Thesis (Ph.D. - Hydrology and Water Resources)--University of Arizona. / Includes bibliographical references (leaves 267-288).

Acrylonitrile based engineering random copolymers were prepared via one step emulsion polymerization using ammonium persulfate (initiator), 1-dodecanthiol (chain transfer agent) and DOWFAX 8390 (surfactant) in the presence of water at approximately 65 0C. Three copolymer compositions were studied for novel polyacrylonitrile, (PAN)-polyhydroxyethyl acrylate (PHEA), PAN-polybutyl acrylate (PBA), novel PAN-polyt-butyl acrylate (PtBA), PAN-polyethyl acrylate (PEA) and PAN-polymethyl acrylate (PMA) with acrylate content varying from 8, 12 and 16 molar percent. Infrared spectroscopy, proton and carbon NMR were successfully utilized to confirm the chemical structure of copolymers. In order to determine the comonomer compositions in the copolymer structure, proton nuclear magnetic resonance, 1H NMR studies were carried out. Thermal (TGA, DSC) and mechanical properties of homo and copolymers were also investigated. Intrinsic viscosity (IV) measurements in dimethyl formamide (DMF) solution revealed that the molecular weight of the copolymers were quite enough to form ductile films. In this study, hydrogels and their copolymers of acrylonitrile (PAN-PHEA) were also studied. Some properties of the free standing copolymer films such as / swelling behaviors and densities were evaluated. It was also demonstrated that the nanocomposites of these copolymers could be utilized in filtration technology. Hence, novel PAN(88)-co-PMA(12) and polyaniline (PANI) nanocomposites were prepared at various PANI loadings to remove toxic chromium(VI) solution from water. Chemical structure, swelling and fracture morphology of the nanocomposites membranes were studied. It was observed that PANI had a great impact on the chromium removal. Permeate flux and rejection of chromium(VI) were demonstrated for various pHs and chromium(VI) concentrations. Finally, influences of comonomer composition on the thermal properties of the copolymers were investigated to input their structure property relation.

Acrylonitrile were copolymerized with 2-ethylhexyl acrylate and hexyl acrylate via one step emulsion polymerization using ammonium persulfate (initiator), 1-dodecanthiol (chain transfer agent) and DOWFAX 8390 (surfactant) in the presence of water at about 68 0C. Poly (acrylonitrile-2ethylhexyl acrylate) and poly (acrylonitrile-hexyl acrylate) copolymers with three different comonomer composition (8, 12 and 16 molar percent) were prepared. FTIR and 1H-NMR were used in order to clarify the chemical structure of copolymers. The comonomer amount incorporated into copolymers was determined by using 1H-NMR spectra. The thermal behavior of copolymers was determined by DSC and TGA. Molecular weights of copolymers were determined by intrinsic viscosity (IV) measurements. IV measurements revealed that both poly (acrylonitrile-2ethylhexyl acrylate) and poly (acrylonitrile-hexyl acrylate) have sufficient molecular weight to form nanoporous filtration membranes. Nanoporous filtration membranes were prepared and tested for chromium (IV) removal. It was observed that chromium (VI) rejections of nanoporous filtration membrane were highly dependent on the concentration and the pH of the solutions. Almost complete removal (99, 9 percent Cr (VI)) rejection was achieved at pHs 2, 5 and 7 for solution containing 50 ppm, chromium (VI) with permeate flux within a range from 177 to 150 L/m2h at 689.5 kPa. Also, chemical structure, swelling ratios, sheet resistivity and fracture morphologies of the nanoporous filtration membrane were studied. It should be noted that the nanoporous filtration membranes were fouling resistant.