Ball milling has been shown to produce nanostructures in metal powders through severe repetitive deformation. Ball milling at cryogenic temperatures (cryomilling) is more effective in this capacity due to the low temperature by slowing recovery and minimizing diffusion distances between different components. Nanostructured metals are of interest because of their unique physical and mechanical properties. The result of cryomilling is powder consisting of crystallites on the order of 30 – 50 nm. In order to characterize the properties of this material, it is often necessary to consolidate the powder, which is often difficult without causing significant grain growth. In this work, aluminum-rich and magnesium-rich alloys of varying composition are produced by cryomilling and characterized by x-ray diffraction. A novel consolidation process called high shear powder consolidation (HSPC) is used to densify as-received and as-milled powders with minimal growth. The construction of a cryomill, along with a modification for improving process yield, has provided a platform for the study of nanocrystalline metals. It has been shown that bulk nanocrystalline materials are attainable and that alloy composition influences mechanical properties. / Master of Science

Feldspars are one of the archetypical families of framework silicates. They not only comprise around 60% volumetrically of the Earth's crust, but are among some of the most structurally complicated minerals. Investigation into the structural behavior of various intermediate plagioclases at pressure has been undertaken with the intent of categorizing the elastic behavior with pressure across the solid solution series and establishing a conceptual model to characterize feldspar compression. Complex behavior has been observed in the Equation of State for plagioclase feldspars in excess of 3 GPa, including an anomalous softening of ordered albite in excess of 8.4 GPa (Benusa et al 2005: Am Min 90:1115-1120). This softening was not observed in the EoS for the more intermediate plagioclase compositions containing between 20 and 40 mol% of end-member anorthite. The calculated elastic compliance tensor sums at room pressure show a general stiffening with increasing anorthite component, small elastic changes at the C-1 to I-1 transition, and a dominantly first-order response at the P-1 to I-1 transition near end-member anorthite. The crystal structure of An37 plagioclase was determined by single-crystal X-ray diffraction. The compression mechanisms in An37 are similar to those in albite at lower pressures. The softening in albite at higher pressures is therefore attributed to the structural shearing in albite that is absent in An37 plagioclase up to 9.5 GPa. / Master of Science

No / Solvent influences on the crystallization of polymorph and hydrate forms of the nootropic drug piracetam (2-oxo-pyrrolidineacetamide) were investigated from water, methanol, 2-propanol, isobutanol, and nitromethane. Crystal growth profiles of piracetam polymorphs were constructed using time-resolved diffraction snapshots collected for each solvent system. Measurements were performed by in situ energy dispersive X-ray diffraction recorded in Station 16.4 at the synchrotron radiation source (SRS) at Daresbury Laboratory, CCLRC UK. Crystallizations from methanol, 2-propanol, isobutanol, and nitromethane progressed in a similar fashion with the initial formation of form I which then converted relatively quickly to form II with form III being generated upon further cooling. However, considerable differences were observed for the polymorphs lifetime and both the rate and temperature of conversion using the different solvents. The thermodynamically unstable form I was kinetically favored in isobutanol and nitromethane where traces of this polymorph were observed below 10°C. In contrast, the transformation of form II and subsequent growth of form III were inhibited in 2-propanol and nitromethane solutions. Aqueous solutions produced hydrate forms of piracetam which are different from the reported monohydrate; this crystallization evolved through successive generation of transient structures which transformed upon exchange of intramolecular water between the liquid and crystalline phases

No / Four new ternary crystalline molecular complexes have been synthesised from a common 3,5-dinitrobenzoic acid (3,5-dnda) and 4,4'-bipyridine (bipy) pairing with a series of amino-substituted aromatic compounds (4-aminobenzoic acid (4-aba), 4-(N,N-dimethylamino)benzoic acid (4-dmaba), 4-aminosalicylic acid (4-asa) and sulfanilamide (saa)). The ternary crystals were created through the application of complementary charge transfer and hydrogen-bonding interactions. For these systems a dimer was created through a charge-transfer interaction between two of the components, while hydrogen bonding between the third molecule and this dimer completed the construction of the ternary co-crystal. All resulting structures display the same acidpyridine interaction between 3,5-dnba and bipy. However, changing the third component causes the proton of this bond to shift from neutral OHN to a salt form, O(-) HN(+) , as the nature of the group hydrogen bonding to the carboxylic acid was changed. This highlights the role of the crystal environment on the level of proton transfer and the utility of ternary systems for the study of this process.

