Transition Metal (TM) silicides are potential materials for different high temperature applications due to their high melting points and chemical stability at elevated temperatures. In the present work, the possible use of Gr (VIB) disilicides: MoSi2 and CrSi2 for high temperature structural application and thermopower generation respectively are investigated. Literature reports on MoSi2 indicate this material to have excellent mechanical and thermal behaviors at temperatures greater than 1273 K. The major problems limiting its use are the low temperature brittleness and oxidation at intermediate temperatures and form the scope of this work. Also, CrSi2 is reported to be a narrow band gap semiconductor. Its feasibility as a thermoelectric material for power generation is investigated. The first chapter briefly summarizes the literature on MoSi2 and CrSi2 relevant to structural and thermoelectric applications respectively. Based on the available literature, the scope of further work is discussed. The second chapter describes the methods of synthesis employed for these materials and the characterization techniques adopted. Some experimental setups like thermal conductivity and hot pressing unit that were fabricated as part of the work are described in detail. The thermal conductivity apparatus is based on the principle of parallel heat flow technique. It allows accurate measurement of K and S in the temperature range 300-700 K. The induction based hot-pressing unit allows compaction of polycrystalline powders to near theoretical densities thereby allowing quantitative evaluation of the physical properties. In the third chapter, an understanding of ductility/brittleness based of electron charge density distribution is attempted. The electron charge density in Tin and simple metals (BCC and FCC) is analyzed using Bader’s Atoms in Molecule (AIM) theory. Also the relevant surface and dislocation energies in these materials are calculated according to the Rice Model. It is found that the electron densities at the critical points correlate in a simple way with the relevant stacking fault and surface energetics. Based on these results, a ductility parameter (DM odel) based on electron charge distribution, to predict the effects of chemical substitutions on ductility/brittleness in materials is proposed. In the fourth chapter, possible elements to impart ductility in MoSi2 are identified based on the DM odel values. Calculations indicate, Nb, Ta, Al, Mg and Ga to be suitable candidates for improving ductility in MoSi2. Also oxidation studies based on present experiments and reported literature data reveal, Al to improve the intermediate temperature (773-873 K) oxidation behavior. Thus to simultaneously improve the low temperature ductility and oxidation resistance, Nb and Al were identified as suitable candidates. In the fifth chapter, the experimental data of Nb and Al co-substituted MoSi2 samples are reported. Oxidation studies carried out by thermogravimetry show improved oxidation resistance in Nb and Al co-substituted samples compared to pure MoSi2 in the temperature range of 773-873 K. Mechanical characterization was carried out for (Mo0.99Nb0.01)(Si0.96Al0.04)2 co-substituted composition. Compression testing at room temperature show plastic deformation at low strain rates (10−3 /sec). Indentation experiments show a reduction in the hardness and stiffness compared to pure MoSi2. There is also an increase in the fracture toughness (K1C ) value with the fracture modes being predominantly transgranular. The sixth chapter describes the structural, thermal and transport properties of CrSi2. Structural refinement was carried out by Rietveld method and the positional, thermal parameters and occupancy were fixed. Thermo-gravimetric analysis shows oxidation resistance in powdered samples upto 1000 K. Thermal expansion (α) studies reveal anisotropy in the α values with an unusual decrease in the average αV values between 500 and 600 K. Measurements of electrical resistivity and seebeck coefficient indicate a degenerate semiconducting behavior. Electronic band structure calculations indicate a narrow indirect band gap (EG) material with EG~0.35 eV. Thermal conductivity (K) measurements show a decrease in K value with increasing temperature. Calculation of the thermoelectric figure of merit (ZT) show a maximum value of 0.18 at 800 K for the temperature range studied. Based on an analysis of the experimental and theoretical results, it is identified that further improvements in ZT of CrSi2 may be possible by reducing the lattice thermal conductivity and optimization of the carrier concentration. In chapter seven, the effect of particle size on ZT of CrSi2 is studied. Nano powders of CrSi2 were prepared by mechanical milling. Contamination is found to be a major problem during milling and the different milling parameters (milling speed, atmosphere, dispersant etc) were optimized to minimize contamination. The milled powders were further hot pressed to achieve high densities in a short duration thereby minimizing the grain growth. It is observed that the lattice thermal conductivity is reduced significantly with decreasing grain size. Measurements of ZT show a maximum value of 0.20 in the milled sample compared to 0.14 in arc melted CrSi2 at 600 K. In chapter eight the effect of chemical substitutions on ZT of CrSi2 is studied. Mn substitutions in Cr site were carried out to study the effect of atomic mass on lattice thermal conductivity (KP ). Al substitutions in Si site were carried out to tune the Fermi level. Results of Mn substitution show a large decrease in KP but also a reduction in the thermoelectric power factor (S2σ). The maximum ZT observed in the Mn substituted samples was 0.12 at 600 K. Al substitution results in an increase in the thermoelectric power factor and a subsequent increase in ZT. The maximum ZT observed was 0.27 at 700 K for 10% substitution of Al in Si site. The work reported in the thesis has been carried out by the candidate as a part of the Ph.D. training programme at Materials Research Centre, Indian Institute of Science, Bangalore, India. He hopes that this work would constitute a worthwhile contribution towards (a) basic understanding of ductility/brittleness in materials and understanding the effects of chemical substitutions, (b) Suitability of chemically substituted MoSi2 to overcome the problems of low temperature brittleness and oxidation. (c) Development of CrSi2 as a high temperature thermoelectric material.

