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At least 37 records · Page 2

The physical basis for solvent flow in organic solvent nanofiltration

Organic solvent nanofiltration (OSN) is an emerging membrane technology that could revolutionize chemical separations in numerous vital industries. Despite its significance, there remains a lack of fundamental understanding of solvent transport mechanisms in OSN membranes. Here, we use an extended Flory-Rehner theory, nonequilibrium molecular dynamic simulations, and organic solvent transport experiments to demonstrate that solvent flow in OSN membranes is driven by a pressure gradient. We show that solvent molecules migrate as clusters through interconnected pathways within the membrane pore structure, challenging the widely accepted diffusion-based view of solvent transport in OSN. We further reveal that solvent permeance is dependent on solvent affinity to the OSN membrane, which, in turn, controls the membrane pore structure. Our fundamental insights lay the scientific groundwork for the development of next-generation OSN membranes.

42 ENGINEERING↗

Bench-Top Antigen Detection Technique that Utilizes Nanofiltration and Fluorescent Dyes which Emit and Absorb Light in the Near Infrared

This article discusses the development of a bench-top technique to detect antigens in fluids. The technique involves the use of near infrared NIR fluorescent dyes conjugated to antibodies, centrifugation, nanofilters, and spectrometry. The system used to detect the antigens utilizes a spectrometer, fiber optic cables, NIR laser, and laptop computer thus making it portable and ideally suited for desk top analysis. Using IgM as an antigen and the secondary antibody, anti-IgM conjugated to the near infrared dye, IRDye (trademark) 800, for detection, we show that nanofiltration can efficiently and specifically separate antibody-antigen complexes in solution and that the complexes can be detected by a spectrometer and software using NIR laser excitation at 778 nm and NIR dye offset emission at 804 nm. The peak power detected at 778 nm for the excitation emission and at 804 nm for the offset emission is 879 pW (-60.06 dBm) and 35.7 pW (-74.5 dBm), respectively.

Varaljay-Spence, Vanessa A.↗

Benchtop Antigen Detection Technique using Nanofiltration and Fluorescent Dyes

The designed benchtop technique is primed to detect bacteria and viruses from antigenic surface marker proteins in solutions, initially water. This inclusive bio-immunoassay uniquely combines nanofiltration and near infrared (NIR) dyes conjugated to antibodies to isolate and distinguish microbial antigens, using laser excitation and spectrometric analysis. The project goals include detecting microorganisms aboard the International Space Station, space shuttle, Crew Exploration Vehicle (CEV), and human habitats on future Moon and Mars missions, ensuring astronaut safety. The technique is intended to improve and advance water contamination testing both commercially and environmentally as well. Lastly, this streamlined technique poses to greatly simplify and expedite testing of pathogens in complex matrices, such as blood, in hospital and laboratory clinics.

Scardelletti, Maximilian C.↗

Physicochemical and Performance Characterization of Six Commercial Organic Solvent Nanofiltration Membranes

This work introduces a novel, gradient-free metamaterial design method based on Gaussian process regression to represent the density field of a unit cell. The dimension of the design space is determined by the covariance matrix dimension in the Gaussian process regression. We propose compressing this matrix using an autoencoder, enabling the decoder to generate the density field and effectively reduce the originally large design space to a lower-dimensional subspace. In this compressed space, we employ an active learning method, Bayesian Adaptive Direct Search (BADS), for efficient exploration of the design space. We demonstrate that for simple 2D designs aimed at maximizing unit cell stiffness, our method yields results comparable to those of standard topology optimization. Furthermore, we extend our approach to various mechanical problems, from linear elasticity to hyperelastic large deformation and elasto-plasticity under finite deformation, to 3D metamaterial design. This illustrates the method’s versatility and effectiveness across a range of applications.

