The elastic properties of a solid are of considerable interest to both science and technology. Not only do they contain fundamental information about the nature of the inter-atomic bonding in the material, but they also determine the mechanical behavior of solids. In the past few years, considerable effort has been devoted to the study of elastic properties of bulk metallic glasses (BMGs), a relatively new class of metallic materials that display a unique combination of mechanical and physical properties. Our research has focused on Zr-based, Cu-based and Ca-based metallic glasses. Zr-based BMGs are known to have superior glass forming ability and high strength, but their ductility is too low for wide-spread practical applications. Cu-based BMGs recently received wide interest because of their low cost and good mechanical properties. Ca-based BMGs have low glass transition temperature Tg, around 390 K, which make them very attractive to be studied near Tg. In this work, resonant ultrasound spectroscopy (RUS) has been applied to study the elastic properties of above mentioned BMGs from 5 K to their glass transition temperature Tg. RUS is a novel technique for determining the elastic moduli of solids, based on the measurement of the resonances of a freely vibrating body. In an RUS experiment, the mechanical resonances of a freely vibrating solid of known shape are measured, and an iteration procedure is used to “match” the measured lines with the calculated spectrum. This allows determination of all elastic constant of the solid from a single frequency scan. Below Tg, the elastic constants of the BMGs under investigation show “normal” behavior, i.e. with increasing temperature, all moduli decrease and Poisson ratio increases. Above Tg changes in the trends occur due to structural relaxation and crystallization. We confirmed the suggested link between ductility and Poisson ratio: BMGs showing good ductility display high Poisson ratio. By increasing palladium content in Zr50Cu40-xAl10Pdx alloys, BMGs with high Poisson ratio and thus good ductility have been obtained. In addition, we developed a simple model to provide fast and good estimate of the temperature dependence of elastic constants of BMGs from room temperature measurements. Keywords: Elastic properties; Bulk metallic glasses (BMGs); Resonant ultrasound spectroscopy (RUS); Internal friction.

This dissertation addresses two critical issues in the mechanical behaviors and structures of bulk-metallic glasses (BMGs): (1) the effect of composition, fabrication method, and pretreatment of plastic deformation on mechanical properties and structures of BMGs; (2) the mechanical response and structural evolution of BMGs in the elastic and plastic region. (Cu50Zr50)94Al6 and (Cu50Zr50)92Al8 amorphous alloys were used to study the effect of composition on mechanical properties and structures of BMGs. The (Cu50Zr50)94Al6 alloy exhibits lower yield stress and Young’s modulus, higher Poisson’s ratio, worse thermal stability, and better plasticity than (Cu50Zr50)92Al8. Both the topological and chemical effects of Al addition account for the differences of mechanical and physical properties between them. A Zr55Ni5Al10Cu30 glass-forming alloy with injection casting (the melting temperatures are 1,550 K and 1,250 K, respectively) and with suction casting was fabricated. The results indicate that despite their amorphous structures, the suction-casting samples exhibit a lower yield stress, lower Young’s modulus, and larger plastic strain than the injection-casting samples (the melting temperature is 1,550 K) due to more quenched-in free volumes in suction casting, which results from the higher cooling rate. The inhomogeneous plastic deformation in Zr50Cu40Al10 BMG samples was introduced by four-point-bend fatigue. There is almost no difference of the stress-strain behaviors between the deformed and undeformed samples. Elastostatic compression was used to introduce homogeneous deformation in Zr70Cu6Ni16Al8 BMG samples. The preloaded samples are softer with decreases of yield strength and Young’s moduli. Anisotropy was observed in the preloaded samples despite their small magnitudes, which even occurred at a relatively low temperature and applied stress level. The structural evolution of Zr70Cu6Ni16Al8 BMG in the elastic region was analyzed with anisotropic pair density function. The analysis of the first shell of Zr70Cu6Ni16Al8 glass confirms the structural changes in the elastic region. The bond reorientation leads to direction dependent changes in the chemical short-range order. The structural evolution in the plastic region of Zr70Cu6Ni16Al8 BMG is investigated as well. The serrations were observed for both the stress-displacement and full width at half maximum-displacement curves. The excess free volume was measured, which increases with increasing the displacement.

