Polyelectrolyte multilayer films as backflushable nanofiltration membranes with tunable hydrophilicity and surface charge

A diverse set of supported polyelectrolyte multilayer (PEM) membranes with controllable surface charge, hydrophilicity, and permeability to water and salt was designed by choosing constituent polyelectrolytes and by adjusting conditions of their deposition. The membranes were characterized in terms of their water and MgSO4 permeabilities and resistance to colloidal fouling. The commercial nanofiltration membrane (NF270) was used as a comparative basis. Highly hydrophilic and charged PEMs could be designed. For all membranes, MgSO4 permeability coefficients of NF270 and all PEM membranes exhibited a power law dependence on concentration: Ps ∝ C−τ, 0.19 < τ < 0.83. PEM membranes were highly selective and capable of nearly complete intrinsic rejection of MgSO4 at sufficiently high fluxes. With the deposition of colloids onto the PEM surface, the separation properties of one type of polyelectrolyte membrane showed similar rejection and superior flux properties compared to NF270 membranes. We hypothesize that a PEM-colloid nanocomposite was formed as a result of colloidal fouling of these PEM films. The feasibility of regenerating the PEM membranes fouled by colloids was also demonstrated. In summary, the PEM-based approach to membrane preparation was shown to enable the design of membranes with the unique combination of desirable ion separation characteristics and regenerability of the separation layer.

[1]  G. Decher,et al.  Buildup of Ultrathin Multilayer Films by a Self‐Assembly Process: II. Consecutive Adsorption of Anionic and Cationic Bipolar Amphiphiles and Polyelectrolytes on Charged Surfaces , 1991 .

[2]  K. V. Van Vliet,et al.  Substrata mechanical stiffness can regulate adhesion of viable bacteria. , 2008, Biomacromolecules.

[3]  Johannes Schmitt,et al.  Buildup of ultrathin multilayer films by a self-assembly process: III. Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces , 1992 .

[4]  J. Schlenoff,et al.  Polyelectrolyte Multilayers Containing a Weak Polyacid: Construction and Deconstruction , 2001 .

[5]  K. Lunkwitz,et al.  Polyelectrolyte complex layers: a promising concept for anti‐fouling coatings verified by in‐situ ATR‐FTIR spectroscopy , 1999 .

[6]  Merlin L. Bruening,et al.  Electrochemical and in Situ Ellipsometric Investigation of the Permeability and Stability of Layered Polyelectrolyte Films , 2000 .

[7]  A. Katchalsky,et al.  Thermodynamic analysis of the permeability of biological membranes to non-electrolytes. , 1958, Biochimica et biophysica acta.

[8]  M. Bruening,et al.  Size-Selective Transport of Uncharged Solutes through Multilayer Polyelectrolyte Membranes , 2004 .

[9]  J. Schlenoff,et al.  Protein adsorption modalities on polyelectrolyte multilayers. , 2004, Biomacromolecules.

[10]  B. Tieke,et al.  Composite membranes with ultrathin separation layer prepared by self-assembly of polyelectrolytes , 1999 .

[11]  Wanqin Jin,et al.  Use of Polyelectrolyte Layer-by-Layer Assemblies as Nanofiltration and Reverse Osmosis Membranes , 2003 .

[12]  Matthew D. Miller,et al.  Controlling the nanofiltration properties of multilayer polyelectrolyte membranes through variation of film composition. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[13]  G. Prestwich,et al.  Layer by layer buildup of polysaccharide films: physical chemistry and cellular adhesion aspects. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[14]  K. S. Spiegler,et al.  Thermodynamics of hyperfiltration (reverse osmosis): criteria for efficient membranes , 1966 .

[15]  Merlin L. Bruening,et al.  Ultrathin, Multilayered Polyelectrolyte Films as Nanofiltration Membranes , 2003 .

[16]  Michael F. Rubner,et al.  Controlling Bilayer Composition and Surface Wettability of Sequentially Adsorbed Multilayers of Weak Polyelectrolytes , 1998 .

[17]  How Yong Ng,et al.  Influence of colloidal fouling on rejection of trace organic contaminants by reverse osmosis , 2004 .

[18]  K. V. Van Vliet,et al.  Tuning compliance of nanoscale polyelectrolyte multilayers to modulate cell adhesion. , 2005, Biomaterials.

[19]  Kenneth S. Pitzer,et al.  Thermodynamics of electrolytes. I. Theoretical basis and general equations , 1973 .

[20]  Merlin L. Bruening,et al.  Correlation of the Swelling and Permeability of Polyelectrolyte Multilayer Films , 2005 .

[21]  P. Schaaf,et al.  Polyelectrolyte multilayers with a tunable Young's modulus: influence of film stiffness on cell adhesion. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[22]  Gero Decher,et al.  Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites , 1997 .

[23]  C. Egles,et al.  Polyelectrolyte multilayer films with pegylated polypeptides as a new type of anti-microbial protection for biomaterials. , 2004, Biomaterials.

