Highly Hydrophilic Thin-Film Composite Forward Osmosis Membranes Functionalized With Surface-Tailored Nanoparticles

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Article
Highly Hydrophilic Thin-Film Composite Forward Osmosis
Membranes Functionalized with Surface-Tailored Nanoparticles
Alberto Tiraferri, Yan Kang, Emmanuel P. Giannelis, and Menachem Elimelech
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/am301532g • Publication Date (Web): 04 Sep 2012
Downloaded from http://pubs.acs.org on September 10, 2012
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14 Highly Hydrophilic Thin-Film Composite Forward
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Osmosis Membranes Functionalized with Surface-
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25 ACS Applied Materials & Interfaces
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27 Revised: August 27, 2012
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Alberto Tiraferria, Yan Kangb, Emmanuel P. Giannelisb, and Menachem
34 Elimelecha,*
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37 a
38 Department of Chemical and Environmental Engineering, Yale University
39 New Haven, CT 06520-8286 (USA)
40 b
41 Department of Materials Science and Engineering, Cornell University
42 Ithaca, NY 14853 (USA)
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54 *Tel. +1 (203) 432-2789; Fax: +1 (203) 432-4387; email: menachem.elimelech@yale.edu
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ACS Applied Materials & Interfaces Page 2 of 29
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4 ABSTRACT
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Thin-film composite polyamide membranes are the state-of-the-art materials for membrane-
7 based water purification and desalination processes, which require both high rejection of
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9 contaminants and high water permeabilities. However, these membranes are prone to fouling
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11 when processing natural waters and wastewaters due to the inherent surface physicochemical
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13 properties of polyamide. The present work demonstrates the fabrication of forward osmosis
14 polyamide membranes with optimized surface properties via facile and scalable functionalization
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16 with fine-tuned nanoparticles. Silica nanoparticles are coated with superhydrophilic ligands
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18 possessing functional groups that impart stability to the nanoparticles and bind irreversibly to the
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20 native carboxyl moieties on the membrane selective layer. The tightly tethered layer of
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nanoparticles tailors the surface chemistry of the novel composite membrane without altering the
23 morphology or water/solute permeabilities of the membrane selective layer. Surface
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25 characterization and interfacial energy analysis confirm that highly hydrophilic and wettable
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27 membrane surfaces are successfully attained. Lower intermolecular adhesion forces are
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29 measured between the new membrane materials and model organic foulants, indicating the
30 presence of a bound hydration layer at the polyamide membrane surface that creates a barrier for
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32 foulant adhesion.
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36 Keywords: thin-film composite membranes, forward osmosis, superhydrophilic, membrane
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functionalization, nanocomposite membranes, fouling, antifouling
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5 INTRODUCTION
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8 Membrane-based technologies for desalination and wastewater reuse have the potential to
9 sustainably increase the supply of potable and agricultural water.1, 2
Forward osmosis, a
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11 membrane-based separation process, is particularly attractive because it can reduce the energy of
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13 separation.3 Polyamide thin-film composite membranes are at the core of this technology,1, 4 due
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15 to their superior selectivity and water permeability.4, 5
However, polyamide membranes have
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relatively high fouling propensity due to their inherent surface physicochemical properties.6, 7
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18 Further development and implementation of processes utilizing polyamide membranes require
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20 significant improvement in their fouling resistance. The rational optimization of polyamide
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22 surface properties is a critical step in this endeavor.
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24 Significant efforts have been made in membrane surface modification via post-fabrication
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26 procedures.4, 8, 9 Recently, the use of nanomaterials has shown the potential as a novel strategy to
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28 tailor membrane surface characteristics.10-12 Nanoparticles can be fine-tuned in terms of size,
29 shape, and surface chemistry to achieve desired characteristics. Well-designed nanoparticles can
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31 have strong interactions with the membrane surface to ensure irreversible functionalization and
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33 retain the targeted property during operation. The effective combination of such materials with
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35 polymeric membranes would consist of non-depleting and scalable surface functionalizations
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that do not affect other crucial transport parameters of the membrane.
