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1. Hydrophobicity versus pore size: polymer coatings to improve membrane wetting resistance for membrane distillation

   https://doi.org/10.1021/acsapm.9b01133  

   McGaughey, Allyson L. ; Karandikar, Prathamesh ; Gupta, Malancha ; Childress, Amy E. ( February 2020 , ACS applied polymer materials)

   Initiated chemical vapor deposition (iCVD) was used to coat two porous substrates (i.e., hydrophilic cellulose acetate (CA) and hydrophobic polytetrafluoroethylene (PTFE)) with a crosslinked fluoropolymer to improve membrane wetting resistance. The coated CA membrane was superhydrophobic and symmetric. The coated PTFE membrane was hydrophobic and asymmetric, with smaller pore size and lower porosity on the top surface than on the bottom surface. Membrane performance was tested in membrane distillation experiments with (1) a high-salinity feed solution and (2) a surfactant-containing feed solution. In both cases, the coated membranes had higher wetting resistance than the uncoated membranes. Notably, wetting resistances were better predicted by LEP distributions than by minimum LEP values. When LEP distributions were skewed towards high LEP values (i.e., when small pores with high LEP were greater in number), significant (measurable) salt passage did not occur. For the high-salinity feed solution, the coated PTFE membrane had greater wetting resistance than the coated CA membrane; thus, reduced surface pore size/porosity (which may reduce intrapore scaling) was more effective than increased surface hydrophobicity (which may reduce surface nucleation) in preventing scaling-induced wetting. Reduced pore size/porosity was equally as effective as increased hydrophobicity in resisting surfactant-induced wetting. However, reduced porosity can negativelymore »impact water flux; this represents a permeability/wetting resistance tradeoff in membrane distillation – especially for high-salinity applications. Membrane and/or membrane coating properties must be optimized to overcome this permeability/wetting resistance tradeoff and make MD viable for the treatment of challenging streams. Then, increasing hydrophobicity may not be necessary to impart high wetting resistance to porous membranes. These results are important for future membrane design, especially as manufacturers seek to replace perfluorinated materials with environmentally friendly alternatives.« less
2. Accelerated Reaction Rates within Self-Assembled Polymer Nanoreactors with Tunable Hydrophobic Microenvironments

   https://doi.org/10.3390/polym12081774  

   Harrison, Andrew ; P. Zeevi, Michael ; L. Vasey, Christopher ; D. Nguyen, Matthew ; Tang, Christina ( August 2020 , Polymers)

   Performing reactions in the presence of self-assembled hierarchical structures of amphiphilic macromolecules can accelerate reactions while using water as the bulk solvent due to the hydrophobic effect. We leveraged non-covalent interactions to self-assemble filled-polymer micelle nanoreactors (NR) incorporating gold nanoparticle catalysts into various amphiphilic polymer nanostructures with comparable hydrodynamic nanoreactor size and gold concentration in the nanoreactor dispersion. We systematically studied the effect of the hydrophobic co-precipitant on self-assembly and catalytic performance. We observed that co-precipitants that interact with gold are beneficial for improving incorporation efficiency of the gold nanoparticles into the nanocomposite nanoreactor during self-assembly but decrease catalytic performance. Hierarchical assemblies with co-precipitants that leverage noncovalent interactions could enhance catalytic performance. For the co-precipitants that do not interact strongly with gold, the catalytic performance was strongly affected by the hydrophobic microenvironment of the co-precipitant. Specifically, the apparent reaction rate per surface area using castor oil (CO) was over 8-fold greater than polystyrene (750 g/mol, PS 750); the turnover frequency was higher than previously reported self-assembled polymer systems. The increase in apparent catalytic performance could be attributed to differences in reactant solubility rather than differences in mass transfer or intrinsic kinetics; higher reactant solubility enhances apparent reaction rates. Full conversionmore »of 4-nitrophenol was achieved within three minutes for at least 10 sequential reactions demonstrating that the nanoreactors could be used for multiple reactions.« less
3. Bioinspired cellular sheath-core electrospun non-woven mesh

   https://doi.org/10.1007/s42247-019-00043-7  

   Rizvi, H.R. ; D’Souza, N. ; Ayre, B. ; Ramesh, D. ( January 2019 , Emergent materials)

