Viatcheslav Freger

TFC polyamide membranes modified by grafting of hydrophilic polymers: an FT-IR/AFM/TEM study

Abstract Surface modification using grafting of a hydrophilic polymer onto the membrane surface is a possible route to improving the fouling properties of polyamide thin-film composite membranes. The structure of nanofiltration (NF) and reverse osmosis (RO) membranes modified using graft polymerization of acrylic (AA) monomers was visualized and analyzed using attenuated total reflection–Fourier transform infrared spectroscopy, atomic force microscopy and transmission electron microscopy. The results show that a layer of AA polymer is indeed formed on the polyamide surface, which could be accompanied by a change of the surface morphology. It was observed that for the NF membranes studied polymerization could also take place inside the pores of the support as a result of penetration of the monomer through the active layer, particularly for high degrees of grafting. It suggests that the modification procedures should be optimized so that the latter effect is minimized.

Separation of concentrated organic/inorganic salt mixtures by nanofiltration

This paper considers nanofiltration (NF) of concentrated organic/inorganic mixtures using the FILMTEC™ NF-200B membrane. Mixtures of salt (up to 17% (w/v)) and lactic acid (2% (w/v)) were used as model solutions. The work centres on the effects of salt concentration, pH and temperature on the flux and rejection of lactate. For all solutions under study, the rejection of salt was low, while the rejection of lactate was maximal at neutral pH, and decreased with salt concentration and temperature. The flux was found to decrease with salt concentration and increase with temperature, the activation energy being higher for low fluxes. The flux for pure water and 2% (w/v) lactic acid was at a maximum at neutral pH, but for salt-containing solutions, it increased with pH in the whole range analysed (pH 3–10). The observed flux and rejection patterns suggest that the effects of skin shrinkage in concentrated salt solutions, and sorption of lactate by the membrane, affect behaviour in addition to the conventional effects of charge, solute size and osmotic difference between the retentate and permeate streams.

Bacterial attachment to RO membranes surface-modified by concentration-polarization-enhanced graft polymerization.

Concentration polarization-enhanced radical graft polymerization, a facile surface modification technique, was examined as an approach to reduce bacterial deposition onto RO membranes and thus contribute to mitigation of biofouling. For this purpose an RO membrane ESPA-1 was surface-grafted with a zwitterionic and negatively and positively charged monomers. The low monomer concentrations and low degrees of grafting employed in modifications moderately reduced flux (by 20-40%) and did not affect salt rejection, yet produced substantial changes in surface chemistry, charge and hydrophilicity. The propensity to bacterial attachment of original and modified membranes was assessed using bacterial deposition tests carried out in a parallel plate flow setup using a fluorescent strain of Pseudomonas fluorescens. Compared to unmodified ESPA-1 the deposition (mass transfer) coefficient was significantly increased for modification with the positively charged monomer. On the other hand, a substantial reduction in bacterial deposition rates was observed for membranes modified with zwitterionic monomer and, still more, with very hydrophilic negatively charged monomers. This trend is well explained by the effects of surface charge (as measured by ζ-potential) and hydrophilicity (contact angle). It also well correlated with force distance measurements by AFM using surrogate spherical probes with a negative surface charge mimicking the bacterial surface. The positively charged surface showed a strong hysteresis with a large adhesion force, which was weaker for unmodified ESPA-1 and still weaker for zwitterionic surface, while negatively charged surface showed a long-range repulsion and negligible hysteresis. These results demonstrate the potential of using the proposed surface- modification approach for varying surface characteristics, charge and hydrophilicity, and thus minimizing bacterial deposition and potentially reducing propensity biofouling.

Supported lipid bilayer membranes for water purification by reverse osmosis.

Some biological plasma membranes pass water with a permeability and selectivity largely exceeding those of commercial membranes for water desalination using specialized trans-membrane proteins aquaporins. However, highly selective transport of water through aquaporins is usually driven by an osmotic rather mechanical pressure, which is not as attractive from the engineering point of view. The feasibility of adopting biomimetic membranes for water purification driven by a mechanical pressure, i.e., filtration is explored in this paper. Toward this goal, it is proposed to use a commercial nanofiltration (NF) membrane as a support for biomimetic lipid bilayer membranes to render them robust enough to withstand the required pressures. It is shown in this paper for the first time that by properly tuning molecular interactions supported phospholipid bilayers (SPB) can be prepared on a commercial NF membrane. The presence of SPB on the surface was verified and quantified by several spectroscopic and microscopic techniques, which showed morphology close to the desired one with very few defects. As an ultimate test it is shown that hydraulic permeability of the SPB supported on the NF membrane (NTR-7450) approaches the values deduced from the typical osmotic permeabilities of intact continuous bilayers. This permeability was unaffected by the trans-membrane flow of water and by repeatedly releasing and reapplying a 10 bar pressure. Along with a parallel demonstration that aquaporins could be incorporated in a similar bilayer on mica, this demonstrates the feasibility of the proposed approach. The prepared SPB structure may be used as a platform for preparing biomimetic filtration membranes with superior performance based on aquaporins. The concept of SPBs on permeable substrates of the present type may also be useful in the future for studying transport of various molecules through trans-membrane proteins.

