Doctor of Philosophy, The Ohio State University, 2013, Food, Agricultural and Biological Engineering

Abstract This study focused on the development of bio-based polyols and polyurethanes (PU) from biodiesel-derived crude glycerol and lignocellulosic biomass. Polyols were produced via liquefaction of lignocellulosic biomass using crude glycerol as a liquefaction solvent. The polyols produced were used directly to prepare PU foams. The effects of liquefaction parameters on the properties of polyol and PU foams were investigated. Under optimal liquefaction conditions, the polyols and PU foams produced had properties comparable to their analogs derived from petrochemical solvent-based liquefaction processes. Certain impurities in crude glycerol are critical for the improvement of polyol and PU foam properties. The composition of five representative biodiesel-derived crude glycerol samples was determined to identify their components. All crude glycerol samples contained glycerol, soap, methanol, FAMEs (methyl esters of fatty acids), water, glycerides, FFAs (free fatty acids), and ash, but their proportions varied widely with the origins of crude glycerol. The effects of crude glycerol impurities on the properties of polyols and PU foams derived from base- and acid-catalyzed biomass liquefaction processes were studied. For both liquefaction processes, increasing levels of organic impurities (i.e. FFA, FAMEs, and glycerides) in crude glycerol decreased biomass conversion and polyol hydroxyl numbers and increased polyol molecular weight. The presence of suitable amounts of organic impurities, especially FFA and FAMEs, in crude glycerol improved the properties of polyols and PU foams produced. For both processes, valid regression models (R2=0.99) were developed to predict the hydroxyl numbers of polyol from the contents of organic impurities in crude glycerol. In contrast to their negligible effects on the base-catalyzed process, inorganic salts, including NaCl and Na2SO4, negatively affected the properties of polyols produced from the acid-catalyzed process. A two-ste (open full item for complete abstract)

Committee: Yebo Li (Advisor) Subjects: Agricultural Engineering; Energy; Engineering; Materials Science; Polymers

Master of Science (MS), Wright State University, 2006, Chemistry

Thermal and microwave polyol methods were investigated in the synthesis of various iron and cobalt core-shell nanoparticles. The reaction involved 1 mmol of an Fe+2 or Co+2 salt, bis-acetylacetanato [(Acac)2] iron (II), cobalt (Acac)2 or iron (II) acetate along with 1 mmol of a surfactant capping agent. The salt was reduced with 2 mmol of a 1,2 diol. When 1,2-hexadecanediol solid was used as a reducing agent, it was dissolved along with the metal salt and capping agent in octyl ether. When 1,2-hexanediol liquid was used as the reducing agent, it was also the solvent, and octyl ether was eliminated. For reactions in which octyl ether acted as the solvent, the capped nanoparticles were precipitated using ethanol. For reactions in which the solvent also acted as the reducing agent, the particles precipitated after nucleation and supersaturation of the polyol solvent/reducing agent.

Committee: Eric Fossum (Advisor) Subjects: Chemistry, Inorganic