Les façades des nouveaux bâtiments et des bâtiments existants sont altérées par la pénétration de l'eau. Afin de protéger les bâtiments et surfaces exposées aux intempéries, des traitements contenant des agents hydrophobes doivent être appliqués. Les traitements utilisés à l’heure actuelle sont des traitements de surface qui se dégradent au cours du temps. L'agent hydrophobe, présent en surface, est soumis à des conditions très rudes telles que des rayonnements ultraviolets, de grandes variations de température, de l'abrasion ..., qui réduisent l’efficacité et la durabilité des traitements. La plupart des traitements aujourd'hui disponibles, fournisse une barrière efficace au passage de l’eau à court terme, mais doivent donc être réappliqués régulièrement. Le projet de recherche, présenté ici, traite de la mise en place d'un traitement de masse de matériaux cimentaires utilisés dans la protection de structures (joints, crépi ...). Ce traitement devrait offrir une protection à long terme, mais ne devrait pas modifier de manière significative les propriétés mécaniques des matériaux. Les avantages d'un traitement de masse sont évidents. Seule une petite partie de l'agent hydrophobe est exposée et dégradée par les conditions climatiques et l'abrasion de surface ne porte pas atteinte à l'intégrité du traitement. Une étude fondamentale a été menée afin d'étudier l'influence de l'incorporation d´agents à base de silicium sur les processus d'hydratation des ciments Portland et de comprendre leur mode d'action. Deux agents (alpha,omega dihydroxypolydimethylsiloxane et n-octyltriethoxysilane) et deux ciments Portland (ordinaire et blanc CEM I 42,5N) ont été choisis et étudiés. Trois modes d´introduction (liquides purs, émulsions et granules) ont été mis en œuvre et comparés. Le but est de déterminer les meilleures conditions pour obtenir un traitement efficace et durable tout en préservant les propriétés mécaniques. Les résultats d'absorption d'eau par capillarité et de perméabilité à la vapeur d’eau sont prometteurs et les essais mécaniques sur mortiers n’ont pas montré de diminutions significatives des résistances mécaniques. La microstructure et la progression de l'hydratation des matrices cimentaires adjuvantées et de référence, ont été caractérisées par calorimétrie à conduction, par calorimétrie différentielle à balayage couplée à la thermogravimétrie, par spectroscopie infra-rouge, par diffraction des rayons X, par porosimétrie au mercure, et par microscopie électronique à balayage. La durabilité des matériaux adjuvantés a été étudiée afin de montrer la pertinence des traitements ainsi que l'évaluation de la progression de l'hydratation. Les performances hydrofuges ainsi que l’évolution de la microstructure, à l’issue des différents vieillissements artificiels et naturels, ont été déterminées. Les mortiers mis en œuvre ont été soumis à des vieillissements artificiels simulant des conditions proches de celles rencontrées en pratique (tels que des cycles rayonnements UV, pluie, sel, gel/dégel…). Une amélioration de la durabilité des mortiers adjuvantés a été observée. Les résultats sont très encourageants et confirment l'intérêt d’un tel traitement dans la masse. /Protection of cement-based materials means above all, moisture protection because water is primarily responsible for inducing damaging physical and chemical processes in building materials. In most cases, water repellents are applied either directly during the construction or insulation process; or as a post-treatment of the exposed surfaces in order to protect the buildings from further decay. A new way is to develop a bulk treatment for cement-based materials which should provide a long term protection without modifying the mechanical properties of the cementitious materials. The advantages of a bulk treatment are obvious i.e. only a small part of the hydrophobic agent is exposed and degraded by the UV. In addition, surface abrasion does not affect the integrity of the treatment. A fundamental study was initiated to investigate the influence of the incorporation of two active silicon-based agents (already used as post-building treatments) on the hydration processes of Portland cements and to understand the involved mechanisms of interaction. Two agents (alpha,omega dihydroxypolydimethylsiloxane and n-octyltriethoxysilane) and two Portland cements (Ordinary and White Portland Cement CEM I 42,5N) were chosen and studied. Three incorporation modes (pure liquids, water emulsions and granules) were investigated. The effects of the three modes were compared. The aim was to determine the best conditions for an efficient and sustainable treatment preserving the mechanical properties of the materials. The results of capillary water penetration and water vapor permeability are promising and are not accompanied by a significant decrease of the mechanical performances The microstructure and progression of hydration of admixtured cement pastes were characterized by conduction calorimetry, differential scanning calorimetry, thermo-gravimetry, infra-red spectroscopy, X-ray diffraction, mercury intrusion porosimetry, and scanning electron microscopy. In addition, the durability of water-repellent additives and of the admixtured cement was studied in order to show the relevance of the treatments as well as the assessment of the progression of hydration and the type of products that were developed. Mortar specimens were submitted to artificial ageing cycles such as freeze-thaw cycles, ultraviolet cycles and rain-sun cycles. The general trend is an improvement of the durability of admixtured mortars. The results are very encouraging and confirm the interest of the bulk mortar treatment.

