Modification of Thin Film Composite PVA/PAN Membranes for Pervaporation Using Aluminosilicate Nanoparticles.

The effect of the modification of the polyvinyl alcohol (PVA) selective layer of thin film composite (TFC) membranes by aluminosilicate (Al2O3·SiO2) nanoparticles on the structure and pervaporation performance was studied. For the first time, PVA-Al2O3·SiO2/polyacrylonitrile (PAN) thin film nanocomposite (TFN) membranes for pervaporation separation of ethanol/water mixture were developed via the formation of the selective layer in dynamic mode. Selective layers of PVA/PAN and PVA-Al2O3·SiO2/PAN membranes were formed via filtration of PVA aqueous solutions or PVA-Al2O3·SiO2 aqueous dispersions through the ultrafiltration PAN membrane for 10 min at 0.3 MPa in dead-end mode. Average particle size and zeta potential of aluminosilicate nanoparticles in PVA aqueous solution were analyzed using the dynamic light scattering technique. Structure and surface properties of membranes were studied using scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle measurements. Membrane performance was investigated in pervaporation dehydration of ethanol/water mixtures in the broad concentration range. It was found that flux of TFN membranes decreased with addition of Al2O3·SiO2 nanoparticles into the selective layer due to the increase in selective layer thickness. However, ethanol/water separation factor of TFN membranes was found to be significantly higher compared to the reference TFC membrane in the whole range of studied ethanol/water feed mixtures with different concentrations, which is attributed to the increase in membrane hydrophilicity. It was found that developed PVA-Al2O3·SiO2/PAN TFN membranes were more stable in the dehydration of ethanol in the whole range of investigated concentrations as well as at different temperatures of the feed mixtures (25 °C, 35 °C, 50 °C) compared to the reference membrane which is due to the additional cross-linking of the selective layer by formation hydrogen and donor-acceptor bonds between aluminosilicate nanoparticles and PVA macromolecules.

The effect of heating rate on the sintering of aluminum nanospheres.

Molecular dynamics simulations have been performed to study the influence of five different heating rates on the sintering of aluminum nanoparticles with a diameter of 4-10 nm, mainly by exploring the atomic migration, radial distribution function (RDF), atomic average displacement, mean square displacement (MSD), radius ratio (i.e., the ratio of the neck radius to the particle radius), shrinkage rate, radius of gyration, sintering temperature and melting point. It is found that the displacement of surface atoms is always larger than the displacement of the internal atoms at the same heating rate during the sintering process. Radius ratio and shrinkage go through three stages as the temperature increases: (1) an abrupt increase after reaching the sintering temperature; (2) an almost plateau region within a wide temperature range; (3) finally a drastic increase again after reaching the melting point. Although the radius of gyration also goes through three stages, nonetheless the trend is opposite to radius ratio and shrinkage. For aluminum nanoparticles with the same diameter, at a lower heating rate, the atomic displacement, mean square displacement, radius ratio, shrinkage, and radius of gyration change more remarkably with increasing temperature. The lower heating rate and smaller nanoparticle diameter correspond to a lower sintering temperature and melting point.

The effect of myeloperoxidase isoforms on biophysical properties of red blood cells.

Myeloperoxidase (MPO), an oxidant-producing enzyme, stored in azurophilic granules of neutrophils has been recently shown to influence red blood cell (RBC) deformability leading to abnormalities in blood microcirculation. Native MPO is a homodimer, consisting of two identical protomers (monomeric MPO) connected by a single disulfide bond but in inflammatory foci as a result of disulfide cleavage monomeric MPO (hemi-MPO) can also be produced. This study investigated if two MPO isoforms have distinct effects on biophysical properties of RBCs. We have found that hemi-MPO, as well as the dimeric form, bind to the glycophorins A/B and band 3 protein on RBC's plasma membrane, that lead to reduced cell resistance to osmotic and acidic hemolysis, reduction in cell elasticity, significant changes in cell volume, morphology, and the conductance of RBC plasma membrane ion channels. Furthermore, we have shown for the first time that both dimeric and hemi-MPO lead to phosphatidylserine (PS) exposure on the outer leaflet of RBC membrane. However, the effects of hemi-MPO on the structural and functional properties of RBCs were lower compared to those of dimeric MPO. These findings suggest that the ability of MPO protein to influence RBC's biophysical properties depends on its conformation (dimeric or monomeric isoform). It is intriguing to speculate that hemi-MPO appearance in blood during inflammation can serve as a regulatory mechanism addressed to reduce abnormalities on RBC response, induced by dimeric MPO.