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39 Recent studies have made use of antimicrobial nanoparticles with the goal to impart biocidal
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properties to polyamide membrane and control their biofouling.11, 12
These studies have
42 suggested ways to permanently tether nanoparticles by exploiting the native functional groups of
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44 polyamide. In addition, it was shown that controlling the surface density and uniform
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46 distribution of the nanoparticle coating is especially important to concentrate the nanoparticle
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48 activity at the membrane surface.12
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50 Inactivation of microorganisms that attach to the membrane would delay the onset of biofilm
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52 formation.13-15 However, the primary attachment mechanism of microorganisms involves the
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secretion of protein-based adhesives.16-18 Additionally, many other organic molecules are
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55 present in feedstreams and contribute significantly to the decrease in process performance due to
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fouling. Therefore, development of surface functionalizations that decrease the adhesion or
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5 increase the release of adsorbed organic molecules is of paramount importance.1, 17
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Wettability and hydrophilicity of the membrane material play a crucial role in controlling
9 fouling resistance and release of adsorbed foulants, as these parameters are directly related to the
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11 material surface tension.1, 17, 19 Specifically, by increasing the number of hydrogen bonding sites
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13 at the surface, the interfacial acid-base forces are maximized, thereby allowing the formation of
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15 an interfacial layer of tightly bonded water molecules that are highly oriented and have slow
16 dynamics. Because the displacement of water molecules involves work that increases the free
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18 energy of the system, this hydration layer provides a repulsive barrier against the adsorption of
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20 foulants.20 Studies have shown that increasing the membrane hydrophilicity can hinder fouling
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22 by microorganisms,21 proteins,22-24 lipopolysaccharides,23 inorganic colloids,25 alginate,26 and
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natural organic matter.26
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26 The present study demonstrates the fabrication of highly hydrophilic thin-film composite
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polyamide forward osmosis membranes by surface functionalization with tailored nanoparticles.
29 The proposed surface functionalization procedure is remarkably simple and effective, and
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31 follows the steps illustrated in Scheme 1. Silica nanoparticles (Step A) are surface-coated with
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33 superhydrophilic cationic ligands (Step B) to create a stable nanoparticle suspension. The
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35 ligands are terminated with either quaternary ammonium or amine functional groups (Step C), to
36 stabilize the nanoparticles and to provide anchor sites for tethering the nanoparticles to the
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38 membranes. A dip-coating protocol is performed, during which the nanoparticles strongly bind
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40 to the native carboxyls of hand-cast polyamide forward osmosis membranes (Step D). The
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42 newly fabricated surfaces (Step E) are extensively characterized and their physicochemical
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properties as well as their interfacial energies are investigated. The new hydrophilic membranes
45 have the potential to significantly improve membrane performance by reducing and delaying
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47 fouling.
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MATERIALS AND METHODS
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53 Fabrication of the Membranes and Characterization of their Transport
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55 Properties. TFC forward osmosis membranes were prepared by interfacial polymerization of
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polyamide onto hand-cast support membranes. The support membranes were fabricated by
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5 nonsolvent (water) induced phase separation of a solution of 9 wt% polysulfone (PSf, Mn: 22,000
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7 Da) dissolved in N-N-dimethylformamide (DMF, anhydrous, 99.8%), following the procedure
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9 outlined in our previous publication.27 The polyamide active layer was then formed on top of the
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PSf support membranes via reaction between 1,3-phenylenediamine (MPD, >99%) and 1,3,5-
12 benzenetricarbonyl trichloride (TMC, 98%) dissolved in Isopar-G (Univar, Redmond, WA), as
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14 described in our previous publication.12
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17 The transport properties of the control and functionalized forward osmosis membranes were
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tested using a cross-flow membrane filtration system in forward osmosis and pressure-retarded
20 osmosis configurations.28, 29
These measurements allowed for the determination of the pure
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22 water permeability of the membrane active layer, A, the salt (NaCl) permeability of the
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24 membrane active layer, B, and the structural parameter of the membrane support layer, S, as 2.46
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26 ± 1.19 L m-2h-1bar-1, 1.70 ± 1.18 L m-2h-1, and 537 ± 182 µm, respectively (Table S4 of the
27 Supporting Information). Details of the characterization protocol can be found elsewhere.30
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30 Fabrication and Characterization of the Superhydrophilic Nanoparticles.
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32 Superhydrophilic nanoparticles were fabricated by surface functionalization of silica
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nanoparticles (Ludox HS-30, 30%, Sigma Aldrich) with two different ligands (Scheme 1, steps
35 A-B-C). In the first instance, 6 g of silica nanoparticles were dispersed in 30 mL of deionized
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37 water and the suspension was sonicated for 30 min. The obtained dispersion was vigorously
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39 stirred with freshly prepared silane solution containing 2.1 g of (3-aminopropyl)trimethoxysilane
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41 (—NH3+/NH2, 97%, Sigma-Aldrich 281778) dissolved in 24 mL of water. For the second
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functionalization, 6 g of silica nanoparticles were suspended in 54 mL of deionized water and
44 sonicated for 30 min. Then, 6.4 g of N-trimethoxysilylpropyl-N,N,N-trimethylammonium
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46 chloride (—N(CH3)3+, 50 wt%, Gelest SIT8415.0) were added to the dispersion under vigorous
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48 stirring. Both procedures were followed by pH adjustment to ~5 and a heating step at 60 °C for
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50 18 hr. Finally, the suspensions were dialyzed in deionized water using SnakeSkin tubing (7k
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MWCO, Pierce) for 48 hours.