Pseudomonas aeruginosa attachment on QCM-D sensors: the role of cell and surface hydrophobicities.

While biofilms are ubiquitous in nature, the mechanism by which they form is still poorly understood. This study investigated the process by which bacteria deposit and, shortly after, attach irreversibly to surfaces by reorienting to create a stronger interaction, which leads to biofilm formation. A model for attachment of Pseudomonas aeruginosa was developed using a quartz crystal microbalance with dissipation monitoring (QCM-D) technology, along with a fluorescent microscope and camera to monitor kinetics of adherence of the cells over time. In this model, the interaction differs depending on the force that dominates between the viscous, inertial, and elastic loads. P. aeruginosa, grown to the midexponential growth phase (hydrophilic) and stationary phase (hydrophobic) and two different surfaces, silica (SiO(2)) and polyvinylidene fluoride (PVDF), which are hydrophilic and hydrophobic, respectively, were used to test the model. The bacteria deposited on both of the sensor surfaces, though on the silica surface the cells reached a steady state where there was no net increase in deposition of bacteria, while the quantity of cells depositing on the PVDF surface continued to increase until the end of the experiments. The change in frequency and dissipation per cell were both positive for each overtone (n), except when the cells and surface are both hydrophilic. In the model three factors, specifically, viscous, inertial, and elastic loads, contribute to the change in frequency and dissipation at each overtone when a cell deposits on a sensor. On the basis of the model, hydrophobic cells were shown to form an elastic connection to either surface, with an increase of elasticity at higher overtones. At lower overtones, hydrophilic cells depositing on the hydrophobic surface were shown to also be elastic, but as the overtone increases the connection between the cells and sensor becomes more viscoelastic. In the case of hydrophilic cells interacting with the hydrophilic surface, the connection is viscous at each overtone measured. It could be inferred that the transformation of the viscoelasticity of the cell-surface connection is due to changes in the orientation of the cells to the surface, which allow the bacteria to attach irreversibly and begin biofilm formation.

Surface properties and reduced biofouling of graft-copolymers that possess oppositely charged groups.

Microbial biofilms and their components present a major obstacle for ensuring the long-term effectiveness of membrane processes. Graft polymerization on membrane surfaces, in general, and grafting with oppositely charged monomers, have been shown to reduce biofouling significantly. In this study, surface forces and macromolecular properties of graft copolymers that possess oppositely charged groups were related to their potent antibiofouling behavior. Graft polymerization was performed using the negatively charged 3-sulphopropyl methacrylate (SPM) and positively charged [2-(methacryloyloxy)ethyl]-trimethylammonium (MOETMA) monomers to yield a copolymer layer on polyvinylidene fluoride (PVDF) surface. Quartz crystal microbalance with dissipation monitoring (QCM-D) technology was used to monitor the reduced adsorption of extracellular polymeric substances (EPS) extracted from a membrane bioreactor (MBR) wastewater treatment facility. Complemented measurements of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy provided evaluation of the antifouling properties of the surface. Increase in water content in grafted layer exposed to 100 mM aqueous NaCl solution was observed by QCM-D. Therefore, the grafted copolymer layer is swelled in the presence of 100 mM NaCl because of reversing of polymer self-association by counterions. Force measurements by atomic force microscopy (AFM) showed an increased repulsion between a carboxylate-modified latex (CML) particle probe and a modified PVDF surface, especially in the presence of 100 mM NaCl. The hydration and swelling of the grafted polymer layer are shown to repel EPS and reduce their adsorption. Delineating the surface properties of antifouling grafted layers may lead to the design of novel antifouling surfaces.

Analysis of ion transport in nanofiltration using phenomenological coefficients and structural characteristics.

