Higher alcohol synthesis (HAS) from syngas or biomass-derived syngas is an important process for the production of oxygenate fuels, fuel additives and other intermediates for valueded chemical feedstock to produce medicine, cosmetics, lubricants, detergents, and polyesters. Chapter I reviews biomass to liquid fuels technology, higher alcohols being used as alternative fuels and fuel additives, the historical perspective and commercial status of higher alcohols, the catalyst system and the reaction mechanism for HAS from syngas. Chapter II discusses the Zn-Mn promoted Cu-Fe based catalyst that was synthesized by the co-precipitation method. The reaction temperature has been tested to study the influence on the catalytic performance. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbon was also very high. Cu was the active site for alcohol synthesis, iron carbide was the active site for olefin and paraffin synthesis. The reaction mechanism of HAS from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Chapter III documents the three-dimensionally ordered macroporous (3DOM) Cu-Fe catalyst developed using a glyoxylate route colloidal crystal template method. The high intrinsic activity was ascribed to three factors. First, the unique ordered structure has a large pore size and interconnected macroporous tunnels of the catalyst with a large accessible surface area to improve the catalytic activity. Second, a high density of uniformly distributed defective Cu0 and Fe5C2 nanoparticles derived from the glyoxylate route helps to provide abundant, active, and stable dual sites. Third, atomic steps on the Cu surface, induced by planar defects and lattice strain, serve as high-activity oxygenation sites. Active Fe5C2 chain-growth sites intimately surround the defective and strained form of the Cu surface, which results in a synergetic effect between the active and stable Cu–FexCy dual site for HAS. In Chapter IV, in situ ambient pressure x-ray photoelectron spectroscopy and in situ synchrotron powder diffraction were applied to identify the active site of 3DOM Cu-Fe catalyst for HAS. The results show that after syngas pretreatment of the 3DOM Cu-Fe catalyst, Cu0 is the active oxygenation site for alcohol synthesis, and Fe5C2 is the active site for carbon chain growth.

Additive Manufacturing (AM) processes are gaining prominence in industry as they can build parts to near-net-shape with minimal postprocessing. Metal laser AM techniques, such as Selective Laser Melting (SLM), offer rapid cooling rates on the order of 10^5-10^6 K/s. This is due to a highly-focused laser heating a microscopic volume in an otherwise lower-temperature environment. Hence, metal laser AM can manufacture novel, out-of-equilibrium microstructures that cannot be produced in near-net-shapes with other processes. It is desirable to optimize feedstocks for metal AM processes to leverage their advantages. One option of optimizing feedstocks is through in-situ alloying, or by using elemental powders. Elemental powders homogenize over the course of multiple laser passes, or intrinsic heat treatments. However, rapid cooling rates prevent the homogenization of a layer when first printed. To investigate the homogenization process, this thesis used synchrotron X-ray Diffraction (sXRD) to track the phase transformations during the SLM of a 14-layer single wall (single-hatch, multilayered) of Ti-1Al-8V-5Fe (Ti-185) from elemental Ti, Fe and an alloyed AlV powders, capturing frames at 250 Hz. Infrared imaging was performed simultaneously on the surface at 1603.5 Hz to observe the temperature changes at the surface. Post-mortem electron microscopy was performed on cross-sections of the wall perpendicular to the scanning direction to observe the changes in the microstructure with respect to the build direction. Specifically, Electron Dispersive X-Ray Spectroscopy and Electron Backscatter Diffraction were performed to observe the alloying elemental distribution and microstructure of the wall with respect to the build direction. The research performed found that in the melted zone, phase transformation times below 50 ms yielded a partially-alloyed microstructure, with regions concentrated and dilute in alloying elements. Partial mixing was diffusion-induced by laser beam heat and the exothermic heat of mixing of Ti-185 from its constituent elements. Further diffusion during reheating cycles yielded an alloyed microstructure. / Thesis / Master of Applied Science (MASc)

