Alberto Tiraferri

High Performance Thin-Film Composite Forward Osmosis Membrane

Recent studies show that osmotically driven membrane processes may be a viable technology for desalination, water and wastewater treatment, and power generation. However, the absence of a membrane designed for such processes is a significant obstacle hindering further advancements of this technology. This work presents the development of a high performance thin-film composite membrane for forward osmosis applications. The membrane consists of a selective polyamide active layer formed by interfacial polymerization on top of a polysulfone support layer fabricated by phase separation onto a thin (40 mum) polyester nonwoven fabric. By careful selection of the polysulfone casting solution (i.e., polymer concentration and solvent composition) and tailoring the casting process, we produced a support layer with a mix of finger-like and sponge-like morphologies that give significantly enhanced membrane performance. The structure and performance of the new thin-film composite forward osmosis membrane are compared with those of commercial membranes. Using a 1.5 M NaCl draw solution and a pure water feed, the fabricated membranes produced water fluxes exceeding 18 L m(2-)h(-1), while consistently maintaining observed salt rejection greater than 97%. The high water flux of the fabricated thin-film composite forward osmosis membranes was directly related to the thickness, porosity, tortuosity, and pore structure of the polysulfone support layer. Furthermore, membrane performance did not degrade after prolonged exposure to an ammonium bicarbonate draw solution.

Thin-film composite pressure retarded osmosis membranes for sustainable power generation from salinity gradients

Pressure retarded osmosis has the potential to produce renewable energy from natural salinity gradients. This work presents the fabrication of thin-film composite membranes customized for high performance in pressure retarded osmosis. We also present the development of a theoretical model to predict the water flux in pressure retarded osmosis, from which we can predict the power density that can be achieved by a membrane. The model is the first to incorporate external concentration polarization, a performance limiting phenomenon that becomes significant for high-performance membranes. The fabricated membranes consist of a selective polyamide layer formed by interfacial polymerization on top of a polysulfone support layer made by phase separation. The highly porous support layer (structural parameter S = 349 μm), which minimizes internal concentration polarization, allows the transport properties of the active layer to be customized to enhance PRO performance. It is shown that a hand-cast membrane that balances permeability and selectivity (A = 5.81 L m(-2) h(-1) bar(-1), B = 0.88 L m(-2) h(-1)) is projected to achieve the highest potential peak power density of 10.0 W/m(2) for a river water feed solution and seawater draw solution. The outstanding performance of this membrane is attributed to the high water permeability of the active layer, coupled with a moderate salt permeability and the ability of the support layer to suppress the undesirable accumulation of leaked salt in the porous support. Membranes with greater selectivity (i.e., lower salt permeability, B = 0.16 L m(-2) h(-1)) suffered from a lower water permeability (A = 1.74 L m(-2) h(-1) bar(-1)) and would yield a lower peak power density of 6.1 W/m(2), while membranes with a higher permeability and lower selectivity (A = 7.55 L m(-2) h(-1) bar(-1), B = 5.45 L m(-2) h(-1)) performed poorly due to severe reverse salt permeation, resulting in a similar projected peak power density of 6.1 W/m(2).

Covalent Binding of Single-Walled Carbon Nanotubes to Polyamide Membranes for Antimicrobial Surface Properties

We propose an innovative approach to impart nanomaterial-specific properties to the surface of thin-film composite membranes. Specifically, biocidal properties were obtained by covalently binding single-walled carbon nanotubes (SWNTs) to the membrane surface. The SWNTs were first modified by purification and ozonolysis to increase their sidewall functionalities, maximize cytotoxic properties, and achieve dispersion in aqueous solution. A tailored reaction protocol was developed to exploit the inherent moieties of hand-cast polyamide membrane surfaces and create covalent amide bonds with the functionalized SWNTs. The reaction is entirely aqueous-based and entails activation of the carboxylate groups of both the membrane and the nanomaterials to maximize reaction with ethylenediamine. The presence of SWNTs was verified after sonication of the membranes, confirming the strength of the bond between the SWNTs and the membrane surface. Characterization of the SWNT-functionalized surfaces demonstrated the attainment of membranes with novel properties that continued to exhibit high performance in water separation processes. The presence of surface-bound antimicrobial SWNTs was confirmed by experiments using E. coli cells that demonstrated an enhanced bacterial cytotoxicity for the SWNT-coated membranes. The SWNT membranes were observed to achieve up to 60% inactivation of bacteria attached to the membrane within 1 h of contact time. Our results suggest the potential of covalently bonded SWNTs to delay the onset of membrane biofouling during operation.