Yes / Spurred by the enormous interest in co-crystals from the pharmaceutical industry, many novel co-crystals of active pharmaceutical ingredients have been discovered in recent years and this has in turn led to an increasing number of reports on polymorphs of co-crystals. Hence, a thorough characterization and understanding of co-crystal polymorphs is a valuable step during drug development. The purpose of this study is to perform in situ structural analysis and to determine thermodynamic stability of a dimorphic co-crystal system, 1:1 caffeine-glutaric acid (CA-GA, Forms I and II). We performed thermal and structural characterizations by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), hot-stage microscopy (HSM), slurry and in situ variable temperature X-ray diffraction (VTXRD). For completeness, we have also re-determined crystal structures of CA-GA Forms I and II at 180 K using single crystal X-ray diffraction. Our results revealed that Form II is stable and Form I is metastable at ambient conditions. Further, the results suggest that the dimorphs are enantiotropically related and the transition temperature is estimated to be 79 Celcius degrees. / This work was supported by Science and Engineering Research Council of A*STAR (Agency for Science, Technology and Research), Singapore.

The objective of this thesis is to improve understanding of the development of corrosion products (scales) that form on the inner walls of carbon steel pipelines in CO2-rich (sweet) oilfield environments. If well adherent to the carbon steel surface, such scales can significantly reduce the metal’s rate of corrosion. Typically, the open literature labels sweet corrosion scale as ferrous (II) carbonate (FeCO3) or siderite, although this may not always be the case. For example, Fe2(OH)2CO3 (chukanovite) and Fe3O4 (magnetite) are known to modify the protective character of a sweet corrosion product scale. Practical electrochemical methods for the assessment of substrate corrosion, and electron/photon-based characterisation techniques for investigating scale structure and composition, have revealed interesting aspects of the nature of sweet corrosion scale development on model high purity Fe and real-world pipeline steel surfaces. Concerning scale development on model Fe substrates immersed in CO2-saturated deionised water (buffered to pH = 6.8, T = 80°C, Ptotal = 1 bar), electrochemical data supplemented by grazing incidence x-ray diffraction (GIXRD) and scanning electron microscopy (SEM) show that a semi-protective mixed corrosion scale comprising siderite and chukanovite becomes a highly protective siderite scale with longer exposure time. The introduction of sodium chloride to the CO2-saturated solution (T = 80°C, pH = 6.8, Ptotal = 1 bar) impedes the rate of scale formation. Increasing [NaCl] from the start of experiment is suspected to limit the precipitation kinetics of sweet corrosion scale crystals, since chukanovite is no longer observed, and siderite formation is somewhat slowed as well. SEM imaging, using an electronic workfunction-sensitive detector (in lens), reveals nanoscale deposits on the corroded Fe surface in regions that are devoid of µm-scale crystals. With the Raman spectra from these regions considered, it is interpreted that the nanoscale deposits are likely amorphous iron carbonate, albeit oxidised to a significant extent. Moving to real-world carbon steel immersion in sweet solutions, a scale comprising predominantly chukanovite is observed (using GIXRD and SEM) on the 1% Ni weld zone (WZ) surface of a pipeline weld-joint, but not on adjacent, distinct regions (heat affected zones (HAZ) and base metal (BM)). This selective scaling is suggested to be due to some initial corrosion of the weld-joint, which generates sufficient [Fe2+(aq)], and a macro-galvanic effect across the weld, i.e. WZ is cathodic to HAZ and BM. Further, to gain mechanistic insight into compositional changes during sweet corrosion scale growth, an electrochemical cell for in situ GIXRD (named E-cell) has been developed and commissioned. Diffraction patterns acquired using synchrotron radiation, from a pipeline steel surface, reveal the formation and temporal evolution of a multicomponent corrosion scale. Accompanying electrochemical data suggest that the scale is quite protective.

No description available.