Preparation and application of stimuli-responsive PET TeMs: RAFT graft block copolymerisation of styrene and acrylic acid for the separation of water-oil emulsions.

Stimuli-responsive membranes play an important role in the fields of biomedicine, food and chemical industries, and environmental applications, including separation of water-oil emulsions. In this study, we present a method to fabricate pH-sensitive membranes using UV-initiated RAFT graft copolymerization of styrene (ST) and acrylic acid (AA) on poly(ethylene terephthalate) (PET) track-etched membranes (TeMs). The optimization of polymerization conditions led to successful grafting of polystyrene (PS) and poly(acrylic acid) (PAA) onto PET TeMs, resulting in membranes with stable hydrophobicity and pH change responsiveness. The membranes show a contact angle of 65° in basic environments (pH 9) and 97° in acidic environments (pH 2). The membranes were characterized by atomic force microscopy (AFM), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), thermogravimetric analyses (TGA), Fourier transform infrared spectroscopy (FTIR), contact angle (CA) methods. The PET TeMs-g-PS-g-PAA exhibited good performance in separating water-oil emulsions with a high efficiency of more than 90% and flux for direct chloroform-water 2500 L m-2 h-1 and reverse emulsions of benzene-water 1700 L m-2 h-1. This method of preparing stimuli-responsive membranes with controlled wettability and responsiveness to environmental pH provides versatility in their use in separating two types of emulsions: direct and reverse.

Effect of hydrophobized PET TeMs membrane pore-size on saline water treatment by direct contact membrane distillation.

This paper describes the desalination process by membrane distillation (MD) using track-etched membranes (TeMs). Hydrophobic track-etched membranes based on poly(ethylene terephthalate) (PET TeMs) with pore diameters from 700 to 1300 nm were prepared by UV-initiated graft polymerization of lauryl methacrylate (LMA) inside the nanochannels. Modified PET TeMs were investigated by Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and contact wetting angle (CA) measurements. Hydrophobic PET TeMs were tested for treating saline solutions of different concentrations by the direct contact membrane distillation (DCMD) method. The influence of membrane pore diameter and salt solution concentration on the water flux and rejection degree were investigated. Membranes with CA 94 ± 4° were tested in the direct contact membrane distillation (DCMD) of 7.5-30 g L-1 saline solution. Hydrophobic membranes with large pore sizes showed water fluxes in the range of 1.88 to 11.70 kg m-2 h-1 with salt rejection values of up to 91.4%.

Atomic insights into thickness-dependent deformation mechanism and mechanical properties of Ag/PMMA ultra-thin nanofilms.

In this work, the nanoindentations on bilayer composite nanofilms composed of metal Ag and polymer PMMA were simulated using molecular dynamics. The effects of the thickness of Ag and PMMA on the elastic moduli of the composite films were analyzed from Hertz contact theory, dislocation evolution and atomic migration. The results show that the maximum penetration depth that the Hertz model could well describe is about 6 Å, and this limiting value is almost independent on the film thickness. The deformation mode of the Ag films gradually changes from bending mode to indentation mode with an increase in Ag thickness, which improves the elastic modulus of the composite films. The rule of mixtures could give a theoretical prediction about the elastic modulus of the composite film close to the nanoindentation, and Hertz theory could also be used as long as the thickness of Ag films exceeded a certain value. The introduction of a PMMA layer impedes the development of dislocation in the Ag layer and improves the elastic limit of the composite films. This work provides an important basis for experimentally measuring the overall elastic modulus of metal/polymer composite film based on nanoindentation or extracting the elastic modulus of metal film from the overall indentation response of the composite film.