Forward with Osmosis: Emerging Applications for Greater Sustainability

Many conventional practices in the production and use of water, energy, and food are unsustainable. Existing technologies and concepts can be improved with the integration of forward osmosis, a membrane-based technology that uses osmosis as its driving force. This Feature highlights five emerging applications of forward osmosis that elegantly bypass the difficult step of draw solution regeneration and make common processes more sustainable. These applications enhance the efficiency of the production and use of water, energy, and food; utilize wastes and abundant, low value resources; and better protect the environment.

Superhydrophilic Thin-Film Composite Forward Osmosis Membranes for Organic Fouling Control: Fouling Behavior and Antifouling Mechanisms

This study investigates the fouling behavior and fouling resistance of superhydrophilic thin-film composite forward osmosis membranes functionalized with surface-tailored nanoparticles. Fouling experiments in both forward osmosis and reverse osmosis modes are performed with three model organic foulants: alginate, bovine serum albumin, and Suwannee river natural organic matter. A solution comprising monovalent and divalent salts is employed to simulate the solution chemistry of typical wastewater effluents. Reduced fouling is consistently observed for the superhydrophilic membranes compared to control thin-film composite polyamide membranes, in both reverse and forward osmosis modes. The fouling resistance and cleaning efficiency of the functionalized membranes is particularly outstanding in forward osmosis mode where the driving force for water flux is an osmotic pressure difference. To understand the mechanism of fouling, the intermolecular interactions between the foulants and the membrane surface are analyzed by direct force measurement using atomic force microscopy. Lower adhesion forces are observed for the superhydrophilic membranes compared to the control thin-film composite polyamide membranes. The magnitude and distribution of adhesion forces for the different membrane surfaces suggest that the antifouling properties of the superhydrophilic membranes originate from the barrier provided by the tightly bound hydration layer at their surface, as well as from the neutralization of the native carboxyl groups of thin-film composite polyamide membranes.

Improved Antifouling Properties of Polyamide Nanofiltration Membranes by Reducing the Density of Surface Carboxyl Groups

Carboxyls are inherent functional groups of thin-film composite polyamide nanofiltration (NF) membranes, which may play a role in membrane performance and fouling. Their surface presence is attributed to incomplete reaction of acyl chloride monomers during the membrane active layer synthesis by interfacial polymerization. In order to unravel the effect of carboxyl group density on organic fouling, NF membranes were fabricated by reacting piperazine (PIP) with either isophthaloyl chloride (IPC) or the more commonly used trimesoyl chloride (TMC). Fouling experiments were conducted with alginate as a model hydrophilic organic foulant in a solution, simulating the composition of municipal secondary effluent. Improved antifouling properties were observed for the IPC membrane, which exhibited lower flux decline (40%) and significantly greater fouling reversibility or cleaning efficiency (74%) than the TMC membrane (51% flux decline and 40% cleaning efficiency). Surface characterization revealed that there was a substantial difference in the density of surface carboxyl groups between the IPC and TMC membranes, while other surface properties were comparable. The role of carboxyl groups was elucidated by measurements of foulant-surface intermolecular forces by atomic force microscopy, which showed lower adhesion forces and rupture distances for the IPC membrane compared to TMC membranes in the presence of calcium ions in solution. Our results demonstrated that a decrease in surface carboxyl group density of polyamide membranes fabricated with IPC monomers can prevent calcium bridging with alginate and, thus, improve membrane antifouling properties.