The objective of this research is to develop a water-based processing method for incorporating large filler loadings into nanocomposite systems. Specifically, cellulose nanocrystal/poly(vinyl alcohol) (CNC/PVA) nanocomposite aqueous suspensions and films were processed and characterized at CNC loadings up to 67 wt.% with respect to polymer concentration. Both aqueous suspended and freeze-dried CNCs were studied with this method. Two methods for incorporating the CNCs were investigated: solution processing and batch mixing of aqueous suspensions. The materials produced by these methods were characterized using rheology of aqueous suspensions and a method for understanding the morphology of these aqueous suspension through rheological characterization was developed. The CNC/PVA suspensions were dried and the structure of the film studied using x-ray diffraction, Fourier transform infrared spectroscopy, and differential scanning calorimetry. With regard to characterization of polymer structure by these methods, PVA crystallinity was seen to increase with increasing CNC loading. Finally, dynamic mechanical analysis and micro-tensile testing were conducted on consolidated films and CNCs were seen to increase modulus, yield stress but decrease strain at failure. Biodegradation studies were also conducted and CNCs were seen to increase the biodegradation characteristics of PVA. While the general trends in experimental data were the same, differences in properties between systems made with solution processing and batch mixing were observed, attributed to differences in the CNC dispersion. Overall, results indicated that this methodology is feasible for the industrially scalable production of highly loaded nanocomposites.

Analysis of the molecular speciation of organic compounds in solution is essential for the understanding of ionic complexation. The Raman spectroscopic technique was chosen for this purpose because it allows the identification of compounds in different states and it can give information about the molecular geometry from the analysis of the vibrational spectra. In this research the ionisation steps of relevant pharmaceutical material have been studied by means of potentiometry coupled with Raman spectroscopy; the protonation and deprotonation behaviour of the molecules were studied in different pH regions. The abundance of the different species in the Raman spectra of aqueous salicylic acid, paracetamol, citric acid and salicylaldoxime have been identified, characterised and confirmed by numerical treatment of the observed spectral data using a multiwavelength curve-fitting program. The non-destructive nature of the Raman spectroscopic technique and the success of the application of the multiwavelength curve-fitting program demonstrated in this work have offered a new dimension for the rapid identification and characterisation of pharmaceuticals in solution and have indicated the direction of further research. The work also covers the formation of novel cocrystal systems with pharmaceutically relevant materials. The existence of new cocrystals of salicylic acid-nicotinic acid, DLphenylalanine , 6-hydroxynicotinic acid, and 3,4-dihydroxybenzoic acid with oxalic acid have been identified from stoichiometric mixtures using combined techniques of Raman spectroscopy (dispersive and transmission TRS), X-ray powder diffraction and thermal analysis. Raman spectroscopy has been used to demonstrate a number of important aspects regarding the nature of the molecular interactions in the cocrystal. Cocrystals of salicylic acid - benzamide, citric acid-paracetamol and citric acid -benzamide have been identified with similar analytical approaches and structurally characterised in detail with single crystal X-ray diffraction. From these studies the high selectivity and direct micro sampling of Raman spectroscopy make it possible to identify spectral contributions from each chemical constituent by a peak wavenumber comparison of single-component spectra (API and guest individually) and the two- component sample material (API/guest), thus allowing a direct assessment of cocrystal formation to be made. Correlation of information from Raman spectra have been made to the X-ray diffraction and thermal analysis results. Transmission Raman Spectroscopy has been applied to the study cocrystals for the first time. Identification of new phases of analysis of the low wavenumber Raman bands is demonstrated to be a key advantage of the TRS technique.

This investigation centers on early concrete technology used in Seguin, Texas, during the mid-19th century. Over the course of fifty years, more than ninety concrete structures were built in Seguin. Over the last century, these have dwindled to twenty extant structures. Much of the previous Seguin concrete era research has focused on the historical narrative and architectural description. This study aims to answer questions that previous research has not — it investigated the raw materials used in making Seguin’s concrete. The results provide new information about the Seguin concrete structures, providing guidance for their long-term maintenance. The materials analysis uses instrumental techniques such as scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray diffraction to determine the chemical composition and crystalline structure of the cement binder from several extant structures in Seguin. Gathering both qualitative and quantitative data for the binder allowed us to identify the raw materials used in the concrete and better understand the construction methods. Studying the materials and methods increased our understanding of these historic structures and will inform future preservation efforts. / text