Polymeric Membranes Research Articles

Enhanced phosphate anion flux through single-ion, reverse-selective mixed-matrix cation exchange membrane

Phosphate recovery from wastewater is vital for both environmental sustainability and resource conservation, offering the dual benefit of reducing phosphate pollution while providing a valuable source of this essential nutrient. We previously reported an approach for synthesizing hydrous manganese oxide (HMO) nanoparticles within a polymeric cation-exchange membrane (CEM) to achieve a phosphate-selective mixed-matrix membrane (PhSMMM); however, the phosphate flux was lower than desired. Herein, we demonstrate a next-generation PhSMMM membrane with enhanced phosphate flux and selectivity. Experimental results confirm the successful incorporation of up to 28 wt% HMO nanoparticles into the polymeric CEM. The new PhSMMM exhibits a phosphate flux of 1.57 mmol∙m–2.hr–1 (an 8.5X enhancement), with selectivity over chloride, nitrate, and sulfate ions of 9, 11, and 104, respectively. This significant enhancement in phosphate flux marks a promising advancement in a sustainable solution for phosphate removal and recovery from wastewater.

Effect of bioceramic inclusions on gel-cast aliphatic polymer membranes for bone tissue engineering applications: An in vitro study.

Polylactic acid (PLA) has been extensively used in tissue engineering. However, poor mechanical properties and low cell affinity have limited its pertinence in load bearing bone tissue regeneration (BTR) devices. Augmenting PLA with β-Tricalcium Phosphate (β-TCP), a calcium phosphate-based ceramic, could potentially improve its mechanical properties and enhance its osteogenic potential. Gels of PLA and β-TCP were prepared of different % w/w ratios through polymer dissolution in acetone, after which polymer-ceramic membranes were synthesized using the gel casting workflow and subjected to characterization. Gel-cast polymer-ceramic constructs were associated with significantly higher osteogenic capacity and calcium deposition in differentiated osteoblasts compared to pure polymer counterparts. Immunocytochemistry revealed cell spreading over the gel-cast membrane surfaces, characterized by trapezoidal morphology, distinct rounded nuclei, and well-aligned actin filaments. However, groups with higher ceramic loading expressed significantly higher levels of osteogenic markers relative to pure PLA membranes. Rule of mixtures and finite element models indicated an increase in theoretical mechanical strength with an increase in β-TCP concentration. This study potentiates the use of PLA/β-TCP composites in load bearing BTR applications and the ability to be used as customized patient-specific shape memory membranes in guided bone regeneration.

Purification of Liquid Fraction of Digestates from Different Origins-Comparison of Polymeric and Ceramic Ultrafiltration Membranes Used for This Purpose.

Circular economy, clean technologies, and renewable energy are key to climate protection and modern environmental technology. Recovering water and valuable minerals from the liquid fraction of digestate is in line with this strategy. Digestate, a byproduct of anaerobic methane fermentation in biogas plants, is a potential source of water, minerals for fertilizers, and energy rather than waste. This study examined digestate from municipal and agricultural biogas plants and highlights the need for research on both due to their differences. The use of membrane techniques for water recovery from liquid digestate offers an innovative alternative to conventional methods. This study used standalone membrane filtration and an integrated system to produce water suitable for agricultural use. Ceramic membranes with cut-offs of 1, 5, 15, and 50 kDa and polymeric membranes of polyethersulfone and regenerated cellulose with cut-offs of 10 and 30 kDa were tested. The results showed that the membrane material significantly affects the transport and separation properties. Higher cut-off values increased permeate flux across all membranes. Ceramic membranes were more susceptible to fouling in standalone ultrafiltration, but were more effective in purifying digestate than polymeric membranes. The best results were obtained with a ceramic membrane with a 1 kDa cut-off (for example, for the integrated process and the municipal digestate, the retention rates of COD, BOD5 and DOC were 69%, 62%, and 75%, respectively).