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Metastable austenitic and duplex stainless steels are widely used materials in industrial anddomestic applications, owing to their attractive characteristics such as good corrosion resistanceand favorable mechanical properties. Both types of steel experience enhanced mechanicalproperties during plastic deformation due to the formation of the martensite phase from theparent austenite phase, this is called deformation-induced martensitic transformation (DIMT).It is therefore of technical interest to study the transformation mechanism and its impact onmechanical properties for a better understanding and ultimately for developing new materialswith improved performance in certain applications. In the present thesis, two austenitic stainless steels (201Cu, HyTens® 301) and two duplexstainless steels (FDX25®, FDX27®) were investigated. Samples were tensile tested during insitusynchrotron radiation experiments performed at the Cornell High Energy SynchrotronSource (CHESS), Ithaca, USA. Tests were performed at both room temperature and at elevatedtemperatures. The collected diffraction data were then processed by software such as Fit2D andMATLAB. Quantitative phase fraction analysis based on the direct comparison method wasperformed successfully. Microstructural analysis of samples before deformation and after thefull tensile testing was also performed using electron microscopy. The deformation induced martensitic transformation took place in HyTens 301, FDX25 andFDX27, but in 201Cu the austenite was stable during the tensile tests conducted here. The a’-martensite formed in a significantly higher fraction than the ε-martensite in all alloys. At roomtemperature, the critical stress levels for martensitic transformation were 490 MPa, 700 MPaand 700MPa for HyTens 301, FDX25 and FDX27, respectively.

The durability of Thermal Barrier Coatings (TBCs) used on the turbine blades of aircraft and power generation engines has been known to be affected by sand particle ingression comprised of Calcium-Magnesium-Alumina-Silicate (CMAS). Previous studies have shown that these effects present themselves through variations in the thermomechanical and thermochemical properties of the coating. This study investigated the impact of CMAS ingression on the Yttria Stabilized Zirconia Topcoat (YSZ) and Thermally Grown Oxide (TGO) strain in sprayed Thermal Barrier Coating (TBC) samples of varying porosity with and without CMAS ingression. In-Situ Synchrotron X-ray Diffraction measurements were taken on the sample under thermal loading conditions from which the YSZ and TGO peaks were identified and biaxial strain calculations were determined at high temperature. Quantitative strain results are presented for the YSZ and TGO during a thermal cycle. In-plane strain results for YSZ near the TGO interface for a complete thermal cycle are presented, for a 6% porous superdense sample with CMAS infiltration. The outcomes from this study can be used to understand the role of CMAS on the strain tolerance of the TBC coating. It is well known that under engine operational conditions the development of the TGO layer, with large critical stresses, has been linked to failure of the coating. The growth of the TGO manifests as undulations in a series of peaks and troughs. Understanding the mechanics of the oxide layer at these locations provides significant information with respect to the failure mechanisms of the TBC coating. This study investigated the stress at the peak and trough of a TGO undulation for a cycled Dense Vertically Cracked (DVC) plasma sprayed TBC sample through photo-luminescence (PL) spectroscopy. High resolution nanoscale stress maps were taken nondestructively in the undulation of the TGO. Preliminary results from first line mapping of TGO peak and trough scan, at a resolution of 200 nm, have shown a non-uniform TGO stress variation. The results obtained from this study can be used to understand the stress variation in the peak and trough of a DVC sample's TGO undulation and how it contributes to the life of the TBC coating.

