The ion implantation process is a very precise, controllable, and reproducible method used to enhance material properties of finished components such as ball bearings. Essentially, the target material is bombarded by accelerated ions to form a thin alloyed layer in the substrate. As the ions deposit their kinetic energy in the target it begins to heat up. To prevent thermal distortion in the finished pieces the ion implantation is performed at dose levels (dependent on the ion fluence and time duration of implantation) to insure that the target pieces stay at relatively low temperatures. Consequently, the low temperature requirement for many applications limits the economic, and probably, the physical success of ion implantation. The purpose of this study was to show the applicability of using a two-dimensional computer code developed to model plasma disruptions and subsequent energy deposition on a fusion reactor first wall to calculate surface and bulk temperature information during ion implantation. In turn the code may assist researchers pursuing development of adequate cooling for target materials in an attempt to overcome the low temperature constraint. All data supported the hypotheses that the two-dimensional code previously developed for fusion reactor applications was adequate to model the ion implantation process. / Graduation date: 1992

This thesis explores the thermal expansion and high pressure behavior of some materials with the ReO₃ structure type. This structure is simple and has, in principle, all of the features necessary for negative thermal expansion (NTE) arising from the transverse thermal motion of the bridging anions and the coupled rotation of rigid units; however, ReO₃ itself only exhibits mild NTE across a narrow temperature range at low temperatures. ReO₃ is metallic because of a delocalized d-electron, and this may contribute to the lack of NTE in this material. The materials examined in this thesis are all based on d⁰ metal ions so that the observed thermal expansion behavior should arise from vibrational, rather than electronic, effects. In Chapter 2, the thermal expansion of scandium fluoride, ScF₃, is examined using a combination of in situ synchrotron X-ray and neutron variable temperature diffraction. ScF₃ retains the cubic ReO₃ structure across the entire temperature range examined (10-1600 K) and exhibits pronounced negative thermal expansion at low temperatures. The magnitude of NTE in this material is comparable to that of cubic ZrW₂O₈, which is perhaps the most widely studied NTE material, at room temperature and below. This is the first report of NTE in an ReO₃ type structure across a wide temperature range. Chapter 3 presents a comparison between titanium oxyfluoride, TiOF₂, and a vacancy containing titanium hydroxyoxyfluoride, Tiₓ(O/OH/F)₃. TiOF₂ was originally reported to adopt the cubic ReO₃ structure type under ambient conditions, therefore the initial goal for this study was to examine the thermal expansion of this material and determine if it displayed interesting behavior such as NTE. During the course of the study, it was discovered that the original synthetic method resulted in Tiₓ(O/OH/F)₃, which does adopt the cubic ReO₃ structure type. The chemical composition of the hydroxyoxyfluoride is highly dependent upon synthesis conditions and subsequent heat treatments. This material readily pyrohydrolyizes at low temperatures (~350 K). It was also observed that TiOF₂ does not adopt the cubic ReO₃ structure; at room temperature it adopts a rhombohedrally distorted variant of the ReO₃ structure. Positive thermal expansion was observed for TiOF₂ from 120 K through decomposition into TiO₂. At ~400 K, TiOF₂ undergoes a structural phase transition from rhombohedral to cubic symmetry. High pressure diffraction studies revealed a cubic to rhombohedral phase transition for Tiₓ(O/OH/F)₃ between 0.5-1 GPa. No phase transitions were observed for TiOF₂ on compression. In Chapter 4, an in situ variable pressure{temperature diffraction experiment examining the effects of pressure on the coefficients of thermal expansion (CTE) for ScF₃ and TaO₂F is presented. In the manufacture and use of composites, which is a possible application for low and NTE materials, stresses may be experienced. Pressure was observed to have a negligible effect on cubic ScF₃'s CTE; however, for TaO₂F the application of modest pressures, such as those that might be experienced in the manufacture or use of composites, has a major effect on its CTE. This effect is associated with a pressure-induced phase transition from cubic to rhombohedral symmetry upon compression. TaO₂F was prepared from the direct reaction of Ta₂O₅ with TaF₅ and from the digestion of Ta₂O₅ in hot hydro uoric acid. The effects of pressure on the two samples of TaO₂F were qualitatively similar. The slightly different properties for the samples are likely due to differences in their thermal history leading to differing arrangements of oxide and uoride in these disordered materials. In Chapter 5, the local structures of TiOF₂ and TaO₂F are examined using pair distribution functions (PDFs) obtained from X-ray total scattering experiments. In these materials, the anions (O/F) are disordered over the available anion positions. While traditional X-ray diffraction provides detailed information about the average structures of these materials, it is not suffcient to fully understand their thermal expansion. Fits of simple structural models to the low r portions of PDFs for these materials indicate the presence of geometrically distinct M{X{M (M = Ti, Ta; X = O, F) linkages, and a simple analysis of the TaO₂F variable temperature PDFs indicates that these distinct links respond differently to temperature.

Not available / text

Not available / text

No description available.

No description available.

No description available.

The research presented in this thesis focuses on the structural studies and the high pressure behavior of oxide negative thermal expansion (NTE) materials that can be classified as framework materials. First two chapters were devoted to TaO2F which adopts the ReO3-type cubic structure. Our studies under pressure revealed a rather complicated high pressure behavior for this deceivingly simple compound. The diffraction measurements at variable temperature and high pressure indicated that pressure had a significant effect on the linear coefficient of thermal expansion of TaO2F. In the remainder of the thesis, compounds that belong to the Sc2W3O12 family were examined. High-pressure in-situ powder diffraction studies were conducted on Zr2WO4(PO4)2, Zr2MoO4(PO4)2, Hf2WO4(PO4)2, and Sc2W3O12 in order to investigate the effects of pressure on the coefficients of thermal expansion, existence of phase transitions, phase transition pressures and structural changes occurring upon phase transitions.

Thesis (Ph. D.)--Polymer, Textile and Fiber Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Karl I. Jacob; Committee Member: Anselm C. Griffin; Committee Member: C. P. Wong; Committee Member: Rina Tannenbaum; Committee Member: William J. Koros; Committee Member: Yonathan S. Thio.

[From Introduction] The first step in the study of the thermal decompositions of solids is an examination of the kinetics, since this casts much light on the mechanism of the reaction. It must be borne in mind, however, that a theoretical expression, derived on the basis of a particular mechanism, even if it fits the observed experimental results, is not conclusive proof of the validity of the mechanism when applied to the decomposition under examination.