Integrated carboxylic carbon nanotube pathways with membranes for voltage-activated humidity detection and microclimate regulation.

This work describes some single walled carboxylic carbon nanotubes with outstanding transport properties when assembled in a 3D microarray working like a humidity membrane-sensor and an adjustable moisture regulator. Combined nano-assembly approaches are used to build up a better quality pathway through which assisted-charge and mass transport synchronically takes place. The structure-electrical response relationship is found, while controllable and tunable donor-acceptor interactions established at material interfaces are regarded as key factors for the accomplishment of charge transportation, enhanced electrical responses and adjustable moisture exchange. Raman and infrared spectroscopy provides indications about the fine structural and chemical features of the hybrid-composite membranes, resulting in perfect agreement with related morphology and electrical properties. Enhanced and modular electrical response to changes in the surrounding atmosphere is concerned with doping events, while assisted moisture regulation is discussed in relation to swelling and hopping actions. The electro-activated hybrid-composite membrane proposed in this work can be regarded as an attractive 'sense-to-act' precursor for smart long-distance monitoring systems with capability to adapt itself and provide local comfortable microenvironments.

Exfoliated Bi2Te3-enabled membranes for new concept water desalination: Freshwater production meets new routes.

Water scarcity forces the science to find the most environmentally friendly propulsion technology for supplying plentiful freshwater at low energy costs. Membrane Distillation well meets criteria of eco-friendly management of natural resources, but it is not yet competitive on scale. Herein, we use a dichalchogenide compound (Bi2Te3) as a conceivable source to accelerate the redesign of advanced membranes technologies such as thermally driven membrane distillation. A procedure based on assisted dispersant liquid phase exfoliation is used to fill PVDF membranes. Key insights are gained in the crucial role of this topological material confined in hydrophobic membranes dedicated to recovery of freshwater from synthetic seawater. Intensified water flux together with reduced energy consumption is obtained into one pot, thereby gathering ultrafast production and thermal efficiency in a single device. Bi2Te3-enabled membranes show ability to reduce the resistance to mass transfer while high resistance to heat loss is opposite. Permeate flux is kept stable and salt rejection is higher than 99.99% during 23 h-MD test. Our results confirm the effectiveness of chalcogenides as frontier materials for new-concept water desalination through breakthrough thermally-driven membrane distillation, which is regarded as a new low-energy and sustainable solution to address the growing demand for access to freshwater.

A few-layer graphene for advanced composite PVDF membranes dedicated to water desalination: a comparative study.

Membrane distillation is envisaged to be a promising best practice to recover freshwater from seawater with the prospect of building low energy-consuming devices powered by natural and renewable energy sources in remote and less accessible areas. Moreover, there is an additional benefit of integrating this green technology with other well-established operations dedicated to desalination. Today, the development of membrane distillation depends on the productivity-efficiency ratio on a large scale. Despite hydrophobic commercial membranes being widely used, no membrane with suitable morphological and chemical feature is readily available in the market. Thus, there is a real need to identify best practices for developing new efficient membranes for more productive and eco-sustainable membrane distillation devices. Here, we propose engineered few-layer graphene membranes, showing enhanced trans-membrane fluxes and total barrier action against NaCl ions. The obtained performances are linked with filling polymeric membranes with few-layer graphene of 490 nm in lateral size, produced by the wet-jet milling technology. The experimental evidence, together with comparative analyses, confirmed that the use of more largely sized few-layer graphene leads to superior productivity related efficiency trade-off for the membrane distillation process. Herein, it was demonstrated that the quality of exfoliation is a crucial factor for addressing the few-layer graphene supporting the separation capability of the host membranes designed for water desalination.

On the use of ultrasonic dental scaler tips as cleaning technique of microfiltration ceramic membranes.

The use of ultrasonic dental scaler (UDS) tips has been investigated for cleaning ceramic membranes fouled when filtering cactus juice. Thin and long tips having a larger coverage exhibited the best performance for removing the cake layer deposited on the membrane surface. Such tips cleaned an area equivalent to almost one third of total area of the membrane surface. However, the cleaned area could be increased notoriously if the membrane were placed in rotatory disc holder. The resistance-in series model and atomic force microscopy (AFM) technique helped to reveal the effect of the UDS tips as cleaning process of ceramic membranes. The reversible resistances estimated for UDS tips were 58% and 17% lower than the ones obtained by chemical cleaning at transmembrane pressures of 0.3 bar and 0.5 bar, respectively. This was corroborated by microscope images, which showed the detachment of cake layer of the membrane surface. Results of this work showed that UDS tips are an innovative option as cleaning strategy for filtration membranes.