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Soil carbon (C) and nitrogen (N) are predominantly in organic form. Proteins/ peptides, as an important organic form of N, constitute a substantial part of soil organic matter. On one hand, proteins/peptides are an important N source for plants and microorganisms, particularly in soils where inorganic N is limited. On the other hand, their stabilization in soils by forming organo-mineral associates or macromolecule complex reduces the C loss as CO2 into the atmosphere. Therefore, studies on the turnover, abundance, composition, and stability of proteins/peptides are of crucial importance to agricultural productivity and environmental sustainability. In the first part of this study, the bioavailability and distribution of amino acids, (building block of proteins/peptides), were investigated, in soils across the North-South and West-East transects of continental United States. The second part of this study aimed to understand the variations of organic C speciation in soils of continental United States. Previous investigations of the interactions between soil minerals and proteins/peptides were mostly limited to batch sorption experiments in labs, seldom of which gave the details at the molecular scales. Therefore, in the third part of this study, the molecular orientation of self-assembled oligopeptides on mineral surfaces was investigated by employing synchrotron based polarization-dependent Near Edge X-ray Adsorption Fine Structure Spectroscopy (NEXAFS) techniques. Specific aims of this study were: 1) to assess potentially bioavailable pool of proteinaceous compounds and the immediately bioavailable pool of free amino acids in surface and subsurface soils of various ecosystems; 2) to evaluate the relationship between environmental factors and levels/composition of the two pools; 3) to investigate the organic C speciation in soils of various land use; and 4) to understand molecular level surface organization of small peptides on mineral surfaces. The levels of free amino acids and hydrolysable amino acids which represent the potentially bioavailable pool of proteinaceous compounds in A-horizon soils were significantly high than in C-horizon soils due to the accumulation of organic matter in surface. On average, free amino acids accounted for less than 4 % of hydrolysable amino acids which represent the total proteinaceous compounds in soils. The composition of free amino acids was significantly different between surface soil and subsurface soil and was significantly influenced by mean annual temperature and precipitation. A relatively uniform composition of hydrolysable amino acids was observed irrespective of a wide range of land use. Significant variations were observed for the levels of free and hydrolysable amino acids along mean annual temperature and precipitation gradients, as well as among vegetation types of continental USA, suggesting levels of free and hydrolysable amino acids were associated with the above-ground biomass and root distribution. Organic C speciation investigation revealed the presence of carboxylic-C (38%), aliphatic-C (~ 22%), aromatic-C (~ 18%), O/N-alkyl-C (~ 16%), and phenolic-C (< 6%). Factors such as temperature and vegetation cover were revealed in this study to account for the fluctuations of the proportions of aromatic-C and phenolic-C, in particular. Phenolic-C may serve as a good indicator for the effect of temperature or vegetation on the composition of SOC. The average composition of soil organic C, over the continental scale, was relatively uniform over various soil ecosystems and between two soil horizons irrespective of surface organic C content. Polarization dependent NEXAFS analysis showed the oligopeptides tend to orient on mineral surface with an average tilt angle of 40 ° between the molecular chain and the mineral surface. / Ph. D.

Demands for designing prime reliant, energy-efficient, and high performance thermal barrier coatings (TBCs) in gas turbines have led to a growing interest toward comprehensive microstructural characterization. Over the last decade, Synchrotron X-ray Diffraction (XRD) has established itself as a high-resolution strain measurement method for the thermally grown oxide (TGO) layer of thermal barrier coatings (TBCs). In this work, we present in-situ X-ray strain measurements of the TGO layer on cycled TBC specimens under thermo-mechanical loading using powerful high energy X-rays (~80.7- 86 keV) at Sector I-ID of the Advanced Photon Source at the Argonne National Laboratory. The evolution of TGO stresses was examined over one complete thermal cycle on TBC samples at various stages of the life fraction under various mechanical loads. Synchrotron X-Ray Diffraction under thermo-mechanical loading has shown the existence of strain qualitatively within the diffraction patterns. Quantitative results obtained through Pseudo-Voigt peak fitting over selected peaks show the evolution of strain over a thermal cycle. In initial experiments, it was shown that mechanical loading at 32 MPa resulted in a tensile strain (£22 = 0.00053±0.00039 for 7 minutes) along the [024] atomic plane of a-AbO3 that was brief before going into strain relief in the compressive region but higher in magnitude than the 64 MPa (£22 = 0.00039±0.00024 for 14 minutes). Follow-on experiments indicate the presence of tensile strains within the bond coat region of the TBC system. After initial assessment of the effect of mechanical loading, our findings indicate that the effect of mechanical load during the cycle, often neglected in TBC studies, is of significance to the strain evolution within each cycle. This determination of critical conditions for strain evolution ( e.g. the first cycle) will serve to improve overall accuracy in life prediction of these coatings and contribute to developing methods of improving fatigue behavior.