Research

Research Themes

 

Mechanism of salt rejection in desalination membranes

(Noga Fridman-Bishop, Vesselin Kolev, Mikhail Stolov)

In desalination membranes the salts are separated from water in a very thin (10-200 nm) selective layer made of polyamide, however, how that happens and how different ions are separated is still not well understood. We develop models and methods to study  salt transport in RO and NF polyamide membranes and study the mechanism of salt and water transport using various experimental techniques, in particular electrochemical impedance spectroscopy (EIS) and cross flow filtration. We also use atomistic molecular dynamics (MD) simulations to gain better understanding of molecular mechanisms involved in salt and water transport.

sea water composition

Given sea water composition, what will be the composition of permeate and retentate?

Principle of EISPrinciple of EIS:  membrane conductivity supplies unique signatures of transport mechanism.

polymer density distribution

The polymer density distribution of a polyamide membrane obtained by MD and the proposed random resistor network model for water and ion transport.

pH dependence of PA film conductivity

Dependence on pH of polyamide film conductivity in 1 M NaCl solution normalized to conductivity at pH 7

Recent Publications:

M. Stolov, V. Freger, Membrane charge weakly affects ion transport in reverse osmosis Environ. Sci & Technol. Lett.,  7 (2020)  440-445

O Nir, N. Fridman-Bishop, O Lahav, V Freger, Modeling pH variation in reverse osmosis, Water Res., 87 (2015) 328-335

N. Fridman-Bishop, O. Nir, O. Lahav, V. Freger, Predicting the rejection of major seawater ions by spiral-wound nanofiltration membranes, Environ. Sci & Technol., 49 (14) (2015) 8631-8638

V. Kolev, V. Freger, Molecular dynamics investigation of ion sorption and permeation in desalination membranes, J. Phys. Chem. B, 119 (2015) 14168–14179

E. Dražević, K. Košutić, V. Kolev, V. Freger, Does hindered transport theory apply to desalination membranes? Environ. Sci & Technol.  48 (2014)  11471–11478

V. Kolev, V. Freger, Hydration, Porosity and Water Dynamics in the Polyamide Layer of Reverse Osmosis Membranes: a Molecular Dynamics Study, Polymer, 55 (2014) 1420-1426

 

Fouling, biofouling and bacterial deposition

Bacteria may stick to and colonize nearly every surface in an aqueous environment by forming biofilms. In membrane processes this leads to membrane biofouling, which very difficult to predict and control. The first critical step of biofouling is deposition and adhesion of bacteria to the surface.

stages of biofilm formationStages of biofilm formation; stage 1 is initial deposition.

Modeling and analysis of particles and microorganisms deposition on surfaces.

(Maria Bass, Katie Baransi-Karkaby,Eli Margalit, Ariela Tarnapolsky )

We study and model the mechanism of bacterial deposition experimentally (QCM-D, Parallel Plate Flow Cell (PPFC)) and theoretically, with the purpose to understand how it is related to the properties of the surface and to biofouling and how to modify surfaces to minimize their fouling. This work includes collaboration with colleagues from BGU, Technion, Germany and Korea.

a parallel plate flow cellA parallel plate flow cell (PPFC) for studying deposition.

a setup for studying deposition

A setup for studying deposition with a PPFC mounted under microscope

numerical simulations can predict well bacterial deposition data

Numerical simulations can predict well bacterial deposition data

 

Recent Publications:

A. Tarnapolsky, V. Freger, Modeling QCM-D response to deposition and attachment of microparticles and living cells, Anal. Chem., 90 (23) (2018) 13960-13968

R. Bernstein, V. Freger, J.-H. Lee, Y.-G. Kim, J. Lee, M. Herzberg, “Should I stay or should I go?”: Bacterial attachment versus biofilm formation on surface-modified membranes, Biofouling,  30 (2014) 367–376

E. Margalit, A. Leshansky, V. Freger, Modeling and analysis of hydrodynamic and physicochemical effects in bacterial deposition on surfaces, Biofouling, 29(8) (2013)  977-989

I.  Marcus, M. Herzberg, S. Walker, V. Freger, Pseudomonas aeruginosa attachment on QCM-D Sensors: The role of cell and surface hydrophobicities, Langmuir, 28(15) (2012) 6396–6402

Preparation, mechanics and fouling behavior of mesoscopic hydrogel coatings

(Lina Rosental, Aleksandr Leontev)

Surfaces in an aqueous environment, such as water pipes, desalination membranes or even medical implants, are prone to macromolecular and bacterial attachment. We study polymeric coatings that can protect such surfaces from contamination, with a focus on cross-linked and swellable coatings known as hydrogels. After preparing uniform and defined hydrogel coatings on glass slides, we measure their mechanical properties by atomic force microscopy (AFM). Then, we investigate and model the deposition behavior of Polystyrene particles and bacteria on the prepared coatings and on the hydrophobic and hydrophilic surfaces that are not swollen (glass slides). The deposition is analysed along a number of locations in a PPFC channel. The goal is to gain a deeper understanding of foulants interactions with the studied surfaces.

