning electron microscope (SEM) making it possible to observe changes over time, before and after proper cement hydration. Restrained shrinkage cracking of shotcrete, especially in the case of shotcrete sprayed on soft drains that are parts of a tunnel lining not continuously bonded to the rock, can be detrimental for the sustainability of an infrastructure tunnel system. Maintenance and repair costs can be high over time. It is shown that the developed test method realistically captures the behaviour of shotcrete drains on hard rock in situ. The method can be used in the evaluation of different technical solutions for avoiding or minimizing shrinkage cracks in shotcreted soft drains. It can also be used to assess the performance of shotcrete fully bonded to a rock surface, with respect to the ability to prevent cracking or to distribute possible shrinkage damage into several fine cracks instead of one wide. / <p>QC 20140526</p>

Oxide ultra-thin film surfaces have properties and structures that are significantly different from the terminations of the corresponding bulk crystals. For example, surface structures of epitaxial ultra-thin oxide films are highly influenced by the crystallinity and electronegativity of the metal substrates they grown on. Some enhanced properties of the novel reconstructions are related to catalysis, sensing and microelectronics, which has resulted in an increasing interest in this field. Ultra-thin TiO_x films were grown on Au(111) substrates in this work. Two well-ordered structures within monolayer coverage - honeycomb (HC) and pinwheel - were generated and investigated. Special attention has been paid to the uniform (2 x 2) Ti₂O₃ HC phase including its regular structure and imperfections such as domain boundaries (DBs) and point defects. Linear DBs with long-range repeating units have been observed; density functional theory (DFT) modelling has been used to simulate their atomic structures and calculate their formation energies. Rotational DBs/defects show up less frequently, however a six-fold symmetrical 'snowflake' DB loop stands out. Two types of point defects have been discovered and assigned to Ti vacancies and oxygen vacancies/hydroxyl groups. Their diffusion manners and pairing habits have been discussed within an experimental context. The results of growing NbO_x ultra-thin films on Au(111) are also presented in this thesis. An identical looking (2 x 2) HC structure to the Ti₂O₃ ultra-thin film has been formed; a stoichiometry of Nb2O3 is suggested. Another interesting reconstruction is a hollow triangle structure. Various sizes have been found, and sides of these equilateral triangles all show a double-line feature aligned along the { 1 ₁⁻ } directions of the Au(111) lattice. Chemical composition characterisations of NbO_x thin films are still required as is DFT modelling. Experimental techniques used in this thesis include scanning tunnelling microscopy (STM), low energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). Ultra-thin oxide films were created by physical vapour deposition (PVD) in ultra-high vacuum (UHV) systems.

Title: Relativistic Theory of Electron Transport in Magnetic Layers Author: Rudolf Sýkora Department / Institute: Institude of Theoretical Physics Supervisor of the doctoral thesis: doc. RNDr. Ilja Turek, DrSc., Department of Condensed Matter Physics Abstract: We review the density-functional theory (DFT) in detail using the Levy Lieb ap- proach. The Kohn Sham scheme is discussed, starting from the simplest spinless non- relativistic case, then including spin and considering potential spin magnetism, and finally deriv- ing the full Kohn Sham Dirac relativistic scheme. The Linear Muffin-Tin Orbital (LMTO) method for electronic-structure calculation is presented, together with mentioning the necessary changes to include the spin-orbit (SO) interaction effects to an otherwise scalar-relativistic (SR) theory. Derivation of an electronic-conductance formula for a layered system is given, based on the Landauer scattering picture and using simple non-equilibrium Green functions. The formal- ism is applied to layered metallic systems of light elements Co, Ni, Cu elements, and to layered systems with a tunnelling barrier, Fe/MgO/Ag and Fe/GaAs/Ag. The effects of the SO interac- tion on the Giant Magnetoresistance (GMR) ratio and/or the Tunnelling Anisotropy Magnetore- sistance (TAMR) for these systems are discussed....

Afin de permettre le développement de modèles manipulables par les concepteurs, il est nécessaire de pouvoir comprendre le fonctionnement des nanotubes, en particulier le transport des électrons et leurs propriétés électroniques. C’est dans ce contexte général que cette thèse s’intègre. Le travail a été mené sur quatre plans : développement de modèles permettant la description des phénomènes physiques importants au niveau des dispositifs, expertise sur le fonctionnement des nano-composants permettant de dégager les ordres de grandeurs pertinents pour les dispositifs, les contraintes, la pertinence de quelques procédés de fabrication (reproductibilité, taux de défauts, collection de caractéristiques mesurées et développement éventuel d'expériences spécifiques, expertise et conception des circuits innovatifs pour l’électronique numérique avec ces nano-composants. / This PhD work presents a computationally efficient physics-based compact model for the Schottky barrier (SB) carbon nanotube field-effect transistor (CNTFET). This compact model includes a new analytical formulation of the channel charge, taking into account the influence of the source and drain SBs. Compact model simulation results (I–V characteristic and channel density of charge) as well as Monte Carlo simulation results, which are provided by a recent work, will be given and compared to each other and also to experimental data to validate the used approximations. Good agreement is observed over a large range of gate and drain biases. Furthermore, a scaling study is presented to examine the impact of technological parameters on the device figure of merit. Then, for the assessment of the SB on circuit performances, traditional logical circuits are designed using the SB-CNTFET compact model, and results are compared with a conventional CNTFET with zero-SB height. Finally, exploiting the particular properties of SB-CNTFETs, a three-valued static memory that is suitable for high density integration is presented.