Competitive hydrogen-bonding interactions in modified polymer membranes: a density functional theory investigation.

The subject of this work is the density functional theory (DFT) investigation of competitive hydrogen-bonding interactions that occur in modified block poly(ether/amide) (PEBAX) membranes. Previously, an evaluation of hydrogen-bonding interactions occurring between N-ethyl-o,p-toluensulfonamide (KET) modifiers was performed to establish the role of these interactions in affinity processes when the modifier is dissolved in PEBAX matrixes. However, some issues related to polymer-polymer (host-host) and modifier-polymer (host-guest) interactions were not analyzed from a theoretical point of view in the previous analysis. Here, a comparative computational analysis of these intermolecular interactions is discussed. New insights into the role of hydrogen bonding in domino processes are provided. Calculations in solvent and in vacuum have been done, yielding indications about the change in the availability of the polar groups of the polymer, which is considered to be partially responsible for the enhanced hydrophilicity of the membranes. This study can open the way to the construction of new predictive quantum modeling approaches for designing improved modifiers, enabling the optimization of polymer membrane performance.

Adsorption-assisted transport of water vapour in super-hydrophobic membranes filled with multilayer graphene platelets.

The effects of confinement of multilayer graphene platelets in hydrophobic microporous polymeric membranes are here examined. Intermolecular interactions between water vapour molecules and nanocomposite membranes are envisaged to originate assisted transport of water vapour in membrane distillation processes when a suitable filler-polymer ratio is reached. Mass transport coefficients are estimated under different working conditions, suggesting a strong dependence of the transport on molecular interactions. Remarkably, no thermal polarization is observed, although the filler exhibits ultrahigh thermal conductivity. In contrast, enhanced resistance to wetting as well as outstanding mechanical and chemical stability meets the basic requirements of water purification via membrane distillation. As a result, a significant improvement of the productivity-efficiency trade-off is achieved with respect to the pristine polymeric membrane when low amounts of platelets are confined in spherulitic-like PVDF networks.

Combined emulsion and phase inversion techniques for the preparation of catalytic PVDF microcapsules.

In this work, polyvinilydene fluoride (PVDF) microcapsules were prepared by using combined emulsion and phase inversion techniques. With this method, microcapsules with different diameters and porosities have been obtained by just controlling the diameter of the membrane used during the preparation. Using a PVDF solution containing the oxidation catalyst ammonium molybdate (20 wt %), catalytic polymeric microcapsules with diameters ranging from 600 to 1,200 microm have been obtained. Characterization of catalytic microcapsules by means of SEM, BSE, and EDX analyses showed a uniform ammonium molybdate dispersion in the polymeric matrix. Catalytic microcapsules have been tested in the oxidation of aromatic primary alcohols to corresponding aldehydes. In the range 600-1,200 microm, the microcapsule diameter influences the formation of oxidation products: in particular, microcapsule diameters >900 microm slightly diminish the formation of aldehyde due to a beginning diffusion limitation. An interesting structure-reactivity behavior, induced by the interaction between the polymeric membrane and the substituted aromatic alcohol, has been observed.

Treatment of dye solutions by vacuum membrane distillation.

In this work, the vacuum membrane distillation (VMD) process has been applied to treat water containing different types of dyes. The influence of operating parameters, as feed temperature, feed flow rate, feed concentration, on the permeate flux and on rejection has been investigated. In all experimental tests, a complete rejection has been achieved and pure water has been recovered at the permeate side. Furthermore, experiments with water as feed have been carried out before and after the tests with dyes, in order to analyze the effect of fouling on the performance of the VMD. The water vapor fluxes immediately after the tests with dyes were higher than the values registered before the tests, probably due to an interaction with the polymeric membrane material which promotes a swelling of the membrane when in contact with the dye solutions. However, initial fluxes are recovered after prolonged cleaning with only water.

Intermolecular interactions as controlling factor for water sorption into polymer membranes.