 AFM scan and force curves

AFM scan and typical force curves of a hydrogel in water

 Imaged spots in PPFC

The studied locations of deposition in a PPFC

Recent Publications:

A. Leontev, R. Bar-On, M. Bass, M. Jurić, C. Schmetz, V. Freger, Spatial pattern and surface-specificity of particle and microorganism deposition and attachment: Modeling, analytic solution and experimental test, Journal of Colloid and Interface Science, 584 (2021) 45-56

 

“Next-Generation” Membranes

Membranes are a mature field and the performance of current membranes is often good. Nevertheless, we always seek for still better performance and novel, currently unavailable, types of membranes, which requires new research and unorthodox approaches. We are working on a few such projects, such as development of biomimetic membranes based on aquaporins (water channel membrane proteins used by all living organisms), novel nanofiltration membranes that have a uniquely high permeability to salts, and membranes with improved proton conductivity for fuel cells.

 

Energy saving Nafion based nano filtration membranes

(Stanislav (Stas) Levchenko,Michael Zelner)

We develop novel desalination membranes with uniquely high permeation of multivalent ions, highly beneficial for water recycling. Such novel membrane will help to reduce membrane scaling, recover more water for irrigation, and save on chemicals and fertilizers for agriculture.

phoho

Current NF membranes completely remove hardness calcium and phosphate from secondary wastewater, resulting in severe scaling and low recovery.

photo

A commercial NF  gets scaled and looses permeability (blue line), while a novel membrane has a better balanced Ca and PO4 rejection vs NaCl rejection and flux remains stable (red line).

Ion selectivity of nanofiltration (NF) membranes is a critical factor in NF treatment scaling-prone of multi-ion effluents, such as wastewater. When removal of multivalent ions in such effluents is unnecessary or undesired, adjusting their rejection may mitigate scaling, in which case membranes combining oppositely charged electrolytes enable a tunable selectivity towards such ions. Here we report the preparation of a new tunable and highly stable polyelectrolyte complex NF membrane prepared by successively coating an ultrafiltration membrane support with negatively charged Nafion and positively charged polyvinylamine (PVAm) layers. While Nafion thickness controls the membrane permeability, the second PVAm coating is critical for eliminating defects in the Nafion layer and readily tunes the membrane net charge and, hence, ion selectivity via PVAm concentration in the coating solution. In this manner, a membrane with good permeability, balanced charge, and, therefore, equal (“symmetric”) rejection of divalent anions and cations is obtained. The membrane performance is unaffected by exposure to 10% salt in water; such remarkable stability for a polyelectrolyte-based membrane makes it potentially attractive for the treatment of wastewater effluents and brackish water sources.

 Schematic representation of preparation and properties of energy-saving Nafion-based nanofiltration membrane

Schematic representation of preparation and properties of energy-saving Nafion-based nanofiltration membrane

Recent Publications:

M. Zelner, P. Jahn, M. Ulbricht, V. Freger, A mixed-charge polyelectrolyte complex nanofiltration membrane: Preparation, performance and stability,J. Memb. Sci., 636 (2021) 119579

S. Levchenko V. Freger, Breaking the symmetry: Mitigating scaling in tertiary treatment of waste effluents using a positively charged nanofiltration membrane,Environ. Sci & Technol. Lett., 3 (2016) 339-3439

 

Biomimetic  Membranes and Microfluidics

(Rona Ronen, Yair Kaufman)

Inspired by unique characteristics of biological membranes and aquaporins, we explore how to make biomimetic ones. For this purpose we design and use supported biomimetic structures and study them in dedicated microfluidic cells.