Over the last few decades, body-centered-cubic (bcc) beta (β) titanium alloys have largely been exploited as structural alloys owing to the richness in their microstructural features. These features, which lead to a unique combination of high specific strength and ductility, excellent hardenability, good fatigue performance, and corrosion resistance, make these alloys viable candidates for many applications, including aerospace, automobile, and orthopedic implants. The mechanical properties of these alloys strongly depend on the various phases present; which can be controlled by thermomechanical treatments and/or alloy design. The two most important and studied phases are the metastable ω phase and the stable α phase. The present study focuses on the microstructural evolution and the mechanical behavior of these two phases in a model β-Ti alloy, binary Ti-12wt. %Mo alloy, and a commercial β-Ti alloy, β-21S. Microstructures containing athermal and isothermal ω phases in the binary Ti-12wt. %Mo alloy are obtained under specific accurate temperature controlled heat treatments. The formation and the evolution of the ω-phase based microstructures are investigated in detail via various characterization techniques such as SEM, TEM, and 3D atom probe tomography. The mechanical behavior was investigated via quasi-static tensile loading; at room and elevated temperatures. The effect of β phase stability on the deformation behavior is then discussed. Similar to the Ti-12wt. %Mo, the formation and the evolution of the athermal and isothermal ω phases in the commercial β-21S alloy was studied under controlled heat treatments. The structural and compositional changes were tracked using SEM, TEM, HR-STEM, and 3D atom probe tomography (3D-APT). The presence of additional elements in the commercial alloy were noted to make a considerable difference in the evolution and morphology of the ω phase and also the mechanical behavior of the alloys. The Portevin-Le Chatelier (PLC) like effect was observed in iii this alloy at elevated temperature and this has been attributed to the shearing of the ω precipitates and the dynamic precipitation of the α phase within these channels. The formation of the stable α phase in the commercial β-21S alloy due to the influence of precursor phases, like the metastable ω phase, is investigated. It is evident from the microstructural characterization, using SEM, TEM, HR-STEM, and 3D-APT, that the ω phase does play a role on the fine scale α precipitation. The mechanical behavior of the β+α microstructure, investigated via tensile testing, shows that these alloys are ideal candidate for precipitation hardening. The exceptional strength values obtained in this alloy have been attributed to a combination of several factors.

Groundwater inflow is a challenge in construction of tunnels in fractured bedrocks since it affects the safety function of tunnels and leads to potential problems in the surrounding environment, such as subsidence, dropdown of the groundwater table. Quantification of groundwater inflow into the tunnel is also important for design of grouting in the construction of the tunnel. Modelling groundwater flow in fractured bedrocks currently remains a challenge. Commonly used groundwater models are based on continuum assumptions and they do not consider realistic structures of discrete fractures, which leads to high potential uncertainty in prediction of tunnel groundwater inflow. This thesis focuses on prediction of tunnel groundwater inflow, using a discreet fracture-matrix (DFM) model. The DFM model is evaluated and compared with the conventional continuum model based on Darcy’s law. This DFM model considers, in particular, multi-scale heterogeneity, e.g. fracture networks and variable fracture aperture structures. Applying this DFM model, the impact of variable fracture aperture structures on tunnel inflow is investigated through stochastic analysis. The results show that under the same boundary conditions, the traditional continuum model overestimates the inflow compared to the DFM model. The difference in equivalent permeability is 2 to 3 orders of magnitude. The sensitivity analysis shows that the discreet fracture model is sensitive to the variability of fracture aperture. The estimated equivalent permeability values by discreet fracture modelling is in the order of 5×10-6 to 1×10-7 m/s for a fracture density of 1.2 fractures per square meter. This study demonstrates that the DFM represents the more realistic features of fractured rock structures, which is useful and can be used to predict groundwater inflow in fractured rock tunnels. / Grundvatteninflöde är en utmaning vid byggnation av tunnlar i sprucken berggrund eftersom det påverkar tunnlarnas säkerhetsfunktion och leder till potentiella problem i den omgivande miljön, såsom sättningar och Grundvattennivåsänkning. Kvantifiering av grundvatteninflöde till tunneln är också viktig för utformning av injektering i tätning? byggandet av tunneln. Att modellera grundvattenflödet i