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1. Porous hydrophobic-hydrophilic composite membranes for direct contact membrane distillation

   https://doi.org/10.1016/j.memsci.2019.117225  

   Puranik, A.A.; Rodrigues, L.N.; Chau, J.; Li, L.; Sirkar, K.K. (July 2019, Journal of membrane science)

   Direct contact membrane distillation (DCMD) for desalination is attractive for high salt concentrations if low cost steam/waste heat is available and waste brine disposal cost for inland desalination is factored in. A number of innovations have taken place in DCMD in terms of the structure of the porous hydrophobic membrane. Composite membranes are of increasing interest. Composite membrane structures of great interest include a thin hydrophobic porous layer over a porous hydrophilic layer of polyvinylidene fluoride (PVDF) or a thin porous hydrophobic layer over a more conventional hydrophobic porous membrane. These membranes can be in the form of an integral composite or a stacked composite or a laminated composite. A facile method of fabricating such integral composite membranes is plasma polymerization under vacuum. A class of such membranes yielding quite high water vapor fluxes have been characterized using a variety of characterization techniques: Contact angle, liquid entry pressure (LEP), bubble-point pressure, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), atomic force microscopy (AFM). Stacked composites of a hydrophobic ePTFE membrane over a hydrophilic PVDF membrane or a hydrophobic PVDF membrane over another hydrophobic PVDF membrane were also studied. Novel conditions created lead to very high water vapor fluxes compared to those from conventional hydrophobic membranes supported on a mesh support. 

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2. Novel perfluorinated nanofiltration membranes for isolation of pharmaceutical compounds

   https://doi.org/10.1016/j.seppur.2020.117944  

   Chau, John; Sirkar, Kamalesh K; Pennisi, Kenneth J; Vaseghi, Gazelle; Derdour, Lotfi; Cohen, Benjamin (January 2021, Separation and purification technology)

   null (Ed.)

   Polymeric membranes for separation of pharmaceutical intermediates/products by organic solvent nanofiltration (OSN) have to be highly resistant to many organic solvents including high-boiling polar aprotic ones, e.g., N- methyl-2-pyrollidone (NMP), dimethylsulfoxide (DMSO), dimethylformamide (DMF). Unless cross-linked, few polymers resist swelling or dissolution in such solvents; however particular perfluoropolymers are resistant to almost all solvents except perfluorosolvents. One such polymer, designated AHP1, a glassy amorphous hydrophobic perfluorinated polymer, has been studied here. Additional perfluoropolymers studied here are hydrophilically modified (HMP2 and HMP3) versions to enhance the flux of polar aprotic solvents. OSN performances of three types of membranes including the hydrophilically modified ones were studied via solvent flux and solute rejection at pressures up to 5000 kPa. The solutes were four active pharmaceutical ingredients (APIs) or pharmaceutical intermediates having molecular weights (MWs) between 432 and 809 Da and three dyes, Oil Blue N (378 Da), Sudan Black B (456 Da), Brilliant Blue R (826 Da). Solvents used were: ethyl acetate, toluene, n- heptane, iso-octane, DMSO, tetrahydrofuran (THF), DMF, acetone, NMP, methanol. Test cells included stirred cells and tangential flow cells. Pure solvent fluxes through three membrane types were characterized using a particular parameter employing various solvent properties. All three membranes achieved high solute rejections around 91–98% at ambient temperatures. HMP2 membrane achieved 95% solute rejection for an API (809 Da) in DMSO at a high temperature, 75 ◦C. A two-stage simulated nanofiltration process achieved 99%+ rejection of a pharmaceutical intermediate (MW, 432 Da) in 75v% NMP-25v% ethyl acetate solution. 

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3. 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)

   null (Ed.)

   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 negatively 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. 

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4. Multiscale modeling of solute diffusion in triblock copolymer membranes

   https://doi.org/10.1063/5.0127570  

   Cooper, Anthony J.; Howard, Michael P.; Kadulkar, Sanket; Zhao, David; Delaney, Kris T.; Ganesan, Venkat; Truskett, Thomas M.; Fredrickson, Glenn H. (January 2023, The Journal of Chemical Physics)

   We develop a multiscale simulation model for diffusion of solutes through porous triblock copolymer membranes. The approach combines two techniques: self-consistent field theory (SCFT) to predict the structure of the self-assembled, solvated membrane and on-lattice kinetic Monte Carlo (kMC) simulations to model diffusion of solutes. Solvation is simulated in SCFT by constraining the glassy membrane matrix while relaxing the brush-like membrane pore coating against the solvent. The kMC simulations capture the resulting solute spatial distribution and concentration-dependent local diffusivity in the polymer-coated pores; we parameterize the latter using particle-based simulations. We apply our approach to simulate solute diffusion through nonequilibrium morphologies of a model triblock copolymer, and we correlate diffusivity with structural descriptors of the morphologies. We also compare the model’s predictions to alternative approaches based on simple lattice random walks and find our multiscale model to be more robust and systematic to parameterize. Our multiscale modeling approach is general and can be readily extended in the future to other chemistries, morphologies, and models for the local solute diffusivity and interactions with the membrane. 

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5. Micropatternable Janus Paper as a Wearable Skin Patch for Sweat Collection and Analysis

   https://doi.org/10.1002/admt.202300396  

   Gao, Yang; Choi, Seokheun (May 2023, Advanced Materials Technologies)

   Abstract Single‐use paper‐based wearable devices are receiving increasing attention as a novel platform for disposable, inexpensive, noninvasive, and real‐time sweat monitoring. The bidirectional liquid transport nature of paper is the most critical barrier to effectively controlling sweat samples for reliable and accurate sweat analysis. Excessive or additionally released sweat significantly interferes with analysis when mixed with old sweat. Moreover, bio‐receptors pre‐loaded in the sensing areas can backflow and move to another sensing region generating a cross‐talk issue. This work enables effective sweat sampling and delivery in paper by facilitating unidirectional sweat transport from the skin to the sensing reservoir. The design and fabrication of a single‐layered paper membrane to achieve Janus‐type properties, which only allow moisture to flow in one direction is introduced. When the hydrophobic side of the Janus paper is placed on the skin, sweat is unidirectionally self‐pumped from the hydrophobic side to the hydrophilic sensing areas, but not the reverse. The fabrication takes two steps including easy automatic and scalable printing of hydrophobic micropatterns on paper and simple heating of the printed paper for the wax penetration. Quantitative colorimetric assessment of pH, chloride, sodium, and glucose in sweat is simultaneously performed without cross‐talk between the sensing regions. 

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