A multidisciplinary approach was used for delineating the mechanisms controlling water sorption into modified block co-poly-(ether/amide) (PEBAX) membranes. In particular, incorporation of aromatic sulfonamide (KET) into the polymer matrix led to a nonlinear increase of water sorption in the membrane. The modification in sorption was accompanied by a nonlinear behavior in membrane surface energies. Infrared analysis revealed a different availability and accessibility of free polar groups supporting the formation of hydrogen bonding as a function of modifier concentration. A combination of both experimental and theoretical procedures was used to analyze the molecular processes of water sorption on PEBAX membranes. Molecular dynamics (MD) and quantum chemical (QC) calculations demonstrated that the formation of KET-KET dimers in the polymeric matrix led to a decrease in the interaction energy between water and modifiers. In addition, no variations in the dipole moments of water-dimer structures were found in comparison to a single KET and water-KET molecule. The formation of water-dimer complexes at higher concentration of modifier decreases the number of the dipole moment, thus preventing the polarization of polymer chains.

New PVDF membranes: The effect of plasma surface modification on retention in nanofiltration of aqueous solution containing organic compounds.

New nanofiltration membranes were prepared by non-solvent-induced phase inversion from a PVDF/DMF/water system. The effect of exposure time before coagulation on the membrane characteristics (morphology, thickness, overall porosity, tensile strength) was investigated. PVDF membrane prepared at a fixed exposure time of 45s (PF45) was further plasma surface modified (RF 13.56 MHz) (PF45psm), introducing amino groups on the membrane. The performances of PF45, PF45psm and of a commercial nanofiltration membrane (N30F) were tested in the removal of two dyes from aqueous solution, characterized by different charge and molecular weight (congo red and methylene blue). The observed rejections depended more on the charge of the compound than on their molecular weights and results were optimized for the plasma modified membrane (PF45psm) with respect to unmodified (PF45) and commercial N30F membranes. In particular, methylene blue was retained for 100% by PF45psm with a relative flux of 65% compared to 38% of rejection and 59% of relative flux observed for N30F.

Force balance conditions for droplet formation in cross-flow membrane emulsifications.

The membrane emulsification process is becoming of growing interest in many industrial fields. For monitoring the influence of process and membrane parameters on the droplet formation, quantitative information on the droplet detachment, during this process, is important. Until now, droplet formation has theoretically been described using computational fluid dynamics and global force equations. Unlike computational fluid dynamics methods, the global force models are less accurate but easier to handle and instructive. On this basis, in the present paper we present new force balance equations to describe droplet detachment during cross-flow membrane emulsification. In a first approximation, the droplet is supposed to grow leaning on the pore border as long as a force balance exists along the contact line located on the membrane surface. During this phase the base of the droplet, still stuck on the pore border, begins to bend on the membrane surface until its final detachment. Using force balance equations made along the contact lines, we obtain the minimum and maximum sizes that a droplet could have during cross-flow membrane emulsification. This approach is tested with different continuous phase velocities, membrane pore sizes and interfacial tensions. The results are compared to various experimental data, reported in literature. In particular, based on the experimentally found linear correlation between droplet and pore sizes, we show how the proposed balance equations can be used to obtain a satisfactory evaluation of the slopes of this linear correlation and how these force balances could be used to obtain an estimation of the interfacial tensions during the droplet formation.

Study of the surface character as responsible for controlling interfacial forces at membrane-feed interface.

The role of the interfacial forces was emphasized in interactive processes, involving membrane surface and penetrating molecules. The surface character controlling the dissolution process of some species (CO2, H2O, C3H6O2, C4H8O2, C5H10O2) was evaluated in relation to the supra-molecular chemistry of membranes based on 80PTMO/PA12. Infrared analyses combined with the estimation of the hydrophilic and hydrophobic domains of the membrane surface yielded useful information about the distribution, availability and accessibility of the polar moieties responsible for the penetrant sorption. At the interface, attractive Lewis acid/base interactions such as H-bonding directed the sorption of vapor species into the membranes, whereas quadrupolar CO2 participated in specific Lifshitz-van der Waals interactions with the modified polymers. In both the cases, the presence of additional polar moieties such as carbonyl, sulfonamide, and hydroxyl groups enhanced the affinity of the Pebax-based membranes for the penetrating species considered in this work. As a result, the quantification of the reactivity of a membrane surface for specific molecules may allow predictive models to be constructed and selective membranes to be designed.