For decades, Metallic Glass, with its isotropic featureless structure while exhibiting outstanding mechanical properties was possible only at a high rate of quenching and with at least one dimension in the submicron regime.  This limitation was overcome with the discovery of Bulk Metallic glasses, BMGs, containing three or more elements following the additional two empirical rules of optimum geometric size differences and negative energy of mixing among the constituent elements. Since then thousands of Fe-, Ni-, Al-, Mg-, Ti- based BMGs have been discovered and comprehensively investigated mainly by groups in Japan and USA. Yet the discovery of new combinations of elements for BMGs is alchemy. We do not know with certainty which element when added will make possible a transition from being a ribbon to a bulk rod.    In this thesis we report a discovery of castable BMGs rods on substitution of Fe by nickel in an alloy of FeBNb which could otherwise have been only melt-spun into ribbons.  For example, we find that substitution of just 6 at.% of Fe raises the glass forming range, GFA, to as much as ∆Tx =40K while the other parameters for GFA like Trg, γ, and δ reach enhanced values 0.57, 0.38, and 1.40 respectively.  Furthermore, the electrical conductivity is found to increase by almost a factor of two.  Magnetically it becomes softer with coercivity 260mOe which further reduces to much lower values on stress relaxation.  Ni does not seem to carry a magnetic moment while it enhances the magnetic transition temperature linearly with Ni concentration. We have investigated the role of Ni in another more stable BMGs based FeBNbY system in which case ∆Tx becomes as large as 94K with comparable enhancement in the other GFA parameters. Due to the exceptional soft magnetic properties, Fe-based bulk metallic glasses are considered potential candidate for their use in energy transferring devices. Thus the effect of Ni substitution on bulk forming ability, magnetic and electrical transport properties have been studied for FeBNb and FeBNbY alloy systems. The role of Ni in these systems is densification of the atomic structure and its consequence. We have exploited the superior mechanical properties of BMGs by fabricating structures that are thin and sustainable.  We have therefore investigated studies on the thin films of these materials retaining their excellent mechanical properties. Magnetic properties of FeBNb alloy were investigated in thin films form (~200-400nm) in the temperature range of 5-300K. These Pulsed Laser deposited amorphous films exhibit soft magnetism at room temperature, a characteristic of amorphous metals, while they reveal a shift in hysteresis loop (exchange anisotropy, HEB=18-25Oe), at liquid helium temperature. When thickness of films is reduced to few nanometers (~8-11nm), they exhibit high transparency (&gt;60%) in optical spectrum and show appreciably high saturation Faraday rotation (12o/μm, λ= 611nm). Thin films (~200-400nm) of Ni substituted alloy (FeNiBNb) reveal spontaneous perpendicular magnetization at room temperature. Spin-reorientation transition was observed as a function of film thickness (25-400nm) and temperature (200-300K), and correlated to the order/disorder of ferromagnetic amorphous matrix as a function of temperature. These two phase films exhibits increased value of coercivity, magnetic hardening, below 25K and attributed to the spin glass state of the system.    Using the bulk and thin films we have developed prototypes of sensors, current meters and such simple devices although not discussed in this Thesis.                                         Ti-based bulk metallic glasses have been attracting significant attention due to their lower density and high specific strength from structural application point of view. High mechanical strength, lower values of young’s modulus, high yield strength along with excellent chemical behaviors of toxic free (Ni, Al, Be) Ti-based glassy metals make them attractive for biomedical applications. In the present work, toxic free Ti-Zr-Cu-Pd-Sn alloys were studied to optimize their bulk forming ability and we successfully developed glassy rods of at least 14mm diameter by Cu-mold casting. Along with high glass forming ability, as-casted BMGs exhibit excellent plasticity. One of the studied alloy (Ti41.5Zr10Cu35Pd11Sn2.5) exhibits distinct plasticity under uniaxial compression tests (12.63%) with strain hardening before failure which is not commonly seen in monolithic bulk metallic glasses. / <p>QC 20120906</p> / Hero-m

