Behavior of Poly electrolyte Gels in Concentrated Solutions of Highly Soluble Salts

Ionic hydrogels are an abundant class of materials with applications ranging from drug delivery devices to high performance concrete to baby diapers. A more thorough understanding of interactions between poly electrolyte networks and ionic solutes is critical as these materials are further tailored for performance applications in highly targeted ionic environments. In this work, we seek to develop structure-property relationships between polyelectrolyte gels and environments containing high concentrations of multivalent ions. Specifically, this work seeks to elucidate the causes behind differences in hydrogel response to divalent ions of main group metals versus transition metals. PANa-co-PAM hydrogels containing low and high fractions of ionic groups are investigated in solutions of DI water, NaCl, CaCl2, and CuSO4 at concentrations ranging from 5 to 100 mM in order to understand 1) the transient or permanent nature of crosslinks produced in these networks by divalent counter-ions, 2) the role of polymer ionic content in these interactions, and 3) how these interactions scale with salt concentration. Gravimetric swelling and mechanical compression testing are employed to characterize water and salt-swollen hydrogels in order to develop guiding principles to control and manipulate material properties through polymer-counter-ion interactions. The work presented here confirms the formation of permanent crosslinks by transition metal ions, offers explanation for the behavioral discrepancy observed between ionic hydrogels and main group versus transition metal ions, and illustrates how such hydrogel properties scale with counter-ion concentration

Contaminant Release from Storm Water Culvert Rehabilitation Technologies: Understanding Implications to the Environment and Long-Term Material Integrity

Millions of miles of existing U.S. storm water culverts are critical for roadway safety but much of this infrastructure requires repair. State departments of transportation (DOT) are increasingly choosing to rehabilitate culverts with spray-on and cured-in-place pipe (CIPP) lining processes. These culvert lining practices involve the manufacture of a new plastic liner inside a damaged culvert. DOTs are selecting these outdoor plastic manufacturing methods partly to avoid open-trench excavation, which can cause traffic disruption and work zone traffic safety issues. This study was conducted to better understand current knowledge about culvert lining caused environmental contamination, final product quality, and recommend improved construction specifications, project oversight, and testing requirements to limit undesirable consequences. Literature reviews, a survey of construction specifications and special provisions for 32 transportation agencies, as well as field- and bench-scale testing for CIPP projects in California, New York, and Virginia, were completed. During this project, the safety of workers, transportation agency employees, and the general public at lining installation sites, was raised as a concern by state and federal agencies. Due to previously unreported hazards which were encountered at multiple CIPP field sites, the provision of worksite safety recommendations for DOTs was added to this study. Recommendations are provided for spray-on lining and CIPP lining culvert repair projects that can (1) limit environmental contamination, (2) improve worksite safety, and (3) aid DOTs in better understanding the quality of their new liners

Hydrophilic-oleophobic stimuli -responsive materials and surfaces

Due to their high surface energy, hydrophilic surfaces are susceptible to contamination which is difficult to remove and often ruins the surface. Hydrophilic-oleophobic coatings have a diverse engineering potential including applications as self-cleaning surfaces, extended life anti-fog coatings, and environmental remediation in the selective filtration of oil-in-water mixtures. A successful design model for hydrophilic-oleophobic behavior has been developed using perfluorinated surfactants covalently bound to a surface. Within this design model, a variety of materials have been explored which the surfactants are covalently bound to a substrate; similarly, the surfactants may also be incorporated as a monomer into bulk copolymers. Surfactant based surfaces exhibited simultaneous hydrophilicity, necessary for anti-fogging, and oleophobicity, necessary for contamination resistance. The combination of these features rendered the surface as self-cleaning. Surfactant based brushes, composed of polyethylene glycol and perfluorinated constituents were grafted on to silica surfaces. The relationship between brush density and stimuli-responsiveness was determined by varying grafting conditions. The resultant surfaces were characterized with respect to chemical composition, brush thickness, and wetting behavior of water and hexadecane. Optimized surfaces exhibited stimuli-responsive behavior such that the surfaces will be wetted by water but not by oil. Surfactants were incorporated into random copolymers to create self-cleaning polymers which could be easily coated on to surfaces post-synthesis. Acrylic acid, methyl methacrylate, and hydroxyethyl methacrylate were used as comonomers; feed ratio was varied to establish compositional limits of stimuli-responsive behavior. Polymer composition dictated coating durability and self-cleaning performance as determined by water and hexadecane contact angle. The ability of select coatings to mitigate fogging was assessed in two extreme environments: transition from -20°C to humid laboratory environment; exposure to steaming water vapor. Silica membranes of varying pore size were modified with stimuli-responsive surfactants. Membranes showed the ability to selectively pass water and restrict passage of oil, demonstrating a reusable method of separating oil-in-water emulsions. Selectivity of oil-in-water emulsions and permeate flow rate of each individual fluid were quantified for the surfactant modified membranes. Permeate flow rate was characterized with respect to individual droplets and bulk fluid

