No description available.

Biofouling has been an economically and environmentally costly problem to mankind ever since they set sail. Biofouling causes frictional drag leading to slow vessel speeds, and increased fuel costs. Antifouling (AF) coatings containing biocides have been used for decades, however, since some biocides have shown undesired effects towards the environment, a non-toxic solution to combat fouling is desired. Subsequently, fouling release (FR) coatings quickly gained acceptance as a non-toxic approach to contend with biofouling. Unlike AF coatings, FR coatings not necessarily prevent settlement of organisms, they permit weak adhesion which is easily released by water shear or light grooming. The siloxane-polyurethane (SiPU) coatings based on the concept of self-stratification is a non-toxic and durable approach to prepare FR coatings. In this work, several approaches were considered to optimize surface properties of SiPU coatings. Incorporation of phenyl-methyl silicone oils led to improved FR properties towards several marine organisms in laboratory assays and in ocean field immersion. Enhancement in FR properties may be attributed to slowly exuding silicone oil providing surface lubricity, weakening the adhesion of marine organisms. Addition of diphenyldimethyl siloxane in to SiPU coatings at different ratios resulted in micro-scale surface topographical features which negatively affected microfouling-release while several coatings displayed good FR performance towards macrofouling organisms. In another study, decreasing the acid group content helped to improve FR performance towards barnacles, but FR performance towards diatoms were compromised. Novel amphiphilic siloxane-polyurethane (AmSiPU) coatings from polyisocyanate pre-polymers modified with polydimethyl siloxane and polyethylene glycol displayed excellent FR properties towards several marine organisms during laboratory assays. These AmSiPU coatings show promise as contenders to commercial FR standards. Initial development of SiPU coatings with hydrophilic surfaces showed promise, as the coatings showed rapidly rearranging surfaces with comparable FR performance to commercial standards which claim hydrophilic surface properties. During freshwater field immersion trials, SiPU coatings displayed excellent mussel FR performance up to 3 years. Surface analysis suggested that solvent content affected self-stratification and morphology of SiPU coatings. The SiPU coating system is a highly tunable, tough, environmentally friendly, and practical FR solution which can evolve along with non-toxic commercial marine coatings. / Office of Naval Research (Grant number N00014-12-1-0482) / SSPC / Valpar / American Coatings Association / North Dakota State University. College of Science and Mathematics

No description available.

Polyrotaxanes possess a molecular architecture resembling that of a wheel and axle: linear polymer chains are threaded by cyclic molecules with no covalent bonds linking the two species. One of two methods can be employed for the preparation of polyrotaxanes: a template method to guide threading or an in situ polymerization of monomers in the presence of cyclic molecules. The research described in this dissertation was divided into two distinct sections, which were devoted to each method of polyrotaxane preparation. The first step of synthesizing polyrotaxanes via the in situ polymerization method was to prepare a cyclic molecule. α,Ï -Dihydroxy-PDMS was cyclized and then efficiently purified by an anion-exchange resin to remove uncyclized, yet anionically charged, linear PDMS. The second part of this dissertation included examining polyrotaxanes created by the template-directed threading of α-CD onto polyoctene (PO). End-capped PO, which was unthreadable by α-CD, was synthesized from 1,9-decadiene and a monovinyl bulky compound by acyclic diene metathesis. PO and ecPO each were sonicated in aqueous solutions of α -CD; PO formed a white precipitate indicative of a rotaxanated polymer, but no precipitate formed by the addition of ecPO. These results provided evidence that PO had been included within the cavity of α-CD.

No description available.

The presence of volatile methylsiloxanes (VMS) in the environment has raised concerns among environmental chemists and regulators about their persistence and the risks they may pose to the environment. This thesis explores the partitioning and persistence of VMS in aquatic environments. In Paper I, we reported new measurements of the organic carbon/water (KOC) and dissolved organic carbon/water (KDOC) partition ratios of three cyclic volatile methylsiloxanes (cVMS) and of three polychlorinated biphenyls (PCBs), which were used as reference chemicals. We combined new measurements with existing data to construct polyparameter linear free energy relationships (PP-LFER) that describe the KOC and KDOC of diverse sets of chemicals. The findings suggest that cVMS do not conform to single-parameter regressions that relate the chemicals’ KOC to their octanol/water partition ratio (KOW). PP-LFERs can accurately describe the KOC and KDOC of cVMS but only if cVMS are included in their training sets. In Paper II, we studied the effect of salinity on the KOC and KDOC of three cVMS, two linear volatile methylsiloxanes (lVMS) and three PCBs. We also evaluated the predictive power of the PP-LFERs constructed in Paper I by testing them on the newly measured KOC values of lVMS. The KOC and KDOC increased with increasing salinities similarly to those of the PCBs. PP-LFERs that were trained with datasets that included siloxanes could predict the KOC and KDOC of other siloxanes more accurately than PP-LFERs without siloxanes in the training set. In Paper III, we evaluated the effect of temperature on the KOC of VMS and we compared our measurements of the enthalpy of sorption to organic carbon (ΔHOC) to existing measurements of the enthalpy of phase change between octanol and water (ΔHOW). Due to the scarcity of ΔHOC data in the literature it is common practice in modeling calculations to use ΔHOW instead when correcting for temperature changes. The KOC of cVMS increased with decreasing temperatures. Moreover, our results indicate that ΔHOC and ΔHOW may be intrinsically different and hence replacing ΔHOC with ΔHOW in modeling calculations could lead to substantial errors, especially for VMS. In Paper IV, we explored the environmental fate of VMS in aquatic environments using multimedia models. In particular, we assessed the differences that may occur in calculations of persistence due to (i) the reported KOC measurements of VMS differing by one log unit (ii) the influence of salinity on KOC, and (iii) the differences in the reported ΔHOC and ΔHOW measurements of VMS. The calculated residence times for decamethylcyclopentasiloxane (D5) in a site-specific scenario for a Norwegian fjord receiving siloxanes in wastewater ranged from 200 to 1000 days, and demonstrated that the selection of KOC values can result in substantially different calculated persistence. Future partitioning measurements of VMS in the real environment and mass-balance modeling studies in aquatic environments combined with field measurements could help us to deepen our understanding about their persistence and to assess the risks VMS may pose to the environment. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Manuscript. Paper 3: Submitted.</p>

Thesis (Ph. D.)--Lehigh University, 2001. / Includes bibliographical references and vita.

Dissertation (Ph.D.)--Auburn University,2006. / Abstract. Vita. Includes bibliographic references (p.138-140).

Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: Michael A. Brook. Includes bibliographical references.

Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1992. / Vita. Abstract. Includes bibliographical references (leaves 122-130). Also available via the Internet.