The langasites are a class of geometrically frustrated compounds with the formula A3XY3Z2O14 where A,X,Y,Z are cationic sites and site A is occupied by a magnetic ion. The interactions of the magnetic ions form a star shaped pattern called the Kagomé lattice. The langasites have been widely studied by the solid state community because of their functional properties such as piezoelectricity, multiferroicity, ferroelectricity, dielectricity and for use in the telecommunication industry. It was also realized that some langasite materials exhibit exotic magnetic ground states at low temperatures. A thorough understanding of their ground state is limited by the difficulty in synthesizing new members belonging to this series due to the formation of competing phases such as the garnets. In this study, four new magnetic langasites A3Ga3Ge2BeO14 (A= Pr, Nd, Sm and Eu) and a non-magnetic lattice standard La3Ga3Ge2BeO14 were synthesized. These were further structurally characterized by powder X-ray diffraction, Rietveld refinement and bond valence analysis. Further characterization of the low-temperature magnetism was done by performing magnetization, magnetic susceptibility (field cooled and zero field cooled) and heat capacity measurements. The low temperature spin dynamics were probed using muon spin resonance performed at TRIUMF (Vancouver) and elastic and inelastic neutron scattering measurements performed at the DCS (NIST) and D7 (ILL). From all the above measurements it can be concluded that the new Be langasites exhibit net antiferromagnetic interactions at low-temperatures with clear signs of diffuse scattering for Nd3Ga3Ge2BeO14 using inelastic neutron scattering measurements. There was no evidence of magnetic long-range ordering down to as low as 0.025 K. Based on the obtained measurements these new Be-langasite compounds can be classified as potential spin liquid candidates. / February 2017

Abstract Methylammonium lead (II) iodide has recently attracted considerable interest which may lead to substantial developments of efficient and inexpensive industrial photovoltaics. The application of this material as a light-absorbing layer in solid-state solar cells leads to impressive efficiency of over 22% in laboratory devices. However, for industrial applications, fundamental issues regarding their thermal and moisture stability need to be addressed. MAPbI3 belongs to the perovskite family of materials with the general formula ABX3 ,where is the organic cation (methylammonium) which is reported to be a major source of instability. In this work, a variety of alkyammonium lead (II) iodide materials have been synthesized by changing the organic cation, to study the relationship between the structural and physical properties of these materials. [(A)PbI3] and (A)PbI4 series were studied. Three dimensional (3D) networks (MAPbI3,MAPbBr3), two dimensional (2D) layered systems (BdAPbI4, HdAPbI4, OdAPbI4), and one dimensional (1D) columns (EAPbI3, PAPbI3, EAPb2I6) were found for the materials. [PbI6] octahedral structural units were repeated through the material network depending on the dimensionality and connectivity of the materials. Where a bulkier cation was introduced, the crystallographic unit cell increased in size which resulted in lower symmetry crystals. The connectivity of the unit cells along the material networks was found to be based on corner-sharing and face-sharing. Lower dimensionality resulted in larger bandgaps and lower photoconductivity, and hence a lower light conversion efficiency for the related solar cells. The thermal and moisture stability was greater in the 1D and 2D materials with bulkier organic cations than with methylammonium. In total, an overview is provided of the relationship between the chemical dimensionality and physical properties of the organic-inorganic lead halide materials with focus on the solar cell application. / Svenska sammandrag: Metylammoniumbly(II)jodid har under de senaste åren genererat ett stort intresse som ett möjligt material for utveckling av effektiva och på industriell skala billiga solceller. Detta material har använts som ljusabsorberande skikt i fasta solceller med imponerande omvandlingseffektiviteter på över 22% för solceller i laboratorieskala. För att denna nya typ av solceller ska bli intressanta för produktion på industriell skala, så behöver grundläggande frågeställningar kring materialens stabilitet avseende högre temperaturer och fukt klargöras. MAPbI3 har formellt perovskitstruktur med den allmänna formel ABX3, där A utgörs av den organiska katjonen (metyammoniumjonen) och som kan kopplas till materialets instabilitet. I denna avhandling har olika alkylammoniumbly(II)jodidmaterial syntetiserats där den organiska katjonen modifierats med syftet att studera växelverkan mellan struktur och fysikaliska egenskaper hos de resulterande materialen. Material av olika dimensionalitet erhölls; tredimensionella (3D) nätverk (MAPbI3, MAPbBr3), tvådimensionella (2D) skiktade strukturer (BdAPbI4, HdAPbI4, OdAPbI4), och endimensionella (1D) kedjestrukturer (EAPbI3, PAPbI3, EAPb2I6). Flera nya lågdimensionella material (2D och 1D) tillverkats och karaktäriserats för första gången. Enkristalldiffraktometri har använts för att erhålla materialens atomära struktur. Strukturen hos material tillverkade i större mängder konfirmerades genom jämförelse mellan resultat från pulverdiffraktion och enkristalldiffraktion. Den oktaedriska strukturenheten [PbI6] utgör ett återkommande tema i materialen sammankopplade till olika dimensioner. Då större organiska katjoner används karaktäriseras i regel strukturerna av större enhetsceller och lägre symmetri. De lågdimensionella materialen ger typiskt störe elektroniskt bandgap, lägre fotoinducerad ledningsförmåga och därför sämre omvandlingseffektiviteter då de används i solceller. De lågdimensionella materialen (1D och 2D) som baseras på de större organiska katjonerna uppvisar bättre stabilitet med avseende på högre tempereratur och fukt. De tvådimensionella materialens elektroniska struktur har karaktäriserats med hjälp av röntegenfotoelektronspektroskopi, liksom röntgenabsorptions- och emissionsspektroskopi. Resultat från teoretiska beräkningar stämmer väl överens med de experimentella resultaten, och de visar att materialens valensband huvudsakligen består av bidrag från atomorbitaler hos jod, medan atomorbitaler från bly främst bidrar till edningsbandet. Sammantaget erbjuder avhandlingen en översikt av sambandet mellan kemisk dimensionalitet och fysikaliska egenskaper hos ett antal organiska/oorganiska blyhalogenidmaterial med fokus på tillämpning i solceller. / <p>QC 20170123</p>