Investigation of the factors that influence lead accumulation onto polyethylene: Implication for potable water plumbing pipes

The influence of polymer aging, water pH, and aqueous Pb concentration on Pb deposition onto low density polyethylene (LDPE) was investigated. LDPE pellets were aged by ozonation at 85 °C. ATR-FTIR and X-ray photoelectron spectroscopy (XPS) analysis of aged LDPE surfaces showed that a variety of polar functional groups (\u3eC–O\u3c, \u3eC[dbnd]O, \u3eCOO) were formed during aging. These functional groups likely provided better nucleation sites for Pb(OH)2 deposition compared to new LDPE, which did not have these oxygen-containing functional groups. The type and amount of Pb species present on these surfaces were evaluated through XPS. The influence of exposure duration on Pb deposition onto LDPE was modeled using the pseudo-first-order equation. Distribution ratios of 251.5 for aged LDPE and 69.3 for new LDPE showed that Pb precipitates had greater affinity for the surface of aged LDPE compared to new LDPE. Aged LDPE had less Pb surface loading at pH 11 compared to loading at pH 7.8. Pb surface loading for aged LDPE changed linearly with aging duration (from 0.5–7.5 h). Pb surface loading on both new and aged LDPE increased linearly with increasing Pb initial concentration. Greater Pb precipitation rates were found for aged LDPE compared to new LDPE at both tested pH values

Assessment of early onset surface damage from accelerated disinfection protocol

Abstract Background The objective of this study was to evaluate the extent and potential mechanisms of early onset surface damage from simulated wiping typical of six-months of routine disinfection and to assess the subsequent microbial risk of surfaces damaged by disinfectants. Methods Eight common material surfaces were exposed to three disinfectants and a neutral cleaner (neutral cleaner, quaternary ammonium, hydrogen peroxide, sodium hypochlorite) in accelerated aging tests to simulate a long-term disinfection routine. Materials were also immersed in dilute and concentrated chemical solutions to induce surface damage. Surfaces were chemically and physically characterized to determine extent of surface damage. Bactericidal efficacy testing was performed on the Quat-based disinfectant using a modified version of EPA standard operating procedure MB-25-02. Results The wiping protocol increased surface roughness for some material surfaces due to mechanical abrasion of the wiping cloth. The increased roughness did not correlate with changes in bactericidal efficacy. Chemical damage was observed for some surface-disinfectant combinations. The greatest observed effects from disinfectant exposure was in changes in wettability or water contact angle. Conclusions Early onset surface damage was observed in chemical and physical characterization methods. These high-throughput material measurement methods were effective at assessing nanoscale disinfectant-surface compatibility which may go undetected though routine macroscale testing

Enhanced Wettability and Transport Control of Ultrafiltration and Reverse Osmosis Membranes with Grafted Polyelectrolytes

End-functionalized poly­(acrylic acid) (PAA-silane) was synthesized with reversible addition–fragmentation chain-transfer (RAFT) polymerization and attached to both polysulfone ultrafiltration (UF) and polyamide reverse osmosis (RO) membranes through a nonimpairing, one-step <i>grafting to</i> approach in order to improve membrane surface wettability with minimal impact on membrane transport performance. After PAA grafting, composition and morphology changes on the membrane surface were characterized with Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM). Static contact angle on PAA grafted membranes exhibited an increase in surface hydrophilicity and hence a potential enhancement in antifouling performance. The native contact angle on the polysulfone membrane systems was 86° and was reduced to 24° after modification, while the polyamide film contact angle decreased from 58° to 25°. The PAA layer endowed the porous UF membrane with dynamic control over the permeability and selectivity through the manipulation of the solution pH. The UF membrane with a 35 nm average pore size displayed a 115% increase in flux when the contact solution was changed from pH 11 to pH 3. This effect was diminished to 70% and 32% as the average pore size decreased to 20 and 10 nm, respectively. Modified RO membranes displayed no reduction in membrane performance indicating that the underlying materials were unaffected by the modification environment or added polymer. Model polyamide and polysulfone surfaces were reacted with the PAA-silane inside a quartz crystal microbalance (QCM) to help inform the deposition behavior for the respective membrane chemistries