sprucken berggrund är för närvarande en utmaning. Grundvattenmodeller man normalt använder är baserade på kontinuumantaganden, och de tar inte hänsyn till realistiska strukturer av diskreta sprickor, vilket leder till hög potentiell osäkerhet i uppskattning av tunnelgrundvatteninflöde. Denna avhandling fokuserar på förutsägelse av tunnelinläckage, med hjälp av en diskret sprickmatris (DFM) modell. DFM-modellen utvärderas och jämförs med den konventionella kontinuummodell vilken är baserad på Darcys lag. Denna DFM-modell tar särskilt hänsyn till multi-skala heterogenitet, till exempel spricknätverk och variabla dubbelkolla. Genom att tillämpa denna DFM-modell undersöks effekten av strukturer med variabel spricköppning på grundvatteninflödet genom stokastisk analys. Resultaten visar att under samma randvillkor överskattar den traditionella kontinuummodellen inflödet jämfört med DFM-modellen. Skillnaden i ekvivalent permeabilitet är 2 till 3 storleksordningar. Känslighetsanalysen visar att den diskreta sprickmodellen är känslig möt variationen i spricköppningen. De uppskattade ekvivalenta permeabilitetsvärdena med diskret sprickmodellering är i storleksordningen 5x10-6 till 1x10-7 m/s för en spricktäthet på 1,2 sprickor per kvadratmeter. Denna studie visar att DFM representerar de mer realistiska egenskaperna hos sprickiga bergstrukturer, vilket är användbart och kan användas för att uppskatta grundvatteninflöde i sprickiga bergtunnlar.

Since the origin of the automotive at the end of the 19th century, the traffic flow is subject to a constant increase and, unfortunately, involves a constant augmentation of road accidents. Research studies such as the one performed by the World Health Organization, show alarming results about the number of injuries and fatalities due to these accidents. To reduce these figures, a solution lies in the development of Advanced Driver Assistance Systems (ADAS) which purpose is to help the Driver in his driving task. This research topic has been shown to be very dynamic and productive during the last decades. Indeed, several systems such as Anti-lock Braking System (ABS), Electronic Stability Program (ESP), Adaptive Cruise Control (ACC), Parking Manoeuvre Assistant (PMA), Dynamic Bending Light (DBL), etc. are yet market available and their benefits are now recognized by most of the drivers. This first generation of ADAS are usually designed to perform a specific task in the Controller/Vehicle/Environment framework and thus requires only microscopic information, so requires sensors which are only giving local information about an element of the Vehicle or of its Environment. On the opposite, the next ADAS generation will have to consider more aspects, i.e. information and constraints about of the Vehicle and its Environment. Indeed, as they are designed to perform more complex tasks, they need a global view about the road context and the Vehicle configuration. For example, longitudinal control requires information about the road configuration (straight line, bend, etc.) and about the eventual presence of other road users (vehicles, trucks, etc.) to determine the best reference speed. [...]

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By studying self-avoiding polygons (SAPs) in (L, M )-tubes (a tubular sublattice of the simple cubic lattice) as a sequence of 2-spans, transfer matrices can be used to obtain theoretical and numerical results for these SAPs. As a result, asymptotic properties of these SAPs, such as pattern densities in a random SAP and the expected span of a random SAP, can be calculated directly from these transfer matrices. These same results can also be obtained for compact polygons, as well as SAPs under the influence of an external force (called compressed or stretched polygons). These results can act as tools for examining the entanglement complexity of SAPs in (L, M )-tubes. In this thesis, it is examined how transfer matrices can be used to develop these tools. The transfer matrix method is reviewed, and previous transfer matrix results for SAPs in (L, M )-tubes, as well as SAPs subjected to an external force, are presented. The transfer matrix method is then similarly applied to compact polygons, where new results regarding compact polygons are obtained, including proofs for a compact concatenation theorem and for a compact pattern theorem. Also in this thesis, transfer matrices are actually generated (via the computer) for relatively small tube sizes. This is done for the general case of SAPs in (L, M )-tubes, as well as for the compact and external force cases. New numerical results are obtained directly from these transfer matrices, and a new algorithm for generating polygons is also developed from these transfer matrices. Compact polygons are actually generated (via the computer) for relatively small tube sizes and spans by using the developed polygon generation algorithm, and new numerical results for pattern densities and limiting free energies are obtained for stretched and compressed polygons.