Ce travail de thèse vise à étudier les propriétés structurales et diélectriques des échantillons céramiques appartenant au système Ba1-xRxTi1-yZryO3 (R = Ca, Sr). Les échantillons sous forme de poudre, micro ou nano structurées, ont été respectivement obtenus par la méthode des mélanges d'oxydes et la méthode du précurseur polymèrique. À partir des échantillons sous forme de poudre micro ou nano-structurés, les échantillons céramiques ont été obtenus grâce à un procédé de frittage à haute température. Les échantillons sous forme de céramiques en poudres micrométriques ont été obtenus par la méthode traditionnelle de frittage à haute température alors que céramiques constituées de particules de taille nanométrique ont été obtenus en utilisant la technique de Spark Plasma (ou Spark Plasma Sintering, SPS). Les propriétés structurales et électriques de ces deux séries d'échantillons ont été caractérisées par diffraction des rayons X à haute résolution (XRD), spectroscopie d'impédance complexe, spectroscopie d'absorption des rayons X et la spectroscopie Raman. Grâce aux données de diffraction des rayons X il a été possible de suivre le processus de transition de phase dû à la substitution des atomes de titane par du zirconium. Les mesures électriques montrent que lorsque la quantité de Zr augmente, l'échantillon passe d'u n état ferroelectrique normal à un état ferroélectrique relaxeur. Les mesures du spectre d'absorption et le spectre Raman ont été utilisées pour établir une relation entre la structure locale et des propriétés électriques de ces matériaux. Enfin, l'analyse des résultats obtenus avec des céramiques nanostructurés montrent que la réduction de la taille des particules entraîne une diminution de la température maximale et un petit élargissement de la courbe de la permittivité diélectrique. Toutefois, il n'y avait aucun changement de l'état ferroélectrique, normal ou relaxeur, de ces échantillons / The aims of this work is to study the structural and electrical properties of ceramic samples belonging to the Ba1-xRxTi1-yZryO3 (R = Ca, Sr) system. The powder samples presenting a micro or nanosize were respectively obtained by using a mixture of oxides and by the modified polymeric precursor methods. From the samples in a powder form, micro or nanosize, sintered ceramic samples were obtained through a sintering process at high temperature. Micrometer scale ceramic samples were obtained through the traditional method of sintering at high temperature while nano-sized particles ceramics were obtained using the spark Spark Plasma Sintering SPS technique. The structural and electrical properties of these two sets of samples were characterized using High resolution X-ray diffraction (XRD), complex impedance spectroscopy and X-ray absorption and Raman spectroscopy's. Through the data of XRD it was possible to follow the processes of phase transition due to the substitution of Ti by Zr atoms. Electrical measurements showed that as the amount of Zr increases, the sample passes from a normal ferroelectric state to a relaxor state. Measurements of the absorption and Raman spectra were used to establish a relationship between local structure and electrical properties displayed by these materials. These properties were characterized by the shape of the dielectric permittivity curves versus temperatures. Two principal characteristics were analysed : the maximum Tm and the width ∆T. Finally, the analysis of results obtained with nanostructured ceramic samples showed that reducing the particle size leads to a decrease of Tm, and a small increase of ∆T. However, there was no change from normal to relaxor ferroelectric states

