Water is becoming increasingly scarce as the demand for fresh water continues to rise. One potential new water resource is purified produced water. Produced water is generated during oil and gas production, and it is often contaminated with emulsified oil, high levels of salt, and particulate matter. Produced water purification using polymer membranes has been investigated, but its implementation is limited by membrane fouling. This study focused on the preparation and application of poly(ethylene glycol) (PEG) hydrogels as fouling-resistant coatings for commercial reverse osmosis (RO) membranes. To prepare fouling-resistant coatings for RO membranes, three series of copolymer hydrogel networks were synthesized using poly(ethylene glycol) diacrylate (PEGDA) as the crosslinker and acrylic acid (AA), 2-hydroxyethyl acrylate (HEA), or poly(ethylene glycol) acrylate (PEGA) as comonomers, and their transport properties were evaluated. The hydrogels have high water uptake and high water permeability, and crosslink density strongly influences water uptake and water permeability. For example, a 100 mol% PEGDA hydrogel contained 61% water by volume, but 80PEGA, which has essentially the same chemical composition but lower crosslink density, contained 72% water by volume. Hydrogel water permeability ranged from 10 to 26 (L [mu]m)/(m² hr bar) and correlates well with water uptake; high water uptake often leads to high water permeability. Additionally, the copolymers have hydrophilic surfaces with a low affinity for oil, based on contact angle measurements using n-decane in water. Commercial RO membranes (AG RO membrane from GE Water and Process Technologies) were coated with PEG hydrogels, and the desalination and fouling resistance properties of the coated membranes were tested. The water flux of coated membranes and a series-resistance model were used to estimate coating thickness; the coatings were approximately 2 [mu]m thick. NaCl rejection for both uncoated and coated membranes was 99.0% or greater. As determined by zeta potential measurements, both uncoated and coated RO membranes are negatively-charged, but coated membranes are less negatively-charged than uncoated RO membranes. Model oil/water emulsions, prepared with either a cationic or an anionic surfactant, were used to probe membrane fouling. In the absence of oil, surfactant charge, and therefore, electrostatic interactions play a significant role in membrane fouling. In the presence of DTAB, a cationic surfactant, the AG RO membrane water flux immediately dropped to 30% of its initial value, but in the presence of SDS, an anionic surfactant, its water flux gradually decreased to 74% of its initial value after 24 hours. However, in both cases, coated membranes exhibited less flux decline than uncoated membranes. Coated membranes also experienced little fouling in the presence of an n-decane/DTAB emulsion. After 24 hours, the water flux of a PEGDA-coated AG RO membrane was 73% of its initial value, while the water flux of an AG RO membrane fell to 26% of its initial value. Conversely, both coated and uncoated membranes fouled significantly in the presence of an n-decane/SDS emulsion, indicating that oil fouling is controlled both by electrostatic and hydrophobic interactions. Overall, this work provides answers to some of the fundamental questions posed regarding the viability of using modified membranes for produced water treatment. / text

Surface-assisted directed assembly allows ultrasoft and replusive functional polymeric “colloids” to assemble into the organized supramolecular ultrathin films on a monomolecular level. This study aims at achieving a fundamental understanding of molecular morphology and responsive behavior of major classes of branched star-shaped polymers (star amphiphilic block copolymers and star polyelectrolytes) and their aggregation into precisely engineered functional ultrathin nanofilms. Thus, we focus on elucidating the role of molecular architecture, chemical composition, and intra/intermolecular interactions on the assembly behavior of highly-branched entities under variable environmental and confined interfacial conditions. The inherent molecular complexity of branched architectures facilitates rich molecular conformations and phase states from the combination of responsive dynamics of flexible polymer chains (amphiphilic, ionizable arms, multiple segments, and free chain ends) and extened molecular design parameters (number of arms, arm length, and segment composition/sequence). These marcromolecular building components can be affected by external conditions (pH, salinity, solvent polarity, concentration, surface pressure, and substrate nature) and transformed into a variety of complex nanostructures, such as two-dimensional circular micelles, core/shell unimicelles, nanogel particles, pancake & brush micelles, Janus-like nanoparticles, and highly nanoporous fractal networks. The fine balance between repulsive mulitarm interactions and surface energetic effects in the various confined surfaces and interfaces enables the ability to fabricate and tailor well-organized ultrathin nanofilms. The most critical findings in this study include: (1) densely packed circular unimicelle monolayers from amphiphilic and amphoteric multiblock stars controlled by arm number, end blocks, and pH/pressure induced aggregation, (2) monolayer polymer-metal nanocomposites by in-situ nanoparticle growth at confined interfaces, (3) on-demand control of exponentially or linearly grown heterogeneous stratified multilayers from self-diffusive pH-sensitive star polyelectrolyte nanogels, (4) core/shell umimicelle based microcapsules with a fractal nanoporous multidomain shell morphology, and (5) preferential binding and ordering of Janus-like unimicelles on chemically heterogeneous graphene oxide surfaces for biphasic hybrid assembly. The advanced branched molecular design coupled with stimuli responsive conformational and compositional behavior presents an opportunity to control the lateral diffusion and phase segregation of branched compact supermolecules on the surface resulting in the generation of well-controllable monolayers with tunable ordering and complex morphology, as well as to tailor their stratified layered nanostructures with switchable morphological heterogeneity and multicompartmental architectures. These surface-driven star polymer supramolecular assemblies and interfaces will enable the design of multifunctional nanofilms as hierarchical responsive polymer materials.