Heterogeneous mixtures have the potential to be used as synthetic substrates for antenna applications giving the antenna designer new degrees of freedom to control the permittivity and/or permeability in three dimensions such as by a smooth variation of the density of the inclusions, the height of the substrate and the manufacture the whole antenna system in one process. Electromagnetic, fabrication, environmental, time and cost advantages are potential especially when combined with nano-fabrication techniques. Readily available and cheap materials such as Polyethylene and Copper can be used in creating these heterogeneous materials. These advantages have been further explained in this thesis. In this thesis, the research presented is on canonical, numerical and measurement analysis on heterogeneous mixtures that can be used as substrates for microwave applications. It is hypothesised that heterogeneous mixtures can be used to design bespoke artificial dielectric substrates for say, patch antennas. The canonical equations from published literature describing the effective permittivity, ε_eff and effective permeability, μ_eff of heterogeneous mixtures have been extensively examined and compared with each other. Several simulations of homogenous and heterogeneous media have been carried out and an extraction/inversion algorithm applied to find their ε_eff and μ_eff. Parametric studies have been presented to show how the different variables of the equations and the simulations affect the accuracy of the results. The extracted results from the inversion process showed very good agreement with the known values of the homogenous media. Numerically and canonically computed values of ε_eff and μ_eff of various heterogeneous media were shown to have good agreement. The fabrication techniques used in creating the samples used in this research were examined, along with the different measurement methods used in characterising their electromagnetic properties via simulations and measurements. The challenges faced with these measurement methods were explained including the possible sources of error. Patch antennas were used to investigate how the performance of an antenna may be affected by heterogeneous media with metallic inclusions. The performance of the patch antenna was not inhibited by the presence of the metallic inclusions in close proximity. The patch measurement was also used as a measurement technique in determining the ε_eff of the samples.

Toughness enhancements can be induced in cubic-B1 transition metal nitride alloys by an increased occupation of the d-t2g metallic states. In this Licentiate Thesis I use density functional theory to investigate the mechanical properties of TiN and VN and of the ternaries obtained by replacing 50% of Ti and V atoms with M (M = V, Nb, Ta, Mo, and W) to form ordered structures with minimum number of inter-metallic bonds. The calculated values of elastic constants and moduli show that ternary alloys with high valence electron concentrations (M = Mo and W), have large reductions in shear moduli and C44 elastic constants, while retaining the typically high stiffness and incompressibility of ceramic materials. These results point to significantly improved ductility in the ternary compounds. This important combination of strength and ductility, which equates to material toughness, stems from alloying with valence electron richer dmetals. The increased valence electron concentration strengthens metal–metal bonds by filling metallic d-t2g states, and leads to the formation of a layered electronic configuration upon shearing. Comprehensive electronic structure calculations demonstrate that in these crystals, stronger Ti/V – N and weaker M – N bonds are formed as the valence electron concentration is increased. This phenomenon ultimately enhances ductility by promoting dislocation glide through the activation of an easy slip system.

Seja p um primo, considere q = pe com e ≥ 1 inteiro. Dado o polinômio f (x) = x4+ax3+bx2+ cx+d ∈ Fq[x], consideremos o polinômio F(T) = T4 +aT3 +bT2 +cT + d - y ∈ Fq(y)[T], com y = f (x) sobre Fq(y). O objetivo desse trabalho é determinar o número de polinômios f (x) que tem seu grupo de galois associado GF isomorfo a cada subgrupo transitivo (prefixado) de S4. O trabalho foi baseado no artigo: Galois closures of quartic sub-fields of rational function fields, usando equações auxiliares associadas ao polinômio minimal F(T) de graus 3 e 2 (DUMMIT, 1994); bem como uma caraterização das curvas projetivas planas de grau 2 não singulares. Se car(k) ≠ 2, associamos a F(T) sua cúbica resolvente RF(T) e seu discriminante ΔF. Em seguida obtemos condições para GF ≅ C4 (vide Teorema 2.9), que é ocaso fundamental para determinação dos demais casos. Se car(k) = 2, procuramos determinar condições para GRF ≅ A3, associando ao polinômio RF(T) sua quadrática resolvente P(T) (vide a Proposição 2.13). Apos ter homogeneizado P(T), usamos uma das consequências do teorema de Bézout, a saber, uma curva algébrica projetiva plana C de grau 2 é irredutível se, e somente se, C não tem pontos singulares. Nesta dissertação obtemos resultados semelhantes com uma abordagem relativamente diferente daquela usada pelo autor R. Valentini. / Let be p a prime, q = pe whit e ≥ 1 integer. Let a polynomial f (x) = x4+ax3+bx2+cx+d ∈ Fq[x], considering the polynomial F(T)=T4+aT3+bT2+cT +d, with y= f (x) over Fq(y)[T]. The purpose of the current research is to determine the numbers of polynomials f (x) which have its associated Galois group GF, this GF is isomorphic for each transitive subgroup (prefixed) of A4. This project is based on the article: Galois closures of quartic sub-fields of rational function fields, using auxiliary equations associated to the minimal polynomial F(T) of degrees 3 and 2 (DUMMIT, 1994); besides a characterization of non-singular projective plane curves of degree 2 was used. If car(k) ≠ 2, associated to F(T) the resolvent cubic RF(T) and its discriminant ΔF then conditions for GF are obtained as GF ≅ C4 which is the fundamental case for determining the other cases (Theorem 2.9). If car(k) = 2, to find conditions for GRF ≅ A3, associated to the polynomial RF(T) its resolvent quadratic p(T) (Proposition 2.13). Homogenizing p(T), one of the consequences of the Bezout theorem was applied. It is, a projective plane curve C, which grade 2, is irreducible if and only if C is smooth. In the current dissertation, similar results were obtained using a different approach developed by the author R. Valentini.