In accordance with the 2010 Dodd-Frank Act, conflict minerals refer to gold, tantalum, tin, and tungsten bearing minerals sourced from the Democratic Republic of Congo (DRC) that have been mined illegally and used to funnel funds to rebel forces. In response to an increasing demand for these metals used in cellphones, computers, and other popular technologies, Dodd-Frank mandates that industrial consumers demonstrate due diligence and assure that the materials they use have been extracted legally. Because current chain-of-custody methods have not been effective in sourcing ores, a study was undertaken whereby the range of mineralogical characteristics of 15 samples along the wolframite solid solution series were determined in order to ascertain if differences in these characteristics would permit fingerprinting of the source deposit of wolframite, of which the DRC is the world's fifth largest producer. For these 15 samples, single-crystal X-ray structure and powder X-ray diffraction studies have been conducted; major, minor and trace element chemistry has been determined using ICP-MS and ICP-OES; and Raman spectroscopy has been carried out. Finally, statistical methods were used to determine relationships between samples, and the results of that mathematical work show that there is no firm method at the present time of determining the provenance of a sample based on the information of the crystal structure, diffraction patterns, vibrational frequencies/scattering, or major and trace elemental chemistry. This study elucidates the range of mineralogical properties along the hübnerite-ferberite solid solution series while working towards to development of an analytical technique that is affordable, practical, accessible and effective for industrial consumers seeking product certification and compliance with the 2010 Dodd-Frank Act.

This research, is initiated to systematically study the microstructure of AISI 4340 steel prior to impact, after impact and after post-impact annealing to determine the effect of the pre-deformation microstructure on the nucleation and initiation of ASBs, and the mechanism of evolution of ASBs during impact. This study used state-of-the-art microstructural characterization techniques such as the FIB and STEM/HRTEM to reveal that initial microstructural inhomogeneity produces nucleation sites for the initiation of ASBs during impact. It was observed that double misfit interfaces and boundary layers, formed around precipitated carbides (interface between reinforcements and matrix), increased the volume fraction of dislocation sources within the pre-impact specimens. It is demonstrated that the intersection of an activated dislocation source with the direction of maximum shear (regions of stress concentrations) within the specimens during impact, is a necessary condition for the points of intersection to act as possible sites for the nucleation and initiation of ASB depending on the rate of dislocation generation, local strain and strain rate. In addition, the structure that evolves after strain localization starts out with elongation of the grains in the shear direction with the initiation of random and transverse dislocation boundaries along the elongated grains. The elongated grains break along the initiated dislocation boundaries as strain/strain rate increases resulting in the creation of smaller elongated-broken grains and nanograins. Boundary refinement of the broken grains occurring through grain rotation and adiabatic heating results in the evolution of refined grains, subgrains and nanograins. The presence of elongated grains, broken grains, refined grains, subgrains and nanograins within the evolved shear band structures demonstrate that the local deformation is dependent on the imposed local strain and strain rate and that these mechanisms occur concurrently during impact. The results obtained, which are specific to the behavior of BCC ferritic Pearlitic hardenable steels, lead to the conclusion that the evolution of ASBs is a simultaneous layering of microstructures initially driven by dislocations which produce the final structures observed in the shear bands at the end of passage of the stress wave. / February 2015