Recent Publications:

Y. Kaufman, R. Kasher, R G.H. Lammertink, V. Freger, Microfluidic NF/RO Separation: Cell Design, Performance and Application, J. Membr. Sci., 396 (2012) 67-73

Y. Kaufman, S. Grinberg, C. Linder, E. Heldman, J. Gilron, V. Freger, Fusion of Bolaamphiphile Micelles: A method  to prepare stable supported biomimetic membranes, Langmuir, 29 (2013) 1152–1161

Y. Kaufman, S. Grinberg, C. Linder, E. Heldman, J. Gilron, Yue-xiao Shen, M. Kumar, V. Freger, Towards Supported Bolaamphiphile Membranes for Water Filtration: Role of Lipid-Support Interactions, J. Memb. Sci., 457 (2014)  50–61

R. Ronen, Y. Kaufman, V. Freger, Formation of pore-spanning lipid membrane and cross-membrane water and ion transport, J. Memb. Sci., 523 (2017)  247-254

photoNovel Nanofiltration Membranes for Water Recycling

 

Membranes for fuel cells

(Jian Li, Ariel Odess, Matan Cohen, Robert Gloukhovski, Maria Bass)

A proton conducting membrane is at the heart of fuel cells of PEFC type. At present, Nafion is the benchmark membranes material that combines high chemical stability and good proton conductivity. Nafion is composed of elongated polymeric micelles that can be aligned to enhance conductivity in the required direction, as well as stability and selectivity of the membrane. We study various fundamental questions related to Nafion structure and its alignment using theoretical modeling and structural characterization methods, especially, surface-sensitive. In particular, we have found that Nafion with elongated polymeric micelles aligned in the through-membrane direction has enhanced proton conductivity. In collaboration with Prof. Y. Tsur we explored embedding Nafion in nanopores of solid porous membranes, which served as a template for aligning Nafion micelles. Presently, we explore how to fabricate Nafion membrane with through-plane aligned micelles using electrospinning technique combined with the following physical folding of the prepared nanofiber mat. We are attempting to develop a stable and competitive membrane with micelles aligned in the through-membrane direction.

photo

Alignment of Nafion micelles next to different surfaces and interfaces (after Bass et al., 2011)

photo

Straight nanopores of an Anodisc alumina membranes, in which Nafion micelles may be aligned

 Nafion alignment

A-a matrix membrane with parallel transversely oriented nanopores, B-a composite membrane with Nafion-fileed nanopores.

Recent Publications:

A. Odess, M. Cohen, J. Li, M. Dantus, E. Zussman, V. Freger, Electrospun Ion-Conducting Composite Membrane with Buckling-Induced Anisotropic Through-Plane Conductivity, ACS Appl. Mater. Interfaces, 13(30)(2021) 35700–35708.

R. Gloukhovski, V. Freger, Y. Tsur, Understanding methods of preparation and characterization of pore-filling polymer composites for proton exchange membranes: a beginner’s guide, J. Rev Chem Eng, 34(4) (2018) 455-479

R. Gloukhovski, V. Freger, Y. Tsur, A Nafion‐filled Polycarbonate Track‐Etched Composite Membrane with Enhanced Selectivity for Direct Methanol Fuel Cells, Fuel Cells, 17(1) (2017) 56-66

M. Bass, A. Berman, A. Singh, O. Konovalov, V. Freger, Surface-induced orientation of micelles in films of Nafion, Macromolecules, 44 (2011) 2893–2899

V. Freger, Hydration of Ionomers and Schroeder’s Paradox in Nafion, J. Phys. Chem. B, 113(1) (2009) 24-36

 

Water and Ion Transfer to Carbon Nanotube Porins

(Vadim Neklyudov)

Sub-nanometer carbon nanotube porins (CNTPs) are unique mimics of biological water channels, yet the physics behind ion transport and selectivity in CNTPs that would rationalize experimental data remains unclear. In this research project we fill this gap and report thermodynamic analysis of ion and water transfer to CNTP, based on ab initio calculations. The roles of the interior (intra-CNT hydration, interaction with CNT wall) and exterior (dielectric energy) are considering. The model considers the transfer of K+ and Cl- ions, as well as OH- and H+ ions present in water consequently pH dependence and salt concentration effect of conductivity are described. The proposed modeling approach may be extended to other sub-nanometer nanochannels and help design next-generation desalination and osmotic energy harvesting material and devices.

imageA transparent breakdown of the ion transfer energy to three main contributions: binding to CNT, intra-CNT hydration, and dielectric polarization of the matrixr

Recent Publications:

V. Nekludov, V. Freger, Water and Ion Transfer to Narrow Carbon Nanotubes: Roles of Exterior and Interior J. Phys. Chem. Lett.,  12 (2020)  185-190

 

Microfluidics for thin-film characterization

(Mauricio Dantus)

Membrane technology is constantly evolving in a wide range of fields. Nevertheless, there is much room for improvement. Thus, in the field of water purification membrane manufacturing has not seen a major change for decades, undergoing only incremental improvements in permeability and selectivity, while removal of certain non-charged species, such as boron, still awaits a breakthrough. In comparison to the vast amount of work done in the field regarding charged molecules or ions, non-charged moieties remain mostly in the shadows.
In order to tackle this challenge, there is a need to measure and model the flow of mass through a membrane fully. This will help to better understand the fundamental mechanisms governing mass transfer through the membrane which is crucial for developing new and improved membranes for various fields, especially in reverse osmosis and nanofiltration systems. For this goal we want to understand the process of mass flow through the thin active layer that regulates the passage of the different components from one side of the membrane to another. We want to perform the experiments in a controlled environment without applying any external pressure, thus, learning about the mass transport phenomena through the active layer under diffusion flow regime.
We designed a micro-fluidic device and the method to measure all the different components in our flow cell to get a full picture of the mass flow through a membrane. This device and method can help characterize many novel thin active layers that need to be characterized not only for ion related selectivity but for water transport through the membrane as well as other non-charged moieties that can be found in water-related processes. Our system includes our custom made micro-fluidic cell, conductivity measurements for salt concentration measurements, electrochemical impedance spectroscopy for in-situ charge migration measurements and infra-red spectroscopy for the water analysis. We can analyze and characterize a large number of thin films by binding them onto a surface-tunable, well-defined mechanical support. Combining the mentioned devices into one system enables us to draw a full picture of the membrane being characterized.

microfluidic flow cell

Cross-sectrinal scheme of our custom-made microfluidic flow cell (Left). IR spectra of H2O/D2O mixtures (Top right) and an impedance spectrum showing the difference when changing salt concentration in the solutions.

Membrane Modification

(Maria Bass, Katie Baransi-Karkaby, Shiran Shultz)

The selective layer of RO and NF membranes is usually slightly hydrophobic. This helps remove salts, but causes various problems, e.g.  membrane foul by organics and biofilms and poorly remove some uncharged contaminants (bisphenol-A, boric acid etc.). We improve the selectivity towards contaminants and reduce propensity to fouling and facilitate cleaning by grafting a thin layer of acrylic polymer on the polyamide surface. We also insert certain molecules into polyamide structure to improve selectivity.

 polyamide structureprinciple of grafting –  the coating (blue) changes surfaces properties and seals imperfections of the polyamide layer underneath

Plugging for Banother principle –  insertion of “plug” molecules into polyamide as a way to enhance selectivity

 insertion of "plug" molecules into polyamidea STEM cross-section of a modified NF membrane showing the coating (dark) covering a thin polyamide layer (bright line)  on top of a porous support (light grey).

chart before and after modificationEffect of surface grafting on removal of several representative contaminants. Note the log scale for the vertical axis.

 

Recent Publications:

K. Baransi-Karkaby, M. Bass, V. Freger, In situ modification of reverse osmosis membrane elements for enhanced removal of multiple micropollutants. J. Membranes, 9(2) (2019) 28

S. Shultz, V. Freger, In situ modification of membrane elements for improved boron rejection in RO desalination. Desalination, 431 (2018) 66-72

S. Shultz, M. Bass, R. Semiat V. Freger, Modification of polyamide membranes by hydrophobic molecular plugs for improved boron rejection. J. Membr. Sci., 546 (2018) 165-172

K. Baransi-Karkaby, M. Bass, S. Levchenko, S. Eitan V. Freger, Facile modification of reverse osmosis membranes by surfactant-assisted acrylate grafting for enhanced selectivity. Environ. Sci. Technol., 51(4) (2017) 2347-2354

M. Levi Marré Tirado, M. Bass, M. Piatkovsky, M. Ulbricht, M. Herzberg, V. Freger, Assessing biofouling resistance of a polyamide reverse osmosis membrane surface-modified with a zwitterionic polymer. J. Membr. Sci., 520 (2016) 490-498

M. Bass, V. Freger, Facile evaluation of coating thickness on membranes using ATR-FTIR. J. Membr. Sci., 492 (2015) 348-354