Mechanism of Chitosan Adsorption on Silica from Aqueous Solutions

We present a study of the adsorption of chitosan on silica. The adsorption behavior and the resulting layer properties are investigated by combining optical reflectometry and the quartz crystal microbalance. Exactly the same surfaces are used to measure the amount of adsorbed chitosan with both techniques, allowing the systematic combination of the respective experimental results. This experimental protocol makes it possible to accurately determine the thickness of the layers and their water content for chitosan adsorbed on silica from aqueous solutions of varying composition. In particular, we study the effect of pH in 10 mM NaCl, and we focus on the influence of electrolyte type and concentration for two representative pH conditions. Adsorbed layers are stable, and their properties are directly dependent on the behavior of chitosan in solution. In mildly acidic solutions, chitosan behaves like a weakly charged polyelectrolyte, whereby electrostatic attraction is the main driving force for adsorption. Under these conditions, chitosan forms rigid and thin adsorption monolayers with an average thickness of approximately 0.5 nm and a water content of roughly 60%. In neutral solutions, on the other hand, chitosan forms large aggregates, and thus adsorption layers are significantly thicker (∼10 nm) as well as dissipative, resulting in a large maximum of adsorbed mass around the pK of chitosan. These films are also characterized by a substantial amount of water, up to 95% of their total mass. Our results imply the possibility to produce adsorption layers with tailored properties simply by adjusting the solution chemistry during adsorption.

Probing effects of polymer adsorption in colloidal particle suspensions by light scattering as relevant for the aquatic environment: An overview

Modification of particle surfaces by adsorption of polymers is a process that governs particle behavior in aqueous environmental systems. The present article briefly reviews the current understanding of the adsorption mechanisms and the properties of the resulting layers, and it discusses two environmentally relevant cases of particle modification by polymers. In particular, the discussion focuses on the usefulness of methods based on light scattering to probe such adsorbed layers together with the resulting properties of the particle suspensions, and it highlights advantages and disadvantages of these techniques. Measurement of the electrophoretic mobility allows to follow the development of the adsorption layer and to characterize the charge of the modified particles. At saturation, the surface charge is governed by the charge of the adsorbed film. Dynamic light scattering provides information on the film thickness and on the behavior of the modified suspensions. The charge and the structure of the adsorbed layer influence the stability of the particles, as well as the applicability of the classical theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). This fundamental knowledge is presented in the light of environmental systems and its significance for applied systems is underlined. In particular, the article discusses two examples of environmental processes involving adsorption of polymers, namely, the modification of particles by natural adsorption of humic substances and the tailoring of surface properties of iron-based particles used to remediate contaminated aquifers.

Adsorbed Mass of Polymers on Self-Assembled Monolayers: Effect of Surface Chemistry and Polymer Charge

The adsorbed mass of polymers on surfaces with different chemistry is presented, and the related adsorption mechanism is discussed. Strong and weak polyelectrolytes of negative and positive charge are studied, as well as an uncharged polymer. Self-assembled monolayers of alkanethiols on gold are used in reflectometry and quartz crystal microbalance (QCM-D) experiments as adsorbing substrates bearing different terminal moieties, namely, methyl, hydroxyl, carboxyl, and amine groups. The various polymer-surface combinations allow the systematic investigation of the role of surface chemistry and polymer charge on adsorbed amount. Interactions of different nature and range drive polymer adsorption: the measured adsorbed amounts reveal information about their relative contribution. When electrostatic chain-surface attraction is present, the largest adsorbed masses are observed. However, significant mass is measured even when an electrostatic barrier to adsorption is present, suggesting the importance of forces of nonelectrostatic origin, which include both hydrophobic interactions and specific forces acting at short distances. This mechanism results in large adsorbed amounts for the adsorption of weak polyelectrolytes, and it is apparent especially in the adsorption behavior of a neutral polymer.

Controlled Deposition of Particles in Porous Media for Effective Aquifer Nanoremediation

In this study, a model assisted strategy is developed to control the distribution of colloids in porous media in the framework of nanoremediation, an innovative environmental nanotechnology aimed at reclaiming contaminated aquifers. This approach is exemplified by the delivery of humic acid-stabilized iron oxide nanoparticles (FeOx), a typical reagent for in situ immobilization of heavy metals. By tuned sequential injections of FeOx suspensions and of solutions containing a destabilizing agent (i.e. calcium or magnesium), the two fronts, which advance at different rates, overlap at the target location (i.e., the central portion) of the porous systems. Here, the particles deposit and accumulate irreversibly, creating a reactive zone. An analytical expression predicting the position of the clustering zone in 1D systems is derived from first principles of advective-dispersive transport. Through this equation, the sequence and duration of the injection of the different solutions in the medium is assessed. The model robustness is demonstrated by its successful application to various systems, comprising the use of different sands or immobilizing cations, both in 1D and 2D geometries. The method represents an advancement in the control of nanomaterial fate in the environment, and could enhance nanoremediation making it an effective alternative to more conventional techniques.