<p>GaAs1-xBix is a III-V semiconductor alloy which has generated much fundamental scientific interest. In addition, the alloy possesses numerous device-relevant beneficial characteristics. However, the synthesis of this material is very challenging and its properties are not well understood. The focus of this dissertation is to advance the understanding of its synthesis using molecular beam epitaxy (MBE) and, as a result, improve its key as-grown properties that are of great importance to device applications, such as increasing Bi concentration in the alloy and enhancing its optical emission efficiency.</p><p>In chapter 3, the discovery of a trade-off between the structural and optical characteristics of GaAs1-xBix , controlled by the degree to which the growth is kinetically-limited, is described. Chapter 4 discusses the exploitation of a growth method that utilizes the spatial distribution of MBE fluxes to facilitate numerous studies of the critical dependence of GaAs1-xBix characteristics on the V/III flux ratio. Chapter 5 describes the results of experiments utilizing vicinal substrates to modify both Bi incorporation and optical emission efficiency of synthesized GaAs1-xBix and enable new understanding of the Bi incorporation mechanism. Specifically, incorporation primarily at A steps, defined as the steps generated by misorienting the GaAs (001) substrate toward the (111)A surfaces, enhances Bi incorporation but reduces optical emission efficiency. Chapter 6 describes the identification of two new signatures in the Raman spectra of GaAs1-xBix that can be used to determine the Bi content and the hole concentration of nominally undoped GaAs1-xBix. Finally, in Chapter 7 the GaAs1-xBix growth using pulsed Ga fluxes is described. The use of pulsed-growth significantly modifies the incorporation of Bi and suggests it is a promising method for widening the GaAs1-xBix MBE growth window enabling improved synthesis control and materials properties.</p> / Dissertation

Power generation in thermal stations typically relies on large steam turbines. The corrosion resistant steel blades used in the last stage of a typical low pressure rotor set are approximately 1m long and experience high centrifugal loading during service. They operate in a wet steam environment, at approximately 60°C while rotating at 3000rpm, and failure modes include high and low cycle fatigue, stress corrosion cracking or corrosion fatigue. The blades are retained by a fir tree root which is normally shot-peened to generate compressive residual stresses that resist crack initiation. Finite element (FE) modelling has indicated that, in the absence of shot-peening, stresses above yield are induced at the fir tree root during operation. In a shot-peened blade these lead to relaxation of the shot peening residual stresses. To date, no systematic information has been obtained on the level of residual stresses induced in the fir tree by shot-peening and their subsequent relaxation during service loading, nor are there any guidelines as to the magnitude of residual stresses necessary to ensure integrity of the turbine over a life span of at least twenty years. At least one of these blades has suffered catastrophic failure in recent years causing severe damage, in excess of €100M, to the turbine-generator set on a South African power station [1]. This thesis reports results from a comprehensive program of residual stress measurements at the shot-peened fir tree roots of service blades, and in specimens that simulate the root conditions, using diffraction data from laboratory and synchrotron X-ray radiation (SXRD). Shot-peening coverage between 75% and 200% was used and stresses were measured over a depth of 5mm into the blades/specimens. Measurements were made in the as-peened condition and after applying cyclic stresses representative of overspeed proof testing and of service operation. The results were used to calibrate FE modelling of residual stresses and as input into fatigue life prediction.

