THERMODYNMICS AND STRUCTURE OF POLY(ETHYLENE OXIDE) IN MIXTURES OF WATER AND ETHANOL

Poly(ethylene oxide) (PEO) is one of the most researched synthetic polymers due to the complex behavior which arises from the interplay of the hydrophilic and hydrophobic sites on the polymer chain. PEO in ethanol forms an opaque gel-like mixture with a partially crystalline structure. Addition of a small amount of water disrupts the gel: 5 wt % PEO in ethanol becomes a transparent solution with the addition of 4 vol % water. The phase behavior of PEO in mixed solvents have been studied using small-angle neutron scattering (SANS). PEO solutions (5 wt % PEO) which contain 4 vol % - 10 vol % (and higher) water behave as an athermal polymer solution and the phase behavior changes from UCST to LCST rapidly as the fraction of water is increased. 2 wt % PEO in water and 10 wt % PEO in ethanol/ water mixtures are examined to assess the role of hydration. The observed phase behavior is consistent with a hydration layer forming upon the addition of water as the system shifts from UCST to LCST behavior. At the molecular level, two or three water molecules can hydrate one PEO monomer (water molecules form a sheath around the PEO macromolecule) which is consistent with the suppression of crystallization and change in the mentioned phase behavior as observed by SANS. The clustering effect of aqueous PEO solution (M.W of PEO = 90,000 g/mol) is monitored as an excess scattering intensity at low-Q. Clustering intensity at Q = 0.004 Å^-1 is used for evaluating the clustering effect. The clustering intensity is proportional to the inverse temperature and levels off when the temperature is less than 50 ˚C. When the temperature is increased over 50 ˚C, the clustering intensity starts decreasing. The clustering of PEO is monitored in ethanol/ water mixtures. The clustering intensity increases as the fraction of water is increased. Based on the solvation intensity behavior, we confirmed that the ethanol/ water mixtures obey a random solvent mixing rule, whereby solvent mixtures are better at solvating the polymer that any of the two solvents. The solution behavior of PEO in ethanol was investigated in the presence of salt (CaCl2) using SANS. Binding of Ca2+ ions to the PEO oxygens transforms the neutral polymer to a weakly charged polyelectrolyte. We observed that the PEO/ethanol solution is better solvated at higher salt concentration due to the electrostatic repulsion of weakly charged monomers. The association of the Ca2+ ions with the PEO oxygen atoms transforms the neutral polymer to a weakly charged polyelectrolyte and gives rise to repulsive interactions between the PEO/Ca2+ complexes. Addition of salt disrupts the gel, which is consistent with better solvation as the salt concentration is increased. Moreover, SANS shows that the phase behavior of PEO/ethanol changes from UCST to LCST as the salt concentration is increased.

THE DEVELOPMENT EFFECTIVENESS OF INTERNATIONAL WATER AND SANITATION INFRASTRUCTURE PROJECTS: DEFINING “QUALITY AT ENTRY” OF WORLD BANK PROJECTS.

Over the past 15 years, the number of international development projects aimed at combating global poverty has increased significantly. Within the water and sanitation sector however, and despite heightened global attention and an increase in the number of infrastructure projects, over 800 million people remain without access to appropriate water and sanitation facilities. The majority of donor aid in the water supply and sanitation sector of developing countries is delivered through standalone projects. The quality of projects at the design and preparation stage is a critical determinant in meeting project objectives. The quality of projects at early stage of design, widely referred to as quality at entry (QAE), however remains unquantified and largely subjective. This research argues that water and sanitation infrastructure projects in the developing world tend to be designed in the absence of a specific set of actions that ensure high QAE, and consequently have relatively high rates of failure. This research analyzes 32 cases of water and sanitation infrastructure projects implemented with partial or full World Bank financing globally from 2000 – 2010. The research uses categorical data analysis, regression analysis and descriptive analysis to examine perceived linkages between project QAE and project development outcomes and determines which upstream project design factors are likely to impact the QAE of international development projects in water supply and sanitation. The research proposes a number of specific design stage actions that can be incorporated into the formal review process of water and sanitation projects financed by the World Bank or other international development partners.