Wu, Haoran↗

Combinatorial Membrane Synthesis: Fundamentals of Hybrid Metal-Organic Brush (MOB) Membranes for Organic Solvent Nanofiltration (Renewal)

(a) Goals: The goals of our current 3-year research project are (i) expansion of the novel modification technique Single Electron Transfer- Living Radical Polymerization (SET-LRP) to graft polymer brushes on a polyimide stable support followed by characterization and testing of the ensuing membrane (ii) stiffen brush network utilizing (a) metal organic frameworks and (b) covalent bonds formed as a result of crosslinking the grafted brush network. (b) Approach: The approach taken for this research was: (i) to graft branches terminated with a carboxyl group on each bristle (or bristle branch) allowing (a) metal immobilization to form MOF-like structures between branches or (b) crosslink bristles using aliphatic or aromatic diamines; (ii) to test the performance of the membranes using organic dyes, pure solvents (alcohols) and industrially relevant organic solvent separations; and (iii) to characterize these modified brush membranes. (c) Findings: The significant findings from the past one year are summarized below (papers resulting from this work are listed below and in D. PUBLICATIONS and relevant references are found in E. REFERENCES.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monolithic Polyepoxide Membranes for Nanofiltration Applications and Sustainable Membrane Manufacture

The present work details the development of carbon fiber-reinforced epoxy membranes with excellent rejection of small-molecule dyes. It is a proof-of-concept for a more sustainable membrane design incorporating carbon fibers, and their recycling and reuse. 4,4′-methylenebis(cyclohexylamine) (MBCHA) polymerized with either bisphenol-A-diglycidyl ether (BADGE) or tetraphenolethane tetraglycidylether (EPON Resin 1031) in polyethylene glycol (PEG) were used to make monolithic membranes reinforced by nonwoven carbon fibers. Membrane pore sizes were tuned by adjusting the molecular weight of the PEG used in the initial polymerization. Membranes made of BADGE-MBCHA showed rejection of Rose Bengal approaching 100%, while tuning the pore sizes substantially increased the rejection of Methylene Blue from ~65% to nearly 100%. The membrane with the best permselectivity was made of EPON-MBCHA polymerized in PEG 300. It has an average DI flux of 4.48 LMH/bar and an average rejection of 99.6% and 99.8% for Rose Bengal and Methylene Blue dyes, respectively. Degradation in 1.1 M sodium hypochlorite enabled the retrieval of the carbon fiber from the epoxy matrix, suggesting that the monolithic membranes could be recycled to retrieve high-value products rather than downcycled for incineration or used as a lower selectivity membrane. The mechanism for epoxy degradation is hypothesized to be part chemical and part physical due to intense swelling stress leading to erosion that leaves behind undamaged carbon fibers. The retrieved fibers were successfully used to make another membrane exhibiting similar performance to those made with pristine fibers.

Polymer Science↗

Production and Catalytic Upgrading of 2,3-Butanediol Fermentation Broth into Sustainable Aviation Fuel Blendstock and Fuel Properties Measurement

With the increasing demand for sustainable supplies of aviation fuel and need to address climate change, new conversion technologies are needed to efficiently process biomass, produce high quality jet fuel blendstock, and meet carbon emission targets. This study demonstrates the synthesis, conditioning, and catalytic upgrading of 2,3-butanediol (BDO) fermentation broth into a jet fuel blendstock candidate. A high-titer 2,3-BDO fermentation broth (i.e., ~90 g/L) was produced at a 100-L scale and pretreated via nanofiltration to decrease the impurities level in the broth from 4.6 to 0.6 wt%. A novel process for catalytic upgrading of aqueous 2,3-BDO into a jet fuel blendstock candidate was developed, and each step was efficiently demonstrated. The catalytic steps include 1) 2,3-BDO dehydration into methyl ethyl ketone (MEK) over AlPO4, 2) MEK conversion into olefins over Zn1Zr10Ox, 3) oligomerization of olefins over a zeolite beta, and 4) hydrogenation over platinum/carbon. Both the model feed and real 2,3-BDO fermentation broth were tested for upgrading 2,3-BDO to MEK. With the real feed, a continuous loss of conversion (i.e., >50% loss over ~140 h time-on-stream [TOS]) was partly attributed to reversible deactivation from coking species. However, the conversion remained stable with the model feed, which demonstrates the efficiency of the first step for converting aqueous 2,3-BDO (10 wt% in water). For upgrading MEK to olefins, high selectivity to olefins (i.e., 82.5%) was obtained at high conversion levels (i.e., 93-98%) with stable conditions being achieved for > 70-hours TOS. Oligomerization of light olefins, which was demonstrated for > 270 h TOS, mainly led to the formation of dimers (C8-10) and trimers (C13-14). The oligomerized product was hydrogenated and distilled to recover the jet fraction (35 mass% or 40.9% carbon based yield), which consists mostly of desired isoalkanes (31.7 wt%), n-alkanes (24.5 wt%), and cycloalkanes (29.6 wt%). While some improvement is still needed to meet ASTM D7566 specifications for viscosity and final boiling point temperature, freezing point, density, aromatics content, and sulfur content of the jet blendstock candidate were within acceptable ranges, thus highlighting the potential of this process for production of jet fuel blendstock.