A avaliação do risco a contaminação e a escolha de técnicas de remediação de poluentes em aquíferos fraturados depende da quantificação dos fenômenos envolvidos no transporte de solutos. A geometria da fratura, usualmente caracterizada pela abertura, é o principal parâmetro que indiretamente controla o transporte nos aquíferos fraturados. A simplificação mais comum desse problema é assumir que as fraturas são um par de placas planas e paralelas, isto é, com uma abertura constante. No entanto, por causa do limitado número de trabalhos experimentais, não está esclarecida a adequabilidade do uso de uma abertura constante para simular o transporte conservativo em fraturas do Aquífero Serra Geral (ASG), Brasil. O objetivo deste trabalho é avaliar a influência da abertura de uma fratura natural do Aquífero Serra Geral sob o transporte conservativo de solutos. Uma amostra natural de basalto fraturado foi usada em um experimento hidráulico e de transporte de um traçador conservativo (escala de laboratório). O campo de abertura foi medido usando a técnica avançada, de alta resolução e tridimensional, chamada microtomografia computadorizada de raios-X. A concentração de traçador medida foi utilizada para validar uma solução analítica unidimensional da Equação de Advecção-dispersão (ADE). O desemprenho do ajuste da ADE às curvas de passagem experimentais foi avaliado para quatro diferentes tipos de aberturas constantes. Os resultados mostraram que o escoamento de água e o transporte de contaminantes pode ocorrer através de fraturas micrométricas, ocasionando, eventualmente, a contaminação do ASG. A abertura de balanço de massa é a única que pode ser chamada propriamente de \"abertura equivalente\". O uso de aberturas constantes na ADE não permitiu representar completamente o formato das curvas de passagem porque o campo de velocidade não é uniforme e intrinsicamente bidimensional. Portanto, na simulação do transporte deve-se incorporar a heterogeneidade da abertura da fratura. / The contamination risk assessment and the choice of suitable cleanup techniques for pollutants in fractured rock depends on the quantification of the transport phenomena. Fracture geometry often described by the apertures is the major parameter that controls indirectly solute transport in fractured rock. The simplest approach is describing fractures as a pair of smooth parallel plates with constant aperture. However, there is a lack of information about the suitability for using a constant aperture for the conservative solute transport prediction in a single fracture of Serra Geral Aquifer (SGA), Brazil. The aim of this work is to evaluate the effect of aperture variability in a natural single rough-walled fracture of Serra Geral Aquifer on conservative solute transport. A natural core of fractured basalt was used for a hydraulic and tracer tests (laboratory scale). The aperture field was measured using the advanced, high-resolution and tridimensional technique X-ray computed tomography. The measured tracer concentration was validated by means of an analytical solution of the Advection-dispersion Equation (ADE). The ADE fit performance was measured against experimental breakthrough curves for four distinct kind of constant apertures. It was found that water flow and solute transport can take place through micrometric fractures, eventually leading the SGA contamination. Results show that the mass balance aperture is the only appropriate \"equivalent aperture\" for describing solute transport in a single rough-walled fracture. The results showed that ADE is not appropriate for modeling the complete behavior of experimental breakthrough curves because of the dimensional non-uniform velocity field. Therefore, the aperture heterogeneity must be considered in solute transport simulation.