This thesis studies a scheme to fabricate small-scaled metal structures by electrochemical metal deposition and lift off. The key point is the use of self-assembled monolayers (SAMs) to control both interfacial charge transfer in electrodeposition and adhesion of the deposit to the substrate. Patterned SAMs exhibiting blocking and non-blocking areas are applied as templates in electrochemical deposition of Cu or Au. Thiol SAMs on Au substrates are used, namely alkane thiols and thiols combining an aliphatic chain with a biphenyl or biphenyl analogous pyridine-phenyl moieties. The patterning of SAMs is realised with microcontact printing (μCP) and electron beam lithography. Electrochemical deposition based on defects in the SAMs is optimised towards generating small nanostructures and depending on the system single or stepped potential procedures are applied. Generated metal structures are transferred to an insulator by lift off. Au microstructures (~10 μm) have been made with microcontact printing and transferred onto epoxy glue, which can potentially be used as microelectrodes in electroanalytical chemistry. Sub-100 nm Cu features and sub-40 nm Au features have been created with electron beam lithography respectively. Lift off process has successfully transferred Cu nanostructures onto epoxy glue with high precision. In contrast to the deposition mediated by defects, Cu deposition mediated by discharging Pd²⁺ coordinated to a pyridine terminated SAM directly through the SAM molecules has been explored as a new approach. This new approach has potential to decrease the size of the metal structure further and the preliminary results show possibility of sub-10 nm features. SAMs prepared with a newly synthesised molecule, 3-(4'-(methylthio)-[1,1'-biphenyl]-4-yl)propane-1-thiol, are characterised by STM, XPS and NEXAFS. The metal structures are investigated by SEM, AFM and STM.

Les propriétés électroniques et d'autoassemblage de deux composés organiques, le DHTAP et le bis-pyrène, ont été étudiées par microscopie à effet tunnel (STM), sous ultra-vide et à basse température. Les propriétés optiques ont été étudiées par spectroscopie en cavité résonnante (CRD), également sous ultravide.La croissance du DHTAP a été étudiée sur différents métaux nobles. La croissance du bis-pyrène a été étudiée sur Au(111). Dans chaque cas, les conditions de température idéales pour la formation d’une première couche organisée ont été déterminées. Différents modèles sont proposés pour les structures observées en première couche. La formation de la seconde couche moléculaire à également été étudiée.L'évolution des propriétés optiques, étudié par CRD, du bis-pyrène déposé sur du verre borosilicate combinée aux informations obtenues par STM ont permit d’associer ces modifications aux interactions des moments dipolaires de transition des molécules de la première et de la seconde couche et on également permit de déterminer le mode de croissance.Finalement, la possibilité d’induire des modifications chimique de la molécule de DHTAP, intégrée dans une couche auto-assemblée, en utilisant le courant tunnel du STM a été observé. Il s’avère que la molécule de DHTAP intégrée en première couche peut subir une double déshydrogénation pour conduire à la formation d’un composé identifié comme étant le 5,7,12,14-tetraazapentacene (TAP). En seconde couche, la formation de deux radicaux, en plus du TAP, a été observé. La molécule de TAP présente un certain intérêt du fait qu’elle n’est pas synthétisable pas les méthodes conventionnelle de chimie organique. / Electronic and self-assembling properties of two organic compound, the DHTAP and the bis-pyrene, have been studied by the means of low temperature scanning tunnelling microscopy (STM) under ultrahigh vacuum conditions. Optical properties have been studied by cavity ring-down (CRD) spectroscopy, also under ultrahigh vacuum conditions.The growth of DHTAP has been studied on different metallic substrate. The growth of bis-pyrene has been studied on Au(111). In each case, the optimal temperature conditions for the formation of a well-ordered first monolayer have been determined. The formation of second monolayers has also been studied. The evolution of the optical properties, studied by CRD, of bis-pyrene deposited on borosilicate glass combined with information obtained from STM allow us to identify these modifications as interactions between transition dipole moments of molecules in the first and in the second layer, and also determine the growth mode.Finally, the possibility to induce chemical modification of DHTAP molecules embedded in an ordered monolayer using the tunnelling current of the STM has been studied. It appears that the molecule embedded in the first ML can be doubly dehydrogenated which leads to the formation of a compound identified as 5,7,12,14-tetraazapentacene (TAP). In the second layer, the formation of two radicals in addition to the TAP has been observed. The TAP molecule is interesting because of that it cannot be synthesized using common organic chemical methods.