Creative synthesis of pH-dependent nanoporous pectic acid grafted with acrylamide and acrylic acid copolymer as an ultrasensitive and selective riboflavin electrochemical sensor in real samples

In current research, an innovative pectic acid was grafted with poly (acrylamide-co-acrylic acid) [PA-g-poly (AAm-co-AA)] nanoporous membrane using a free radical-mediated grafting copolymerization process. The optimized parameters for the grafting copolymerization reaction such as initiator concentration, monomer concentrations, polymerization reaction time, and temperature were studied. Additionally, the solid content, graft percentage, and conversion were calculated. The unique polymeric membrane was characterized using Fourier-transform infrared spectroscopy (FT-IR), thermal gravimetry (TG), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) supported by energy dispersive X-ray spectroscopy (EDX). The formulated novel PA-g-poly (AAm-co-AA) had a nanoporous structure with a diameter of 113 nm. pH-dependent swelling and biodegradation measurements were also studied. The electrochemical characterizations of PA-g-poly (AAm-co-AA) were conducted through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Furthermore, the screen-printed electrode (SPE) was modified with pure PA and the new generation of its grafted polymeric nanoparticles to detect and quantify the concentration of riboflavin (RF) in real samples using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The modified electrode showed two linear concentration ranges from 0.01 - 2 nM and 2 – 90 nM with low detection limits (LODs) of 0.004 and 0.97 nM, respectively, demonstrating high sensitivity. Besides, the fabricated sensor exhibited more selectivity, simplicity, great reproducibility, repeatability, and good stability. Finally, the PA-g-poly (AAm-co-AA)-modified SPE based sensor was effectively used in real sample analysis of egg yolk, milk, and vitamin B2 drugs with good recovery rates.

Customized 3D-Printed Mesh, Membrane, Bone Substitute, and Dental Implant Applied to Guided Bone Regeneration in Oral Implantology: A Narrative Review.

Background: The new frontiers of computer-based surgery, technology, and material advances, have allowed for customized 3D printed manufacturing to become widespread in guided bone regeneration (GBR) in oral implantology. The shape, structural, mechanical, and biological manufacturing characteristics achieved through 3D printing technologies allow for the customization of implant-prosthetic rehabilitations and GBR procedures according to patient-specific needs, reducing complications and surgery time. Therefore, the present narrative review aims to elucidate the 3D-printing digital radiographic process, materials, indications, 3D printed manufacturing-controlled characteristics, histological findings, complications, patient-reported outcomes, and short- and long-term clinical considerations of customized 3D printed mesh, membranes, bone substitutes, and dental implants applied to GBR in oral implantology. Methods: An electronic search was performed through MEDLINE/PubMed, Scopus, BioMed Central, and Web of Science until 30 June 2024. Results: Three-dimensionally printed titanium meshes and bone substitutes registered successful outcomes in vertical/horizontal bone defect regeneration. Three-dimensionally printed polymeric membranes could link the advantages of conventional resorbable and non-resorbable membranes. Few data on customized 3D printed dental implants and abutments are available, but in vitro and animal studies have shown new promising designs that could improve their mechanical properties and tribocorrosion-associated complications. Conclusions: While 3D printing technology has demonstrated potential in GBR, additional human studies are needed to evaluate the short- and long-term follow-up of peri-implant bone levels and volumes following prosthetic functional loading.

Elucidating the Molecular Mechanisms by which Porous Polymer Networks Affect Structure, Aging Propensity, and Selectivity of Microporous Glassy Polymer Membranes using a Multiscale Approach.

Microporous glassy polymer membranes suffer from physical aging, which adversely affects their performance in the short time frame. We show that the aging propensity of a model microporous polymer, poly(1-trimethylsilyl-1-propyne) (PTMSP), can be effectively mitigated by blending with as little as 5 wt % porous polymer network (PPN) composed of triptycene and isatin. The aging behavior of these materials was monitored via N2 pure gas permeability measurements over the course of 3 weeks, showing a 14% decline in PTMSP blended with 5 wt % PPN vs a 41% decline in neat PTMSP. Noteworthy, PPNs are 2 orders of magnitude cheaper than the porous aromatic frameworks previously used to control PTMSP aging. A variety of experimental and computational techniques, such as Positron Annihilation Lifetime Spectroscopy (PALS), free volume measurements, cross-polarization/magic angle spinning (CP/MAS) 13C NMR, transport measurements and molecular dynamics (MD) simulations were used to uncover the molecular mechanisms leading to enhanced aging resistance. We show that partial PTMSP chain adsorption into the PPN porosity reduces the PTMSP local segmental mobility, leading to improved aging resistance. Permeability coefficients were broken into their elementary sorption and diffusion contributions, to elucidate the mechanism by which the reduced PTMSP local segmental mobility affects selectivity in gas separation applications. Finally, we demonstrate that in these systems, where both chemical and physical interactions take place, transport coefficients must be corrected for thermodynamic nonidealities to avoid erroneous interpretation of the results.