The thesis describes an investigation into the interaction between the conducting polymer and cellulosic materials, and the preparation of electroconductive paper. The adsorption behavior of the conducting polymer onto cellulosic materials was characterized. Poly(3,4-ethylenedioxythiophene) doped with poly(4-styrene sulfonate) (PEDOT:PSS) was used as conducting polymer because of its attractive properties in terms of conductivity, water solubility, and environmental stability. The model substrate used for adsorption was microcrystalline cellulose (MCC). Various pH levels and salt concentrations were explored to completely understand the adsorption behavior of PEDOT:PSS. The variation in surface charge characteristics when the pH and salt concentration were changed was monitored by polyelectrolyte titration and zeta potential measurement. The adsorption isotherm showed a broad molecular distribution of the conducting polymer and considerable interaction between the polymer and MCC. As the pH of the solution was increased, the adsorbed amount decreased. With varying salt concentrations, the adsorption passed through a maximum. The extent of deposition of PEDOT:PSS on the surface of cellulosic fibers was investigated using X-ray Photoelectron Spectroscopy (XPS) with a commercial base paper as substrate. XPS analysis of dip-coated paper samples showed PEDOT enrichment on the surface. The degree of washing the dip-coated paper with acidic water did not significantly affect the PEDOT enrichment on the surface.   A base paper was coated with PEDOT:PSS blends to produce electroconductive papers. The bulk conductivities (σdc) of the coated papers were measured using a four-probe technique and impedance spectroscopy. One-side and two-side coating gave comparable conductivity levels. Various organic solvents added to the PEDOT:PSS dispersion at different concentrations showed various effects on the bulk conductivity of the coated paper. Blends containing sorbitol and isopropanol did not enhance the bulk conductivity of the coated paper, and at high concentrations these organic solvents lowered the conductivity. Paper samples coated with a PEDOT:PSS blend containing N-methylpyrrolidinone (NMP) and dimethyl sulfoxide (DMSO) exhibited a higher conductivity than when coated with pure PEDOT:PSS, due to conformational changes and their plasticizing effect. The effect of calendering was investigated and only the sample subjected to 174 kN/m line load after coating showed significant conductivity enhancement. The addition of TiO2 pigment lowered the bulk conductivity of the paper. Contact angle measurements were made to monitor the effect of coating the paper with PEDOT:PSS blends on the hydrophilicity of the paper samples. The amount of PEDOT:PSS deposited in the fiber network was determined using total sulfur analysis. Thus, this study makes use of conventional paper surface treatment as method for achieving bulk conductivity of paper in the semi-conductor range without significantly decreasing the paper strength. / Printed Polymer Electronics

An increasing number of power plants in Scandinavia are beginning to use biofuel instead of coal or oil. The material in the new fuel is a mixture of woodchips, mostly Pine, Spruce and Salix, bark, GROT (tops and branches from felling waste) and sawdust from sawmills. It is heterogeneous, having a moisture content varying from 15% up to 65%. The moisture content affects the combustion of the fuel and therefore its commercial value. The industry is now interested in obtaining a method for measuring the moisture content of biofuel, quickly and reliably; preferably on delivery at the power plant. The measuring technique presented in this thesis is the first reported in the literature capable of measuring the moisture content of a large sample of such an heterogeneous material as biofuel. The equipment is today calibrated for a sample volume of 0.1 m3. A radio frequent signal is supplied from an antenna and penetrates the biofuel. Its reflection is modeled using partial least squares. As part of the work presented in this thesis, a new type of measuring rig and an analysis method for measurement of the moisture content of large samples of heterogeneous material have been developed. A statistical model for moisture content measurements of five different biofuel materials using radio waves has been built, having a root mean square error of prediction of 2.7. The interactions between biofuels and radio frequent signals have been demonstrated, indicating a variation of the reflection with varying types of biofuel material and variation in the reflection and delay of the signal with varying moisture content.