ADVANCED PROPULSION SYSTEMS,BIOMASS FUELS↗

Polyamide-Based Ion Exchange Membranes: Cation-Selective Transport through Water Purification Membranes

Ion-selective membranes are necessary components of many electrochemical systems including fuel cells, electrolyzers, redox flow batteries, and electrodialyzers. Perfluorinated sulfonated membranes (PFSMs) dominate these applications due to their excellent combination of fast ion transport, stability, and processability. However, perfluorinated cation exchange membranes (CEMs) are expensive, and their production process involves chemistry that generates toxic perfluorinated chemicals. The development of affordable, nonfluorinated membranes with a competitive combination of high ion selectivity, transport, and stability could help enable the widespread use of the technologies listed above while hastening the development of emerging electrochemical systems, including aqueous alkaline CO 2 sorbent regeneration. To this end, we pursue the use of thin-film composite polyamide (PA-TFCs) membranes–those that typically find application in reverse osmosis and nanofiltration desalination–as cation-selective exchange membranes. Given their negative surface charge under neutral-to-alkaline conditions, PA-TFCs can serve as effective CEMs in these pH regimes. We prepared a series of PA-TFCs from traditional monomers (trimesoyl chloride and piperazine) and compared their thicknesses, charge densities, water transport properties, ion transport properties, and long-term stability in a high pH environment to traditional CEMs (Nafion and FKE) and commercial nanofiltration and reverse osmosis membranes. We find that some of the best-performing PA-TFC membranes have similar resistances and Na + transference numbers compared to Nafion 117 in Na 2 SO 4 and NaHCO 3 -containing solutions. This proof-of-principle study suggests that further optimization of PA-TFCs could enable cost-effective ion exchange membrane alternatives to PFSMs.

36 MATERIALS SCIENCE↗

Molecular Simulation of Functionalized Covalent Organic Framework Membranes for Inorganic Salt Separation

Covalent organic frameworks (COFs) enable molecular-level design of nanochannels for selective separation in pressure-driven membrane processes. Through variation of building blocks and, subsequently, the pore structure and chemistry, membrane performance can be tailored. This study employs nonequilibrium molecular dynamics simulations to theoretically demonstrate the tunable selectivity of COF membranes through a bottom-up functionalization approach. Water and salt transport are evaluated for six β-ketoenamine-linked COFs with varying multilayer thicknesses. For the thinnest multilayer (0.64–0.72 nm), all COFs exhibit low sodium sulfate (Na 2 SO 4 ) rejection (55–66%). However, 20 stacked sheets (6.4–7.2 nm) provide 67–98% rejection, with the sulfonated COF providing the highest Na 2 SO 4 rejection. Analysis of time-resolved ion density profiles reveals that solute rejection is primarily governed by interfacial exclusion arising from pore size and functional group chemistry. Although increasing salt rejection compromises water permeance, the permeance of all COF membranes is at least two orders of magnitude greater than that of a commercially available nanofiltration membrane. Overall, this work guides the rational design of COF membranes for aqueous salt separation.

Nanofiltration↗