Chromium (III) removal by supported liquid membranes: a comparison among D2HEPA, DNNSA, and a novel extractant as carriers.

A facilitated transport study in supported liquid membranes (SLM) using the extraction reagents di-2-ethylexilfosphoric acid (D2HEPA), dinonylnaftalene sulfuric acid (DNNSA), and a novel complexing agent, trimethyl cis,cis-1,3,5-tripropyl-1,3,5 cyclohexenetricarboxilic acid (TTCHTCA) as carriers has been carried out. Organic solvents with different dielectric constants as diluents have been used to obtain the highest extraction and transport values. The results obtained have shown that, by using different organic phases (carrier and/or diluent), SLMs with different ion flux and transport ability can be obtained. The carrier concentration in the membrane and the chromium (III) [Cr(III)] ions concentration in aqueous phase have been varied to see the effect on transport of Cr(III) ions across the membrane. For the carriers D2HEPA and TTCHTCA, the transport of Cr(IlI), both in batch and in recirculation operation mode, has been studied. Very good results in terms of flux and transport have been obtained using TTCHTCA.

Diffusive and convective transport through hollow fiber membranes for liver cell culture.

For an efficient membrane bioreactor design, transport phenomena determining the overall mass flux of metabolites, catabolites, cell regulatory factors, and immune-related soluble factors, need to be clarified both experimentally and theoretically. In this work, experiments and calculations aimed at discerning the simultaneous influence of both diffusive and convective mechanisms to the transport of metabolites. In particular, the transmembrane mass flux of glucose, bovine serum albumin (BSA), APO-transferrin, immunoglobulin G, and ammonia was experimentally measured, under pressure and concentration gradients, through high-flux microporous hydrophilic poly-ether-sulphone (PES-HFMs) and poly-sulphone hollow fiber membranes (PS-HFMs). These data were analyzed by means of a model based on the mechanism of capillary pore diffusion, assuming that solute spherical molecules pass through an array of solvent-filled cylindrical pores with a diffusive permeation corrected for friction and steric hindrances. Additionally, resistances to the mass transfer were taken into account. Convective permeation data were discussed in terms of morphological properties of the polymeric membranes, molecular Stokes radius, and solute-membrane interactions according to information given by contact angle measurements. The observed steady-state hydraulic permeance of PS-HFMs was 0.972 L/m2hmbar, about 15.6-fold lower than that measured for PES-HFMs (15.2 L/m2h); in general, PS-HFMs provided a significant hindrance to the transport of target species. Diffusion coefficients of metabolites were found to be similar to the corresponding values in water through PES-HFMs, but significantly reduced through PS-HFMs (D(Glucose)(Membrane)=2.8x10(-6)+/-0.6x10(-6)cm2/s, D(BSA)(Membrane)=6.4 x 10(-7)+/-1 x 10(-7)cm(/s, D(Apotransferrin)(Membrane)=2.3 x 10(-7)+/-0.25 x 10(-7)cm2/s).

Novel composite poly(4-vinylpyridine)/polypropylene membranes with recognition properties for (S)-naproxen.

In the last few years, molecular imprinting technology has entered in different fields of chemistry, biochemistry, biotechnology and medicine. The technique allows us to introduce the molecular memory of the substrate to be recognized in a polymeric material during its preparation. In the present paper, molecularly imprinted enantioselective polymer membranes were prepared by photo-copolymerization of commercial polypropylene membranes with the functional monomer 4-vinylpyridine. The (S)-naproxen was used as a template molecule. Enantioselectivity studies in a dead-end filtration system showed the recognition properties of the imprinted membranes, which exhibited a selective transport of the (S)-enantiomer.

Effects of organic solvents on ultrafiltration polyamide membranes for the preparation of oil-in-water emulsions.