Influences of marine biofouling on the potential responses of polymeric membrane ion-selective electrodes

Using polymeric membrane ion-selective electrodes (ISEs) for reliable long-term marine environmental observations is still a challenge due to the formation of biofilms on electrode surfaces. Unfortunately, the contributions of the specific biofilm components to sensor failure have not been studied. Herein, the influences of the specific biofilm components on the performance of the neutral carrier-based polymeric membrane ISEs are systematically investigated in terms of sensitivity, selectivity, and stability. More importantly, the spatial distributions of these foulants in the fouled sensing membrane phase are studied by confocal laser scanning microscopy for the first time to give insight into the fouling mechanisms. Three typical biochemicals (i.e., proteins, polysaccharides, microbial lipids) in biofilms are selected as the representative foulants. The poly (vinyl chloride)-based CO32--ISEs and K+-ISEs/Ca2+-ISEs have been selected as the model sensors for detection of anions and cations, respectively. Experiments show that depending on the type of the biofoulants, the adsorption of the foulants on the polymeric membrane surface and/or their extraction into the organic membrane phase could occur and induce a change in the potential responses. This study provides a deep insight into the influences of the specific biofilm components on the polymeric membrane ISEs, which is of importance for development of the polymeric membrane marine sensors with high antifouling capabilities for long-term marine monitoring.

Investigation on sulfonated PVC/polymethyl methacrylate (PMMA)/polystyrene sulfonate (PSS) polymer blends as proton-conducting membrane

AbstractThe design and development of cost-effective and increased methanol permeable and proton-conductive membranes are critical concerns in the fabrication of polymeric electrolyte membranes (PEM). A solution-casting process was used to create a low-cost PEM based on sulfonated polyvinyl chloride (SPVC)-Polymethyl methacrylate (PMMA) blended with varying concentrations of Poly(sodium 4-styrenesulfonate) (PSS). The contact angle, oxidative stability, swelling ratio, water uptake, and methanol uptake of SPVC/PMMA/PSS membranes were investigated as a function of PSS molar ratio. FT-IR examination, 1H NMR spectra, Raman spectroscopy, X-ray diffraction, thermogravimetric analysis (TGA), and scanning electron microscope micrographs were additionally utilized for confirming the chemical structure, morphology, and thermal stability of SPVC/PMMA/PSS membranes. Furthermore, the ion exchange capacity (IEC), proton conductivity, and methanol permeability of SPVC/PMMA/PSS membranes were investigated depending on the PSS concentration. The results showed a significant increase in proton conductivity from 1.80 × 10–2 for SPVC/PMMA/1%PSS to 4.7 × 10–2 S/cm for SPVC/PMMA/5%PSS at ambient temperature. On the other hand, the methanol permeability (P = 8.53 × 10–8 cm2/s) was noticeably lower than that of Nafion 117 (3.39 × 10–6 cm2/s). Additionally, the IEC of the manufactured membrane was 1.38 ± 0.7 meq g−1 for SPVC/PMMA/5%PSS compared to 0.91 meq g−1 for Nafion 117 membranes. The maximum water uptake of the synthesized membranes was 48.37 ± 2.27%, whereas Nafion 117 membrane absorption was 65.44%. According to conductivity studies and the membrane efficiency factor, the ideal PSS content in a polymer matrix is 4 wt.%. Finally, the developed SPVC/PMMA/PSS polyelectrolytic membranes show improvements in essential properties such as methanol permeability, proton conductivity, and IEC when combined with low-cost materials, making them an attractive contender as PEM for DMFCs. Graphical abstract

Ten‐Million‐Fold Increase in the Electrical Conductivity of a MOF by Doping of Iodine Into MOF Integrated Mixed Matrix Membrane