Novel Hydrophobic Ultrafiltration Membranes for Treatment of Oil-Contaminated Wastewater.

Cutting fluids are the main source of oily wastewater in the metalworking industry. This study deals with the development of antifouling composite hydrophobic membranes for treatment of oily wastewater. The novelty of this study is that a low energy electron-beam deposition technique was applied for a polysulfone (PSf) membrane with a molecular-weight cut-off of 300 kDa, which is promising for use in the treatment of oil-contaminated wastewater, by using polytetrafluoroethylene (PTFE) as target materials. The effect of the thickness of the PTFE layer (45, 660, and 1350 nm) on the structure, composition, and hydrophilicity of membranes was investigated using scanning electron microscopy, water contact angle (WCA) measurements, atomic force microscopy, and FTIR-spectroscopy. The separation and antifouling performance of the reference and modified membranes were evaluated during ultrafiltration of cutting fluid emulsions. It was found that the increase in the PTFE layer thickness results in the significant increase in WCA (from 56° up to 110-123° for the reference and modified membranes respectively) and decrease in surface roughness. It was found that cutting fluid emulsion flux of modified membranes was similar to the flux of the reference PSf-membrane (7.5-12.4 L·m-2·h-1 at 6 bar) while cutting fluid rejection (RCF) of modified membranes increased compared to the reference membrane (RCF = 58.4-93.3% for modified and RCF = 13% for the reference PSf membrane). It was established that despite the similar flux of cutting fluid emulsion, modified membranes demonstrate 5-6.5 times higher flux recovery ratio (FRR) compared to the reference membrane. The developed hydrophobic membranes were found to be highly efficient in oily wastewater treatment.

Stimuli-Responsive Track-Etched Membranes for Separation of Water-Oil Emulsions.

In this work, we have developed a method for the preparation of pH-responsive track-etched membranes (TeMs) based on poly(ethylene terephthalate) (PET) with pore diameters of 2.0 ± 0.1 µm of cylindrical shape by RAFT block copolymerization of styrene (ST) and 4-vinylpyridine (4-VP) to be used in the separation of water-oil emulsions. The influence of the monomer concentration (1-4 vol%), the molar ratio of RAFT agent: initiator (1:2-1:100) and the grafting time (30-120 min) on the contact angle (CA) was studied. The optimal conditions for ST and 4-VP grafting were found. The obtained membranes showed pH-responsive properties: at pH 7-9, the membrane was hydrophobic with a CA of 95°; at pH 2, the CA decreased to 52°, which was due to the protonated grafted layer of poly-4-vinylpyridine (P4VP), which had an isoelectric point of pI = 3.2. The obtained membranes with controlled hydrophobic-hydrophilic properties were tested by separating the direct and reverse "oil-water" emulsions. The stability of the hydrophobic membrane was studied for 8 cycles. The degree of purification was in the range of 95-100%.

Preparation of Hydrophobic PET Track-Etched Membranes for Separation of Oil-Water Emulsion.

The paper describes the separation of an oil-water emulsion by filtration using poly(ethylene terephthalate) track-etched membranes (PET TeMs) with regular pore geometry and narrow pore size distribution. PET TeMs were modified with trichloro(octyl)silane to increase their hydrophobic properties. Conditions for the modification of PET TeMs with trichloro(octyl)silane were investigated. The results of changes in the pore diameters and the contact angle depend on the concentration of trichloro(octyl)silane and the soaking time are presented. The obtained samples were characterized by FTIR, AFM, SEM-EDX and gas-permeability test. Chloroform-water and cetane-water emulsions have been used as a test liquid for oil-water separation.