Thesis (Ph.D.)--Tufts University, 2000. / Submitted to the Dept. of Physics. Adviser: Peggy Cebe. Includes bibliographical references (leaves 246-251). Access restricted to members of the Tufts University community. Also available via the World Wide Web;

Thesis (M.S.)--Florida State University, 2005. / Advisor: Rufina G. Alamo, Florida State University, FAMU-FSU College of Engineering, Dept. of Chemical and Biomedical Engineering. Title and description from dissertation home page (viewed Jan. 26, 2006). Document formatted into pages; contains xii, 136 pages. Includes bibliographical references.

Graduation date: 1991

Thesis (Ph. D.)--University of Texas at Austin, 1999. / Vita. Includes bibliographical references. Available also in a digital version from Dissertation Abstracts.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1983. / Typescript. Vita. Description based on print version record. Includes bibliographical references.

Single crystal surfaces can be used as substitutes or models for the actual reactive surfaces of heterogeneous catalysts. The advantage in using such models is that the reaction of interest can be isolated on the particular face of the crystal that is thought to be catalytically active. A variety of ordered chlorine covered Ti surfaces were prepared which should be useful as model surfaces for studying Ziegler-Natta reactions. These include a chlorine covered Ti(100) surface on which a 4x6 LEED pattern was observed and a chlorine covered Ti(001) surface, on which a chlorine coincidence lattice was formed. The reactivity of clean and partially chlorine covered Ti(001) and (100) surfaces toward ethylene was also studied. During the investigation of ethylene uptake an epitaxial layer of TiC(lll) was produced on the clean Ti(001) surface. Ethylene uptake curves and carbon segregation to the chlorine covered crystal face are reported for various fractional chlorine coverages. Sulfur segregation from the bulk, to the surface of a Ti single crystal was studied and ordered LEED patterns recorded on ,both the Ti(001) and Ti(100) surfaces. The sulfur covered surfaces were in turn used in additional experiments designed to investigate the uptake of chlorine and the thermal desorption of chlorine from a sulfur covered surface. / Graduation date: 1991

Thesis (Ph. D.)--University of Texas at Austin, 1999. / Vita. Includes bibliographical references. Available also in a digital version from Dissertation Abstracts.

The gas phase polyethylene production process is the most recently developed and boasts many / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, 2006

Thesis (Ph. D.)--Florida State University, 2005. / Advisor: Rufina G. Alamo, Florida State University, FAMU-FSU College of Engineering, Dept. of Chemical and Biomedical Engineering. Title and description from dissertation home page (viewed Jan. 24, 2006). Document formatted into pages; contains xv, 209 pages. Includes bibliographical references.

A systematic study of propylene polymerization using a 4th generation Ziegler-Natta catalyst is presented in this thesis. The apparent kinetic rate constants for propylene polymerization were estimated in the presence and absence of hydrogen and/or donor. The estimated activation energies for activation, propagation, and deactivation were found to be close to values previously reported in the literature for similar catalysts. The polypropylene samples were characterized using high-temperature gel permeation chromatography (GPC), carbon-13 nuclear magnetic resonance (13C NMR), and crystallization elution fractionation (CEF). The effect of hydrogen and external electron donor on polypropylene microstructure was investigated at two polymerization temperatures. In addition to the expected electron donor positive effect on tacticity, hydrogen was also found to increase polypropylene tacticity. The effect of changing these polymerization conditions on molecular weight and polydispersity was also investigated. Finally, CEF profiles show how the distribution of polypropylene crystallizability changes by adding hydrogen and electron donor to the reactor. The concentrations of hydrogen and external donor were also varied to study their effect of polymerization kinetics and polymer microstructure. The estimated activation energies were close to those found in the first part of this investigation in the presence and/or absence of donor and hydrogen. A polypropylene microstructural study showed a positive effect of hydrogen concentration on mmmm pentad at low donor concentration, likely due to an increase in stereoselectivity of the aspecific sites by hydrogen. However, increasing donor concentration over a given threshold seems to transform the aspecific sitess into stereospecific sites that are no longer significantly affected by hydrogen. These experimental results were compared to a previously developed Monte Carlo model and found to agree with the trends predicted by simulation. Finally, the effect of diisopropyldimethoxysilane (P), n-propyltrimethoxysilane (N), paraethoxyethylbenzoate (PEEB), and dicyclopentyldimethoxysilane (D) external donors on catalyst activity and stereoselectivity was investigated. P and D donors were more stereoselective than N and PEEB donors; however, D donor had the best activity among all donors investigated. Therefore, D donor was mixed with PEEB to combine its high activity with the self-extinguishing properties of PEEB. The D/PEEB 90/10 (mol/mol) mixture generated a catalyst with good stereoselectivity but poor activity. When the ratio was increased to 95/5 and 98/2, the resulting catalyst had high activity and good stereoselectivity. Interestingly, the D/PEEB combination with just a small fraction of PEEB has a positive effect on the catalysts activation term which may decrease polymerization costs with this system.