AbstractThe development of electrically conductive membranes is essential for advancing future technologies like electronic devices, supercapacitors, and batteries. Newly synthesized doubly interpenetrated 3D‐Cd‐MOF (Metal‐Organic‐Framework) containing angular tetra‐carboxylate is found to display very poor electrical conductivity (10−11 S cm−1). However, it exhibits an exceptional ability to adsorb I2 (I2@Cd‐MOF) which shows increased electrical conductivity of the order of 10−8 S cm−1. Following these results, the Cd‐MOF is integrated into the PVDF‐PVP (Polyvinylidene fluoride‐Polyvinylpyrrolidone) polymeric mixed matrix membrane (MMM) and explores their I2 adsorption capabilities and electrical conductivities before and after I2 adsorption. Four polymeric MMMs with the loading of Cd‐MOF 0, 20, 40, and 50% are tested for their I2 adsorption ability and their respective electrical conductivities. The 50% Cd‐MOF‐loaded MMM is found to exhibit higher adsorption of I2 (685 mg g−1) and significant enhancement in conductivity from 10−11 to 10−4 S cm−1. The raise in the electrical conductivity by 10 million times is attributed to the synergistic interactions between I2, Cd‐MOF, PVDF, and PVP polymers as well as the increase in the concentration of charge carriers (holes) within the frameworks. This work serves as blueprint for controlling charge transfer in MMM to tune their electrical conductivity which opens a large window for advanced device applications.

Scientific evaluation on biodegradable and biofunctional polyurethane incorporated chitosan/elastin electrospun membranes in compared with synthetic polymeric expanded polytetrafluoroethylene and polyethylene terephthalate vascular membranes

Cardiovascular disease is a life-threatening health problem. Employing vascular membranes is one of the treatment options in cardiovascular surgery to replace damaged vascular tissues. However, certain limitations associated with synthetic polymeric vascular membranes (expanded polytetrafluoroethylene (e-PTFE) and polyethylene terephthalate (PET)) such as low biodegradability and biofunctional, may lead to thrombosis, inflammatory response, and tissue necrosis. Polyurethane (PU) is commonly applied in vascular engineering, owing to its good biocompatibility and biodegradability. Incorporating chitosan (CS) and elastin (EL) into the PU matrix, specifically in the design of electrospun nanofibrous membrane, is expected to enhance the biological properties of PU. These improvements are crucial to overcome the limitations of synthetic vascular membranes. Previously, there was no scientific comparison between synthetic vascular membranes and the improved design of PU-based nanofibrous membranes. This scientific comparison is pivotal to allow more research exploration on biodegradable and biofunctional materials towards the fabrication of vascular membranes. Herein, the physicochemical, biodegradability, and biofunctional capability of the electrospun PU-based electrospun membranes and two synthetic membranes were compared. Both PU and PU/CS/ES electrospun membranes were annotated with N–H, C–H, and C–N groups with the appearance of elongated fibers. The –CF2 group was presented in the e-PTFE membranes with the view of expanded fibril structure and interconnecting nodes. Whereas for the PET membranes, C=C, C=O, and C–O groups were noticed with the appearance of homogeneous knitted morphology. The PU/CS/ES membranes were found to be more hydrophilic than the PU and the synthetic membranes. The incorporation of CS and EL in the matrix of electrospun PU has improved the PU's biodegradability up to 23.86 ± 5.86 % at 60 days of incubation with the view of swollen and degraded elongated fibers, following the degradation test. Both synthetic polymeric membranes were declared non-biodegradable with less than 7 % degradation at similar incubation timepoint. The PU/CS/ES membranes were also found biofunctional with the most 82 ± 0.49 % of cell viability, protruded cell filopodia, and 44.24 ± 13.99 % scratch cell closure within 24 h of incubation. The incorporation of CS and EL into the PU matrix has improved the biodegradability and biofunctionality compared to the pure PU and synthetic polymeric membranes. Thus, highlight the suitability of PU/CS/ES electrospun membranes to be applied in cardiovascular tissue engineering.