This document discusses the concept of drivers implemented within the context of the REMPLI (Real-Time Energy Management over Power line and Internet, see section 1.8.) network. The process image approach and the tunnelling approach are presented and reasoning is given why the tunnelling approach is preferred. Each of the drivers implemented is associated with a specific metering protocol. This document further discusses the general architecture of such a driver structure. The generic software architecture serves as a framework for integrating serial communication based metering protocols over packet-orientated remote networks and meters, by tunnelling the protocol data units to the remote meters. Principally each Protocol Driver consists of three parts, one part situated at the Application Server, one at the Access Point and one at the Node. This document then gives a description of the general driver structure within the REMPLI network and briefly explains the functions of all the modules contained within the driver structure. An example is used to show how these modules, which make up the software architecture of the Protocol Driver, are used to send an application generated request from the Application Server to the Metering Equipment and sending the response back from the remote Metering Equipment to the Application Server. This dissertation further discusses the need for address translation within the REMPLI network and the need to restrict access to meters by using these addresses and an access control list. This document also discusses the need for a “Keep-alive” signalling scheme, if supported by the underlying protocol and gives a general concept as to how it should be implemented. The role of an Optimization Module is also discussed for low bandwidth networks by means of an M-Bus example. Finally the M-Bus protocol driver implementation is discussed. The results achieved are presented, showing that the driver architecture can successfully be used to tunnel the M-Bus protocol to remote meters, provided the underlying network conforms to the quality of service requirements determined by the implemented metering protocol. The work proposed in this document started off as part of the REMPLI project by the REMPLI team but was completed independently. / Dissertation (MEng (Computer Engineering))--University of Pretoria, 2008. / Electrical, Electronic and Computer Engineering / unrestricted

The region between the infrared and microwave region in the electromagnetic spectrum, the Terahertz (THz) gap, provides an exciting opportunity for future wireless communications as this band has been under utilised. This doctoral work takes a two-pronged approach into closing the THz gap with low-dimensional materials. The first attempt addresses the need for a compact THz source that can operate at room temperature. The second approach addresses the need to build optical elements such as filters and modulators in the THz spectrum. Terahertz quantum cascade lasers (THz QCLs) are one of the most compact, powerful sources of coherent radiation that bridge the terahertz gap. However, their cryogenic requirements for operation limit the scope of the applications. This is because of the electron-electron scattering and heating of the 2-dimensional free electron gas which leads to significant optical phonon scattering of the hot electrons. Theoretical studies in laterally confined QCL structures have predicted enhanced lifetime of the upper state through suppression of the non-radiative intersubband relaxation of carriers, which leads to lower threshold, and higher temperature performance. Lithographically defined vertical nanopillar arrays with electrostatic radius less than tens of nm offer a possible route to achieve lateral confinement, which can be integrated into QCL structures. A typical gain medium in a QCL consists of at least 100 repeat periods, with a thickness of 6-14 micron. For practical implementation of the top-down approach, restrictions are imposed by aspect ratios that can be achieved in present dry-etching systems. Typically, for sub-200 nm radius pillars, the thickness ranges from 1-3.5 micron. It is therefore necessary to work with THz QCLs based on 3-4 quantum well active regions, so as to maximise the number of repeat periods (hence gain) within an ultra-thin active region. After an introductory chapter, Chapter 2 presents a theoretical treatise on the realistic electrostatic potential in a lithographically defined nanopillar by scaling from a single quantum well (resonant tunnelling diode) to a THz QCL. Chapter 2 also discusses, the effect of lateral confinement on the intersubband states and the plasmonic mode in a THz QCL. One of the key experimental challenges in scaling down from QCLs to quantum-dot cascade lasers is the electrical injection into the nanopillars. This involves insulation and planarisation of the high aspect-ratio nanopillar arrays. Furthermore, the choice of the planarising layer is critical since it determines the loss of any optical mode. This experimental challenge is solved in Chapter 3. Chapter 4 presents the electro-optic performance of low-repeat period QCLs with an active region thickness that is less than 3.5 micron. Another topic of recent interest in the THz optics community is plasmonics in graphene. This is because the bound electromagnetic modes (plasmons) are tightly confined to the surface and can also be tuned with carrier concentration. Plasmonic resonance at terahertz frequencies can be achieved by gating graphene grown via chemical vapour deposition (CVD) to a high carrier concentration. THz time domain spectroscopy of such gated monolayer graphene shows resonance features around 1.6 THz superimposed on the Drude-like frequency response of graphene which may be related to the inherent poly-crystallinity of CVD graphene. Chapter 5 discusses these results, as an understanding of these features is necessary for the development of future THz optical elements based on CVD graphene. Chapter 5 finally describes how the gate tunability of THz transmission through graphene can be exploited to indirectly modulate a THz QCL. Chapter 6 presents ideas from this doctoral work, which can be developed in future to address the issues of enhanced temperature performance of THz QCLs and to realise realistic THz devices based on graphene.