In this thesis, the microstructure of organic photovoltaic APFO-3:PC61BM bulk-heterojunction blends was examined. Earlier studies have focused on the microstructure after spin coating. This thesis aims to give a better insight into microstructural degradation as the films are annealed above the glass transition temperature, Tg, and the mixture approaches thermodynamic equilibrium. Electro- and photoluminescence studies indicate that the polymer and PC61BM are intermixed on a scale shorter than the exciton diffusion length of 10 nm, even when annealed above Tg. The temperature stability of APFO-3:PC61BM was also investigated with respect to the molecular weight of the polymer. The photovoltaic performance of these blends was found to be stable up to temperatures approaching the glass transition temperature, especially if a high molecular-weight APFO-3 grade was used.   The crystallization of PC61BM was also investigated. Above Tg, PC61BM crystallization was found to commence, albeit slowly at temperatures close to Tg. At elevated temperatures instead, micrometer sized crystals were observed to form. It was also noted that illumination while annealing APFO-3:PC61BM thin films above Tg affected PC61BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.

HgCdTe (MCT) infrared (IR) photodetectors have been used for various military and civilian applications including thermal imaging, medical imaging, and astronomy. These detectors are commonly fabricated on MCT layers grown on a foreign substrate epitaxially using delicate growth techniques such as Molecular Beam Epitaxy (MBE). The crystal quality of epitaxial layers grown on a substrate critically depends on the quality of the substrate. One of the stringent requirements in choosing the substrate material is the lattice match between grown layer and the underlying substrate. With perfectly matching lattice structure, CdZnTe has been the major substrate material for the MCT growth. The production of defect free single crystal CdZnTe bulk crystal has then attracted great attention among the research and industrial community of MCT based photodetectors. This thesis focuses on the growth and characterization of Cd1-xZnxTe crystals with the main objective of obtaining high-quality, CZT bulk crystal with large crystal sizes. To be compatible with the subsequent MCT growth, we aimed to obtain Cd0.96Zn0.04Te crystals with (211) crystal surface orientation. CdZnTe bulk crystal growths were performed in three-zone vertical Bridgman furnace by a high temperature melt process called &ldquo / Modified Bridgman Technique&rdquo / . Difficulties in both growth and characterization are presented and discussed in this report. Characterization of the grown CdZnTe crystal was performed to determine the crystallographic orientation, crystal quality, Zn distribution, IR transmission, resistivity, polarity, etch pit density, and surface properties. For this purpose, electron microscopy with analytical diagnostic tools like EDS and EBSD, XRD, optical transmission spectroscopy, and electrical measurement systems have been employed. We demonstrated the successful growth of single crystal CZT crystals using our simple Bridgman furnace. Physical properties of the grown crystal were very promising and encouraging for future applications. Crystal pieces having sizes larger than 5 x 5 mm2 with uniform Zn distribution and (211) surface orientation were obtained. IR transmission of nearly 60% which is as good as that of the commercial substrates was achieved. The electrical resistivity was much better (higher) than generally accepted values. However, the XRD results indicated the presence of defects and/or micro grains in the bulk crystal. These structures seemed to have prevented obtaining good FWHM values, which are the measure of crystal quality, in the XRD analysis.