[24]  M. Müller,et al.  Use of polyelectrolyte multilayer systems for membrane modification , 2002 .

[25]  W. Jin,et al.  Size- and charge-selective transport of aromatic compounds across polyelectrolyte multilayer membranes , 2005 .

[26]  B. Tieke,et al.  Layer-by-layer assembled membranes of protonated 18-azacrown-6 and polyvinylsulfate and their application for highly efficient anion separation. , 2007, The journal of physical chemistry. B.

[27]  Nidal Hilal,et al.  Rejection and modelling of sulphate and potassium salts by nanofiltration membranes: neural network and Spiegler–Kedem model , 2007 .

[28]  Seong Uk Hong,et al.  Separation of amino acid mixtures using multilayer polyelectrolyte nanofiltration membranes , 2006 .

[29]  Martin Müller,et al.  Selective Interaction Between Proteins and the Outermost Surface of Polyelectrolyte Multilayers: Influence of the Polyanion Type, pH and Salt , 2001 .

[30]  M. Bruening,et al.  High-flux nanofiltration membranes prepared by adsorption of multilayer polyelectrolyte membranes on polymeric supports. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[31]  O. Kedem,et al.  Determination of concentration-dependent transport coefficients in nanofiltration: Defining an optimal set of coefficients , 2008 .

[32]  Jeffrey A. Hubbell,et al.  Thin Polymer Layers Formed by Polyelectrolyte Multilayer Techniques on Biological Surfaces , 1999 .

[33]  Allon I Hochbaum,et al.  Rational design of cytophilic and cytophobic polyelectrolyte multilayer thin films. , 2003, Biomacromolecules.

[34]  J. Schlenoff,et al.  Factors Controlling the Growth of Polyelectrolyte Multilayers , 1999 .

[35]  A. Yaroshchuk Rejection of single salts versus transmembrane volume flow in RO/NF: thermodynamic properties, model of constant coefficients, and its modification , 2002 .

[36]  B. Tieke,et al.  Selective transport and incorporation of highly charged metal and metal complex ions in self-assembled polyelectrolyte multilayer membranes , 2002 .

[37]  V. Tarabara,et al.  Coupled effects of colloidal deposition and salt concentration polarization on reverse osmosis membrane performance , 2007 .

[38]  Kenneth S. Pitzer,et al.  Heat capacity and other thermodynamic properties of aqueous magnesium sulfate to 473 K , 1986 .

[39]  Alain M. Jonas,et al.  Ultrathin polymer coatings by complexation of polyelectrolytes at interfaces: suitable materials, structure and properties , 2000 .

[40]  M. Ballauff,et al.  Polyelectrolytes with Defined Molecular Architecture II , 2004 .

[41]  B. Tieke,et al.  Selective Ion Transport across Self-Assembled Alternating Multilayers of Cationic and Anionic Polyelectrolytes , 2000 .

[42]  Shoji Kimura,et al.  EVALUATION OF PORE STRUCTURE AND ELECTRICAL PROPERTIES OF NANOFILTRATION MEMBRANES , 1995 .

[43]  Seong Uk Hong,et al.  Separation of fluoride from other monovalent anions using multilayer polyelectrolyte nanofiltration membranes. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[44]  S. Schwarz,et al.  Effect of polyelectrolyte complex layers on the separation properties and the fouling behavior of surface and bulk modified membranes , 2000 .

[45]  Lu Ouyang,et al.  Multilayer polyelectrolyte films as nanofiltration membranes for separating monovalent and divalent cations , 2008 .

[46]  M. Rubner,et al.  New class of ultrathin, highly cell-adhesion-resistant polyelectrolyte multilayers with micropatterning capabilities. , 2003, Biomacromolecules.

[47]  M. Elimelech,et al.  Cake-enhanced concentration polarization: a new fouling mechanism for salt-rejecting membranes. , 2003, Environmental science & technology.

[48]  J. Schlenoff,et al.  “Internal pKa's” in Polyelectrolyte Multilayers: Coupling Protons and Salt , 2002 .

[49]  Jia-cong Shen,et al.  Cell adhesion properties of patterned poly(acrylic acid)/poly(allylamine hydrochloride) multilayer films created by room-temperature imprinting technique. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[50]  Menachem Elimelech,et al.  Influence of Crossflow Membrane Filter Geometry and Shear Rate on Colloidal Fouling in Reverse Osmosis and Nanofiltration Separations , 2002 .

[51]  Jia-cong Shen,et al.  Construction of anti-adhesive and antibacterial multilayer films via layer-by-layer assembly of heparin and chitosan. , 2005, Biomaterials.

[52]  K. Eichhorn,et al.  POLYELECTROLYTE MULTILAYERS AND THEIR INTERACTIONS , 2004 .

[53]  Jeremy J. Harris,et al.  Layered Polyelectrolyte Films as Selective, Ultrathin Barriers for Anion Transport , 2000 .