   Fibers are valuable to biomedical applications. Used as sutures or meshes, there is an increased dual need to provide functionality such as drug delivery. Porosity represents a high surface area to volume architecture. Coaxial fibers with porous and non-porous layers offer a new design framework for fiber design that can resolve dual needs of mechanical robustness with transport phenomena. Using preferential solubility of a polymer in supercritical CO2, we develop a new architecture using biocompatible polymers based on porous core-sheath fiber fabrication technique. Polycaprolactone was selected as the CO2 miscible phase and Poly(butyrate adipate terephthalate)(PBAT) as the immiscible phase. The mechanical performance of the fibers was investigated using quasi static and dynamic loading. SEM images indicate no physical detachment of the two polymer surface after CO2 exposure indicating a successful amalgamation of polymers at the boundary of core and sheath. PCL as a sheath and as a core showed an increase of 650% and 468% in tensile strength compared to pristine PCL and PBAT. Introduction of porosity on the surface of coaxial fiber fPCL(cPBAT) further enhanced the yield strength increases by 40%. Dynamic mechanical analysis was used to analyze the viscoelastic properties of the fibers. The storage and loss modulusmore »for coaxial fibers shows superior modulus throughout the glassy, glass transition and rubbery region as compared to the pristine PCL and PBAT, showing enhancement in both the elastic and viscous response of the material. The results indicate a new approach that is free of volatile organic solvents to manipulate the architecture of the cross-section of the electrospun fiber and tailor mechanical properties to the required application.« less
4. Polyelectrolyte Complex Stabilized CO2 Foam Systems for Hydraulic Fracturing Application

   https://doi.org/10.2118/187489-MS  

   Anandan, Rudhra ; Johnson, Stephen ; Barati, Reza ( September 2017 , SPE Liquids-Rich Basins Conference- North America)

   Hydraulic fracturing of oil and gas wells is a water intensive process. Limited availability, cost and increasing government regulations restraining the use and disposal of fresh water have led to the need for alternative fracturing fluids. Using CO2 foam as a fracturing fluid can drastically reduce the need for water in hydraulic fracturing. We address the addition of polyelectrolyte complex nanoparticles (PECNP) to surfactant solutions to improve foam stability, durability and rheological properties at high foam qualities. Polyelectrolyte pH and polyanion/polycation ratios were varied to minimize particle size and maximize absolute zeta potential of the resulting nanoparticles. Rheological tests were conducted on foam systems of varying surfactant/PECNP ratios and different foam quality to understand the effect of shear on viscosity under simulated reservoir conditions of 40°C and 1300 psi. The same foam systems were tested for stability and durability in a view cell at reservoir conditions. Supercritical CO2 foam generated by surfactant alone resulted in short lived, low viscosity foam because of surfactant drainage from foam lamellae. However, addition of PECNP strengthens the foam film by swelling the film due to increased osmotic pressure and electrostatic forces. Electrostatic interactions reduce dynamic movement of surfactant micelles, thereby stabilizing the foammore »lamellae, which imparts high durability and viscosity to supercritical CO2 foams. From the rheology test results, it was concluded that increasing foam quality and the presence of PECNP resulted in improved viscosity. Also, foam systems with PECNP showed promising results compared with foam generated using surfactant alone in the view cell durability test. The addition of optimized polyelectrolyte nanoparticles to the surfactant can improve viscosity and durability of supercritical CO2 foam during hydraulic fracturing, which can lead to large reductions in water requirements.

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5. Enhanced Dielectric Permittivity of Optimized Surface Modified of Barium Titanate Nanocomposites

   https://doi.org/10.3390/polym12040827  

   Sundar, Udhay ; Lao, Zichen ; Cook-Chennault, Kimberly ( April 2020 , Polymers)

   High permittivity polymer-ceramic nanocomposite dielectric films take advantage of the ease of flexibility in processing of polymers and the functionality of electroactive ceramic fillers. Hence, films like these may be applied to embedded energy storage devices for printed circuit electrical boards. However, the incompatibility of the hydrophilic ceramic filler and hydrophobic epoxy limit the filler concentration and therefore, dielectric permittivity of these materials. Traditionally, surfactants and core-shell processing of ceramic fillers are used to achieve electrostatic and steric stabilization for adequate ceramic particle distribution but, questions regarding these processes still remain. The purpose of this work is to understand the role of surfactant concentration ceramic particle surface morphology, and composite dielectric permittivity and conductivity. A comprehensive study of barium titanate-based epoxy nanocomposites was performed. Ethanol and 3-glycidyloxypropyltrimethoxysilan surface treatments were performed, where the best reduction in particle agglomeration, highest value of permittivity and the lowest value of loss were observed. The results demonstrate that optimization of coupling agent may lead to superior permittivity values and diminished losses that are ~2–3 times that of composites with non-optimized and traditional surfactant treatments.