The analysis of salt transport in nanofiltration using extended Nernst-Planck equations or similar models often suffers from the difficulties to establish and independently and transparently verify the consistency between the filtration results, assumed mechanism, and fitted values of parameters. As a general alternative, we propose here a procedure that reduces filtration data to two general phenomenological coefficients, concentration-dependent salt permeability omega(s) and Peclet coefficient A, which does not require that a specific exclusion mechanism be assumed and thus allows a transparent test on consistency with commonly used models. This approach was demonstrated using concentration polarization-corrected filtration data for NF-200 membrane and four monovalent salts, NaCl, NaBr, KBr, and KCl. The coefficient A was found to be very small, which points to the negligible contribution of convection to salt transport. The smallness of A was verified through estimates of the effective pore radius of the membrane, found to be between 0.2 and 0.3 nm, and comparing them with similar independent estimates from the hydraulic permeability L(p) using the data on the thickness and swelling of the selective polyamide layer obtained by AFM. The concentration dependence of omega(s) and its variation for different salts suggested that in the concentration range above 0.01 M the salt exclusion may be dominated by a combination of Donnan and dielectric mechanisms. The values of omega(s) obtained for single salts were also consistent with the selectivity observed for equimolar feed mixtures of NaCl and NaBr. However, the observed variation of omega(s) with concentrations of single salts below 0.01 M reveals a new regime that is inconsistent with all commonly used models of NF based on a Donnan mechanism modified with dielectric and steric effects. In particular, omega(s) appeared to approach a constant value at low salt concentrations, whereas the standard mechanisms predict a linear or even steeper decrease as concentration decreases. This puzzling discrepancy could have passed unnoticed in the standard multiparameter fitting extended Nernst-Planck equations and demonstrates the benefits of the present phenomenological analysis.

Bacterial Attachment and Viscoelasticity: Physicochemical and Motility Effects Analyzed Using Quartz Crystal Microbalance with Dissipation (QCM-D)

This investigation is focused on the combined effect of bacterial physicochemical characteristics and motility on cell adhesion and deposition using a flow-through quartz crystal microbalance with dissipation (QCM-D). Three model flagellated strains with different degrees of motility were selected, including a highly motile Escherichia coli K12 MG1655, an environmental strain Sphingomonas wittichii RW1, and a nonmotile (with paralyzed flagella) Escherichia coli K12 MG1655 ΔmotA that is incapable of encoding the motor torque generator for flagellar movement. Of the three strains, S. wittichii RW1 is highly hydrophobic, while E. coli strains are equally hydrophilic. Consideration of the hydrophobicity provides an alternative explanation for the bacterial adhesion behavior. QCM-D results show that motility is a critical factor in determining bacterial adhesion, as long as the aquatic chemical conditions are conducive for motility and the substratum and bacterial surface are similarly hydrophobic or hydrophilic. Once their properties are not similar, the contribution of hydrophobic interactions becomes more pronounced. QCM-D results suggest that during adhesion of the hydrophobic bacterium, S. wittichii RW1, the initial step of adhesion and maturation of bacteria-substratum interaction on hydrophilic surface includes a dynamic change of the viscoelastic properties of the bond bacterium-surface becoming more viscously oriented.

Surface modification of dense membranes using radical graft polymerization enhanced by monomer filtration.

Surface graft polymerization is a promising way to modify membranes for improved performance. Redox-initiated graft polymerization of vinyl monomers is a facile and inexpensive method carried out at room temperature in aqueous media; however, its use is often limited by slow kinetics, low surface specificity, and excessive consumption of chemicals on undesired homopolymerization. It is shown that in the case of RO or NF membranes these drawbacks may be eliminated by utilizing the selectivity of the membranes toward monomers and carrying out the polymerization while applying pressure, i.e., under filtration conditions. Concentration polarization that ensues raises the concentration of reagents near the membrane surface and thereby drastically increases the rate of reaction and preferentially directs it towards surface grafting. Grafting experiments using 2-hydroxyethyl methacrylate and other monomers and characterization of modified membranes using permeability measurements, ATR-FTIR, AFM, XPS, and contact angle demonstrate that the required monomer concentrations can be drastically reduced, particularly when a small fraction of a cross-linker is added. As an additional benefit, this approach enables broadening the spectrum of utilizable monomers to sparingly soluble hydrophobic, charged, and macro-monomers, as was demonstrated using sparingly soluble ethyl methacrylate and 2-ethoxyethyl methacrylate and other monomers. Even though the kinetics of the process is substantially complicated by evolution and concentration polarization of oligomeric and polymeric species, especially in the presence of a cross-linker, it is well offset by the benefits of higher rate, specificity, and reduced monomer consumption.

Elastic energy in microscopically phase-separated swollen polymer networks

Abstract The paper analyzes a microscopic regime of strain, different from the one conventionally considered, that presumably takes place in swollen polymers showing strong microscopic phase separation, such as ion-exchange resins in water. Such systems show linear dependence of the elastic pressure on swelling in contrast to the Flory–Rehner theory and its modifications. The present work proposes a simple model that predicts this kind of behavior. Swelling is considered as a non-affine ‘inflation’ of the hydrophobic matrix by small aggregates of water molecules (‘droplets’) adsorbed by highly hydrophilic groups, whereas the macroscopic dimensions of the sample change as a result of the compression of the ‘films’ separating the droplets. This compression is then analyzed along the classical lines. In the case of the Dowex resins a partial test of the model based on the reported shear moduli showed reasonable agreement with experiment.