Recently, Heusler alloys are studied for their interesting magnetic and electronic properties. These properties are strongly dependent on the crystallographic struc- ture. This work deals with Heusler alloys of the A2BC type. We have powder samples and single-crystaline samples for our study as well. An object of interest was a description of crystallographic structure of the samples, site occupation numbers of each type of atoms and their possible occupation disorder. Pow- der difraction and EXAFS have been measured on the powder samples. Clasical single-crystal diffractions has been meassured on the single-crystaline samples. In the case of a modulated structure in the samples, satelite difractions have been measured too. 1

The synthesis of NaxCoO2 by Pechini method (with initial sodium stoichiometry x = 1.0, 0.9, 0.8, and 0.7) was studied for the samples heat-treated in the temperature range from 550 řC to 750 řC. The structure characterization and phase composition was carried out by the powder X-ray diffraction (XRD) analysis. The elementary analysis was done using atomic absorption spectroscopy. From the thermoelectric properties, the Seebeck coefficient was measured for both α- and γ- phase. The Weiss constant was determined for α- and γ- phase by linear regression of 1/χ. The real sodium content in sodium cobaltate phase was found to be independent on initial sodium precursor weight and measurement by PXRD and Seebeck coefficient showed that the sodium content in NaxCoO2 falls in the range from x = 0.65 to 0.75. The magnetization measurements showed presence of spinel Co3O4 impurities in the samples and the analysis of magnetic susceptibility showed unusual high values of the Weiss constant for α- phase in comparison with structurally similar γ- NaxCoO2. Thin film of NaxCoO2 with initial sodium stoichiometry x = 1.0, 0.52, 0.32, and 0.175 was deposited by chemical solution deposition method using spin-coating deposition on a 00l-oriented α-Al2O3 single crystal substrate. The formation and structure characterization of...

Doctor of Philosophy / Department of Biological and Agricultural Engineering / Yong Cheng Shi / Donghai Wang / Cellulosic ethanol made from low cost lignocellulosic biomass has been considered as new generation transportation fuel with economic and environmental advantages. Photoperiod-sensitive (PS) sorghum, because of its high biomass yield (2.6 kg dry mass/m2), about 18% of soluble sugar in dry mass, and drought tolerance, is a promising biomass for ethanol production. The overall goals of this study are to develop an efficient approach to convert PS sorghum to ethanol and to understand the structural characteristics of biomass. For increasing the efficiency of biomass conversion, an integrated method, using diluted sulfuric acid pretreatment, has been developed to utilize both the structural polysaccharide (cellulose) and the soluble sugar (sucrose, glucose, and fructose) for fermentation. Response surface methodology was employed to optimize the pretreatment condition for maximizing the cellulose-glucose conversion. Simultaneous enzymatic hydrolysis and yeast fermentation was used for ethanol production. The effects of the buffer concentration, the inoculation dosage and time, and the fermentation temperature were investigated for maximizing ethanol yield. A total conversion efficiency of 77.2% and an ethanol concentration of 2.3% (v/v) were obtained after 72 h fermentation. About 210 kg (~266 Liters) ethanol could be produced from one ton dry mass of PS sorghum under the optimized condition. The structural features of the PS sorghum were studied using techniques including scanning electron microscopy and X-ray diffraction/scattering. Biomass at different botanic locations was investigated. Wide-angle X-ray diffraction (WAXD) study showed that the PS sorghum rind had oriented crystal peaks and the highest degree of crystallinity, whereas the crystalline structures of the inner pith and leaf were less ordered. The results from WAXD suggested that crystalline cellulose was melted at 120 °C before its significant degradation. Both the cellulose crystallinity and the crystal size at the dimension lateral to fiber direction increased as the temperature increased from 120 to 160 °C. The efficiency of enzymatic hydrolysis increased because the protective structure was damaged and most hemicellulose was removed, resulting in the increase in accessible area as suggested by small-angle X-ray scattering result of the increased length of microvoids. The results from WAXD also suggested a simultaneous hydrolysis and crystallization of cellulose by acid.