This research concerns the development and characterization of methylene bis (p-cyclohexyl isocyanate/butanediol) (HMDI/BD) based polyurethanes used in connection with surface-active anti-microbial polyurethanes. Previously studied polyurethanes having an isophorone diisocyanate/butanediol (IPDI/BD) hard block contaminated water during dynamic contact angle (DCA) analyses. This contamination by unknown species confounds results from biocidal studies and jeopardizes the use of the polyurethane as a matrix polyurethane. By contrast, polyurethanes with methylene bis (p-cyclohexyl isocyanate)/butanediol hard block showed no contamination during DCA analysis. For this reason, further study of HMDI/BD/PTMO polyurethanes was conducted. HMDI/BD polyurethanes were synthesized with 15-50wt% hard block and a soft block of PTMO-2000 or PTMO-1000 where PTMO-2000 is poly (tetramethylene oxide) with a molecular weight of 2000g/mol and PTMO-1000 has a molecular weight of 1000g/mol. Characterization was performed with FT-IR and 1H NMR spectroscopy to verify polyurethane composition as well as hard block percentage. Thermal characterization was performed with modulated differential scanning calorimetry (MDSC). From MDSC, the glass transition temperatures of the soft and hard block for polyurethanes with PTMO-2000 as the soft block were -80°C and 86°C, respectively. For corresponding polyurethanes containing PTMO-1000 as the soft block, the measured Tgs for the soft and hard segments were -55°C and 65°C, respectively. The disparity between the respective soft and hard segment Tgs of these polyurethanes of differing soft block molecular weights is due to increased phase mixing that causes an increase in soft block Tg and a decrease in hard block Tg for the PTMO-1000 polyurethanes. From dynamic contact angle analyses of HMDI/BD/PTMO polyurethanes, the advancing and receding contact angles gradually decreased with each cycle but approached 80° and 60°, respectively. Results from force-distance curves with flamed glass slides obtained before and after immersion of the polyurethane coatings indicated that no water contamination occurred. Tensile tests demonstrated that hard block percentage, soft block molecular weight, and the amount of chain extender influences mechanical properties. For example, increasing hard block weight percentage increases the modulus. HMDI/BD(30)/PTMO-2000 (PU-1), HMDI/BD(25)/PTMO-2000, (PU-2) and HMDI/BD(35)/PTMO-2000 (PU-10) exhibited the best elastomeric properties. As the final outcome, lack of contamination and good mechanical properties made PU-2 and PU-9 (HMDI/BD(50)/PTMO-1000) suitable candidates as polyurethane matrices for polymer surface modifier evaluation.

abstract: Water affinity and condensation on Si-based surfaces is investigated to address the problem of fogging on silicone intraocular lenses (IOL) during cataract surgery, using Si(100), silica (SiO2) and polydimethylsiloxane (PDMS) silicone (SiOC2H6)n. Condensation is described by two step nucleation and growth where roughness controls heterogeneous nucleation of droplets followed by Ostwald ripening. Wetting on hydrophilic surfaces consists of continuous aqueous films while hydrophobic surfaces exhibit fogging with discrete droplets. Si-based surfaces with wavelength above 200 nm exhibit fogging during condensation. Below 200 nm, surfaces are found to wet during condensation. Water affinity of Si-based surfaces is quantified via the surface free energy (SFE) using Sessile drop contact angle analysis, the Young-Dupré equation, and Van Oss theory. Topography is analyzed using tapping mode atomic force microscopy (TMAFM). Polymer adsorption and ion beam modification of materials (IBMM) can modify surface topography, composition, and SFE, and alter water affinity of the Si-based surfaces we studied. Wet adsorption of hydroxypropyl methylcellulose (HPMC) C32H60O19 with areal densities ranging from 1018 atom/cm2 to 1019 atom/cm2 characterized via Rutherford backscattering spectrometry (RBS), allows for the substrate to adopt the topography of the HPMC film and its hydrophilic properties. The HPMC surface composition maintains a bulk stoichiometric ratio as confirmed by 4.265 MeV 12C(α, α)12C and 3.045 MeV 16O(α, α)16O, and 2.8 MeV He++ elastic recoil detection (ERD) of hydrogen. Both PIXE and RBS methods give comparable areal density results of polymer films on Si(100), silica, and PDMS silicone substrates. The SFE and topography of PDMS silicone polymers used for IOLs can also be modified by IBMM. IBMM of HPMC cellulose occurs during IBA as well. Damage curves and ERD are shown to characterize surface desorption accurately during IBMM so that ion beam damage can be accounted for during analysis of polymer areal density and composition. IBMM of Si(100)-SiO2 ordered interfaces also induces changes of SFE, as ions disorder surface atoms. The SFE converges for all surfaces, hydrophobic and hydrophilic, as ions alter electrochemical properties of the surface via atomic and electronic displacements. / Dissertation/Thesis / Ph.D. Physics 2011