BiOCl-PVDF nanofibrous membrane for synergic oil-water separation and degradation of dye

Polymeric membranes have garnered remarkable attention, attributed to the significant breakthrough in the filtration of oily wastewater. However, the major setbacks of pristine polymeric membranes include susceptibility to fouling and chemical instability. Addressing such issues, this work focusses in the modification of polymer membranes using a metal oxyhalide, such as Bismuth oxychloride (BiOCl). This modification not only enhances water purification capabilities but also strengthens the membrane, protecting it from environmental deterioration and extending its lifespan. BiOCl was integrated into an electrospun pristine nanofibrous polymeric membrane using hydrothermal technique. The synthesized membrane matrix displayed superhydrophilicity and underwater superoleophobicity, effectively separating oil-in-water mixtures and emulsions. Moreover, BiOCl was effectively utilized to assess organic pollutant adsorption and degradation through photocatalysis. In addition, the membrane exhibited exceptional recyclability and withstood harsh conditions, contributing to its mechanical stability. The numerous advantages, enhance the effectiveness of BiOCl modified membrane in water pollution remediation.

Electroless Deposition for Robust and Uniform Copper Nanoparticles on Electrospun Polyacrylonitrile (PAN) Microfiltration Membranes.

Filtration membranes coated in metals such as copper have dramatically improved biofouling resistance and pathogen destruction. However, existing coating methods on polymer membranes impair membrane performance, lack uniformity, and may detach from their substrate, thus contaminating the permeate. To solve these challenges, we developed the first electroless deposition protocol to immobilize copper nanoparticles on electrospun polyacrylonitrile (PAN) fibers for the design of antimicrobial membranes. The deposition was facilitated by prior silver seeding. Distinct mats with average fiber diameters of 232 ± 36 nm, 727 ± 148 nm and 1017 ± 80 nm were evaluated for filtration performance. Well-dispersed copper nanoparticles were conformal to the fibers, preserving the open-cell architecture of the membranes. The copper particle sizes ranged from 20 to 140 nm. Infrared spectroscopy revealed the PAN fiber mats' relative chemical stability/resistance to the copper metallization process. In addition, the classical cyclization of the cyano functional group in PAN was observed. For model polystyrene beads with average sizes of 3 μm, Cu NP-PAN fiber mats had high water flux and separation efficiency with negligible loss of Cu NP from the fibers during flow testing. Fiber size increased flux and somewhat decreased separation efficiency, though the efficiency values were still high.

Controlled released dynamics of methotrexate from chitosan-based capsules: A detailed energy landscape analysis

Polymeric membranes are extensively used to construct vehicles for various drug delivery applications. In this study, we investigated the potential of chitosan-based membranes as a carrier for the controlled release of methotrexate (MTX), a widely used drug in cancer treatment. The chitosan (CS) chains were cross-linked with sodium tripolyphosphate (STPP) to form a rigid matrix capable of encapsulating MTX. Molecular dynamics simulations were employed to assess the performance of the CS-based membranes in releasing MTX upon exposure to water. We have calculated the potential of mean force to understand the energy landscape in the aqueous medium or ethanol-water solution. We have observed that the free energy in the ethanol-water solution reduced to ∼52.4 kcal/mol as compared to an aqueous solution. In addition, we have shown the effect of the concentration of STPP on the binding of CS with MTX. Understanding how STPP concentration affects MTX release is crucial for designing drug delivery systems. By adjusting the concentration of STPP, one can fine-tune the release profile of the drug. We have also shown the comparative study of energy requirement to release a drug molecule from the CS matrix with and without STPP molecules. The pair correlation displayed that the water molecules have a stronger interaction with the STPP molecules compared to CS chains and MTX molecules. Our findings indicate that the CS nanoparticles exhibit promising characteristics for controlled drug release, making them a potential candidate for improving the efficacy and safety of MTX therapy in cancer treatment.