Hydrophilic ultrafiltration membranes made of polyamide with molecular weight cutoff 10 and 50 kDa have been studied for the preparation of oil-in-water emulsions by a cross-flow membrane emulsification technique. Isooctane and phosphate buffer were used as disperse and continuous phase, respectively. The permeation of apolar isooctane through the polar hydrophilic membrane was achieved by pretreatment of membranes with a gradient of miscible solvents of decreasing polarity to remove water from the pores and replace it with isooctane. Four different procedures were investigated, based on the solvent mixture percentage and contact time with membranes. After pretreatment, the performance of the membranes in terms of pure isooctane permeate flux and emulsion preparation was evaluated. The influence of organic solvents on polyamide (PA) membranes has been studied by SEM analysis, which showed a clear change in the structure and morphology of the thin selective layers. The effects proved stronger for PA 10 kDa than for 50 kDa. In fact, similar pretreatment procedures caused larger pore size and pore size distribution for PA 10 kDa than for 50 kDa. The properties of emulsions in terms of droplet size distribution reflected the membrane pore sizes obtained after pretreatment. The correlation between pore size and droplet size, for the physicochemical and fluid dynamic conditions used, has been evaluated.

Hybrid membrane operations in water desalination and industrial process rationalisation.

Membrane science and technology are recognized today as powerful tools in resolving some important global problems, and developing newer industrial processes, needed from the imperative of sustainable industrial growth. In seawater desalination, for resolving the dramatic increase of freshwater demand in many regions of the world, membrane unitary operations or the combination of some of them in integrated systems are already a real means for producing water from the sea, at lower costs and minimum environmental impact, with a very interesting prospective in particular for poor economy countries. However, membranes are used or are becoming used in some important industrial fields, for developing more efficient productive cycles, with reduced waste of raw-material, reducing the polluting charge by controlling byproduct generation, and reducing overall costs. In the present paper, other than for seawater desalination applications, some industrial applications where membrane technology has led already to match the goal of process intensification are discussed.

Biocatalytic membrane reactors: applications and perspectives.

Membranes and biotechnological tools can be used for improving traditional production systems to maintain the sustainable growth of society. Typical examples include: new and improved foodstuffs, in which the desired nutrients are not lost during thermal treatment; novel pharmaceutical products with well-defined enantiomeric compositions; and the treatment of waste-water, wherein pollution by traditional processes is a problem.

New modified polyetheretherketone membrane for liver cell culture in biohybrid systems: adhesion and specific functions of isolated hepatocytes.

There has been growing interest in innovative materials with physico-chemical properties that provide improved blood/cell compatibility. We propose new polymeric membranes made of modified polyetheretherketone (PEEK-WC) as materials with potential for use in biohybrid devices. PEEK-WC exhibits high chemical, thermal stability and mechanical resistance. Owing to its lack of crystallinity this polymer can be used for preparing membranes with cheap and flexible methods. We compared the properties of PEEK-WC membranes to polyurethane membranes prepared using the same phase inverse technique and commercial membranes. The physico-chemical properties of the membranes were characterised by contact angle measurements. The different parameters acid (gamma+), base (gamma-) and Lifshitz-van der Waals (gammaLW) of the surface free energy were calculated according to Good-van Oss's model. We evaluated the cytocompatibility of PEEK-WC membranes by culturing hepatocytes isolated from rat liver. Cell adhesion and metabolic behaviour in terms of ammonia elimination, urea synthesis and protein synthesis were evaluated during the first days of culture. Liver cells adhered and formed three-dimensional aggregates on the most tested membranes. PEEK-WC membranes promoted hepatocyte adhesion most effectively. Urea synthesis, ammonia elimination and protein synthesis improved significantly when cells adhered to PEEK-WC membrane. The considerable metabolic activities of cells cultured on this membrane confirmed the good structural and physico-chemical properties of the PEEK-WC membrane that could be a promising biomaterial for cell culture in biohybrid devices.

Characterization and control of an immobilized allosteric enzyme system.

Both immobilization techniques described in this work seem appropriate for this allosteric enzyme. However, the kinetic behavior of the dCMP deaminase trapped in a protein membrane is markedly different from that observed with the enzyme in solution and with the enzyme gelled on an artificial membrane. The enzyme, in fact, in all instances loses its cooperative action toward the substrate and even the allosteric ligands, or they do not affect the activity, or it behaves in a completely different way. In particular, dTTP seems to behave as a noncompetitive inhibitor. These effects can be attributed either to the freezing of the enzyme in one of its conformations or, more generally, to the effect of physical constraints and diffusional resistances. Further studies are in progress to distinguish between the contributions of each one of these phenomena to the kinetic behavior of the enzyme.