Electric power systems are experiencing dramatic changes with respect to structure, operation and regulation and are facing increasing pressure due to environmental and societal constraints. Bulk electric system reliability is an important consideration in power system planning, design and operation particularly in the new competitive environment. A wide range of methods have been developed to perform bulk electric system reliability evaluation. Theoretically, sequential Monte Carlo simulation can include all aspects and contingencies in a power system and can be used to produce an informative set of reliability indices. It has become a practical and viable tool for large system reliability assessment technique due to the development of computing power and is used in the studies described in this thesis. The well-being approach used in this research provides the opportunity to integrate an accepted deterministic criterion into a probabilistic framework. This research work includes the investigation of important factors that impact bulk electric system adequacy evaluation and security constrained adequacy assessment using the well-being analysis framework.<p> Load forecast uncertainty is an important consideration in an electrical power system. This research includes load forecast uncertainty considerations in bulk electric system reliability assessment and the effects on system, load point and well-being indices and reliability index probability distributions are examined. There has been increasing worldwide interest in the utilization of wind power as a renewable energy source over the last two decades due to enhanced public awareness of the environment. Increasing penetration of wind power has significant impacts on power system reliability, and security analyses become more uncertain due to the unpredictable nature of wind power. The effects of wind power additions in generating and bulk electric system reliability assessment considering site wind speed correlations and the interactive effects of wind power and load forecast uncertainty on system reliability are examined. The concept of the security cost associated with operating in the marginal state in the well-being framework is incorporated in the economic analyses associated with system expansion planning including wind power and load forecast uncertainty. Overall reliability cost/worth analyses including security cost concepts are applied to select an optimal wind power injection strategy in a bulk electric system. The effects of the various demand side management measures on system reliability are illustrated using the system, load point, and well-being indices, and the reliability index probability distributions. The reliability effects of demand side management procedures in a bulk electric system including wind power and load forecast uncertainty considerations are also investigated. The system reliability effects due to specific demand side management programs are quantified and examined in terms of their reliability benefits.

The Publish/Subscribe (pub/sub) model has been widely applied in a variety of application scenarios which demand loose-coupling and asynchronous communication between a large number of information sources and sinks. In this model, clients are granted the flexibility to specify their interests at a high level and rely on the pub/sub middleware for delivery of their publications of interest. This increased flexibility and ease of use on the client side results in substantial complexity on part of the pub/sub middleware implementation. Furthermore, for several reasons including improved scalability, availability and avoiding a single point of failure, the pub/sub middleware is commonly composed of a set of collaborating message routers, a.k.a. brokers. The distributed nature of this design further introduces new challenges in ensuring end-to-end reliability as well as efficiency of operation. These challenges are largely unique to the pub/sub model and hence absent in both point-to-point or multicast protocols. This thesis develops solutions that ensure the dependable operation of the pub/sub system by exploiting the notion of overlay neighborhoods in a formal manner. More specifically, brokers maintain information about their neighbors within a configurable distance in the pub/sub overlay and exploit this knowledge to construct alternative forwarding paths or make smart forwarding decisions that improves efficiency, bandwidth utilization and delivery delay, all at the same time. Furthermore, in the face of failures overlay neighborhoods enable fast reconstruction of forwarding paths in the system without compromising its reliability and availability. Finally, as an added benefit of overlay neighborhoods, this thesis develops large-scale algorithms that bring the advantages of the pub/sub model to the domain of file sharing and bulk content dissemination applications. Experimental evaluation results with deployments as large as 1000 nodes illustrate that the pub/sub system scales well and outperforms the traditional BitTorrent protocol in terms of content dissemination delay.