Eco-friendly electrochemical assay of oxytetracycline and flunixin in their veterinary injections and spiked milk samples

Two solid-contact electrochemical sensors were developed for detection of each of oxytetracycline HCl (OXY), and the co-formulated non-steroidal anti-inflammatory drug flunixin meglumine (FLU) in veterinary formulations and animal-derived food products. The designed sensors were based on a glassy carbon electrode as the substrate material and high molecular weight polyvinyl chloride (PVC) polymeric ion-sensing membranes doped with multiwalled carbon nanotubes (MWCNTs) to improve the potential stability and minimize signal drift. For determination of OXY, the sensing membrane was modified with potassium tetrakis (4-chlorophenyl) borate (K-TCPB), which was employed as a cation exchanger, and 2-hydroxypropyl-β-cyclodextrin (HP-ßCD), which was used as an ionophore. A linear response within a concentration range of 1 × 10− 6-1 × 10− 2 M with a slope of 59.47 mV/decade over a pH range of 1–5 was recorded. For the first time, two potentiometric electrodes were developed for determination of FLU, where the sensing membrane was modified with tetra dodecyl ammonium chloride (TDDAC) as an anion exchanger. A linear response within a concentration range of 1 × 10− 5-1 × 10− 2 M and a slope of -58.21 mV/decade over a pH range of 6–11 was observed. The suggested sensors were utilized for the selective determination of each drug in pure powder form, in veterinary formulations, and in spiked milk samples, with mean recoveries ranging from 98.50 to 102.10, and without any observed interference. The results acquired by the proposed sensors were statistically analyzed and compared with those acquired by the official methods, and the results showed no significant difference.Graphical

Fabrication and Customization of Highly Porous PLGA Membranes Utilizing Near‐Field Electrospinning, Thermal Transitions, and Multilayer Strategies

Polymer porous membranes are crucial in various applications, including water filtration, tissue engineering, and drug administration. Conventional far‐field electrospinning (FFES) is widely used for producing polymeric membranes due to its cost‐effectiveness, scalability, and flexibility in using many polymers. However, FFES has limitations in controlling pore form and size, as it produces randomly oriented fibers that lead to inconsistent and noncustomizable pore sizes. To address these limitations, this work combines near‐field electrospinning (NFES) with thermal treatment of polymer fibers and membranes. NFES offers more precise control over fiber placement and alignment, producing well‐defined fiber patterns with consistent and customizable pore sizes without compromising the thickness of membranes. By exploring the interplay between polymer behavior, thermal effects, and capillary action, the differences in pore area under various temperatures and fiber spacings are characterized. Additionally, this study investigates the influence of multilayer infusion on pore size and geometric arrangement by examining multilayer configurations stacked at various angles. The results indicate that increasing the number of layers leads to decreased pore size, while the alignment of infused fibers affects pore shape. This integrated approach enhances control over membrane characteristics, improving the performance and consistency of polymer porous membrane fabrication across various applications.

Designing new sulfate ionophores for potentiometric membrane sensors: Selectivity assessment and practical application

Developing potentiometric chemical sensors for sulfate determination is a rather challenging task due to a considerable hydrophilicity of this anion and its poor affinity to lipophilic plasticized polymeric membranes – one of the most popular sensor membrane materials nowadays. Not too many research works were devoted to this problem in the last years. Here we report on the successful development of several novel sulfate ionophores based on the synthetic modification of the commercially available sulfate ionophore I. The newly developed sensors outperform commercial analogue in terms of elelctrochemical sensitivity and selectivity. We have highlighted certain problems with numerical selectivity assessment in case when primary and interfering ions have different charges. The counterintuitive results yielded by conventional selectivity quantification methods implies the relevance of using alternative approach – visualizing sensor response curves towards primary ion in the presence of interfering ions. Novel sulfate sensors were applied for direct potentiometric measurements of sulfate content in river water samples demonstrating real applicability of the developed sensor membranes.

Design Rules for Capillary Force-Induced Clustering and Recovery of Monolithic Microbridges on Microapertured Polymer Membrane.

Microbridge structures have been widely used in microelectromechanical systems. When the devices with microbridges operate in diverse environments, including wet conditions, structural failures such as crumples, clustering, and collapse of micro/nanostructures occur due to the capillary force of liquid in this environment. It is necessary to establish comprehensive design criteria to address this. Herein, we investigate the structural stability of microbridges on microsized apertures in wet conditions. The multiscale structure is fabricated with microbridge width, spacing of 10 μm, and height of 6 μm while varying the supporting micro aperture size. The behavior of the microbridges is observed through an optical microscope during water dispensing on the bridges and evaporation. It is found that the microbridges remain stable on apertures of 100 μm in diameter, while clustering occurs on larger-sized apertures (300, 500 μm). Interestingly, in contrast to the 500 μm-sized aperture, the clustered microbridges on the 300 μm-sized aperture gradually recover to their original configuration after completely evaporating water. A simple theoretical model for capillary force-induced clustering and recovery is proposed to elucidate this phenomenon, which agrees with the experimental results. The microbridges constructed following the design rule can ensure robust and stable operation even in wet conditions. These findings contribute to advancing micro/nanoscale engineering and offer insights for developing innovative microdevices.

Practical limits of the quartz crystal microbalance and surface plasmon resonance for elucidating salt or ion partitioning into membrane polymers

Determining the partitioning of sodium chloride into polyamide (PA) reverse osmosis membranes used for seawater desalination is indispensable for optimizing the salt retention of the membranes. Furthermore, the recent quest for ion-selective membranes requires physico-chemical characterization techniques capable of elucidating partitioning phenomena of ions into membrane polymers in general. Quartz-crystal microbalance with dissipation monitoring (QCM-D) has been explored for this purpose as it has in theory a sensitivity in the range of pg/cm2 and is an accessible and apparently simple method to use. However, it is a technique that intrinsically lacks an internal reference, and it is affected by liquid bulk changes. As the conventional applications of QCM-D are of biophysical nature where changes in solute concentrations are in the nano to micromolar range, we investigated systematically in how far QCM-D yields reliable results for determining salt partitioning coefficients at concentrations relevant for the industrial-scale. We could clearly demonstrate that QCM-D possibly detects salt absorption only at salt concentrations higher than that in seawater (0.6 M). Furthermore, the variation in the liquid bulk response was so significant that it overlapped with a possibly perceived response due to salt absorption. Therefore, we concluded that salt partitioning coefficients derived from QCM-D data have a low confidence and, in any case, should always be reported accompanied by the raw data. We corroborated these findings with multi-parameter surface plasmon resonance (MP-SPR) which widely confirmed the trends observed with QCM-D.

A transition in diffusion behaviors of organic liquid mixtures in dense polymer membranes

Multi-component mass transfer frameworks, such as the Maxwell-Stefan approach, parameterized with the pure component diffusion and sorption behaviors of different substances in polymer materials have been used in predicting complex mixture permeation through polymer membranes. However, a change in the physical state of a polymer membrane (e.g., swelling) or the polymer dynamics (e.g., plasticization) is likely when the membrane is exposed to a high activity organic solvent mixture with strong chemical affinity for the polymer. These changes complicate the accurate estimation of diffusion coefficients for mixtures of solvents based on knowledge of pure component diffusivities within the polymer. Here, we present 120 organic solvent reverse osmosis (OSRO) permeation test results for hydrocarbon liquid mixtures with varying compositions in three different polymers and compare the experimental results to the predictions of a Flory-Huggins coupled Maxwell-Stefan model with two different diffusion modalities. The effect of the chemical affinity between the mixture and the membrane – estimated by the Hansen solubility difference – on the diffusion behaviors of individual solvents permeating through the membrane was investigated via the usage of this model. Our work demonstrates that polymer membranes undergo a reduction for the effectiveness of diffusion-based separation near a specific threshold level of solubility difference (8 MPa0.5) from the mixture and that this difference is consistent across several different membrane materials.

Impact of compliant electrodes on the dynamics of electromagnetoactive membranes

The dynamics of electromagnetoactive polymer (EMAP) membranes have attracted much attention recently because of their wide range of modern robotic applications. Such applications majorly centered on how the dynamics of this novel class of membranes are affected by the mechanical behavior of the compliant electrode. This article presents the dynamic modeling and analysis of EMAP membranes, examining how the inertia of the electrode, coupled with its inherent viscoelastic properties, impacts its dynamic performance. Both the compression and suspension stages of the membrane are covered here in broad terms. An Euler–Lagrange equation of motion is implemented to deduce the governing dynamic model equation of the membrane system. The findings of the model solutions provide preliminary insights to characterize the dynamic response, instability analysis, periodic behavior, and resonance properties across varying parameters such as inertia, electric field, magnetic field, and prestress. Moreover, the study also evaluates the periodicity and stability of the nonlinear oscillations using Poincaré maps and phase portraits, facilitating an assessment of quasi-periodic to periodic transitions.