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54 Dynamic light scattering (DLS) experiments were performed to determine the effective
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56 hydrodynamic diameters of the functionalized nanoparticles using a multi-detector light
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scattering unit (ALV-5000, Langen, Germany) following the procedure outlined in our previous
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5 publication.31 The electrophoretic mobility of the particles was determined by a Zetasizer Nano-
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7 Z (Malvern Instruments, Worcestershire, U.K.) in deionized water at three different pH values of
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9 5, 6, and 7. For thermogravimetric analysis (TGA) (Exstar TG/DTA 6200, Seiko Instruments
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Inc., Torrance, CA), the nanoparticle solution was freeze-dried and TGA was performed from 40
12 to 600 °C at a heating rate of 20 °C/min. Transmission Electron Microscopy (TEM)
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14 micrographs of the nanoparticles were acquired using a Tecnai T12 apparatus operating at 120
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16 keV (FEI, Eindhoven, The Netherlands).
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Membrane Functionalization and Characterization. The density of carboxyl
20 functional groups at the surface of polyamide membranes was evaluated by binding and elution
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22 of toluidine blue O dye (TBO), as described in our recent publication.32 Carboxyl moieties were
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24 exploited to irreversibly bind the functionalized silica nanoparticles to the membranes, following
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26 a simple dip coating protocol (Scheme 1, steps D-E). Briefly, the polyamide membranes were
27 immersed into the nanoparticle suspension for 16 hr at room temperature (23 °C), with only the
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29 membrane active layer side accessible for contact with the suspension. The pH of the
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31 suspensions was adjusted to between 6.4 and 7.4 before the dip-coating step. In the case of
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33 membrane functionalization with nanoparticles coated with amine-terminated ligands, the
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tethering procedure was preceded by contact of the polyamide layer with a solution of ~2 mM N-
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36 (3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC, 98%) and ~5 mM N-
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38 hydroxysuccinimide (NHS, 98%) for 15 min. The polyamide surface treatment with EDC and
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40 NHS converts the native carboxylate groups of the polyamide surface into intermediate amine-
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42 reactive esters33 for crosslinking with the amine functional groups at the nanoparticle surface.
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44 The elemental composition of the membrane surface was analyzed by x-ray photoelectron
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46 spectroscopy (XPS, SSX-100 UHV, Surface Science Instruments). The sample was irradiated
47 with a beam of monochromatic Al K-alpha X-rays with energy of 1.486 keV. Attenuated Total
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49 Reflectance (ATR-IR, ThermoScientific Nicolet 6700) was performed using a germanium crystal
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51 on desiccator-dried samples. Membrane surface morphology was investigated by scanning
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53 electron microscopy (SEM, LEO 1550 FESEM). Before imaging, membranes were sputter
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coated with a layer of carbon (BTT-IV, Denton Vacuum, LLC, Moorestown, NJ). Membrane
56 surface roughness was analyzed using a Multimode AFM (Veeco Metrology Group, Santa
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Barbara, CA) in tapping mode. Symmetric silicon probes with 30-nm-thick back side aluminum
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5 coating were employed (Tap300A, Bruker Nano, Inc., Camarillo, CA). The probe had a spring
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7 constant of 40 N/m, resonance frequency of 300 kHz, tip radius of 8 ± 4 nm, and cantilever
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9 length of 125 ± 10 µm. Air-dried membranes were scanned in air at 12 randomly selected scan
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11 positions.
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13 Surface wettability was evaluated from contact angle measurements of deionized water using
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15 the sessile drop method (VCA Video Contact Angle System, AST Products, Billerica, MA). The
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system is equipped with software to determine the left and right contact angles (VCA Optima
18 XE). To account for variations between different measurements on the same surface, at least 4
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20 desiccator-dried samples from separately cast and functionalized membranes were tested on a
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22 minimum of six random locations, and the data were averaged. The relative wettability of the
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24 membranes was evaluated by calculating the membrane-liquid interfacial free energy
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 cos θ  , where θ is the average contact angle and γ is the pure water surface
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=ML γ L 1 +  L
27  r 
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29 tension (72.8 mJ/m2 at 25 °C), and r is the roughness area ratio (i.e., the ratio of actual surface
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area for a rough surface to the planar area, r = 1 + SAD , with SAD being the surface area
32 difference parameter).34, 35
Contact angles of deionized water were also used as a proxy to
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34 confirm the irreversibility of the nanoparticle-membrane bonds with functionalized membrane
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36 surfaces, after these were subjected to chemical or physical stress. Chemical stress was applied
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38 by contacting the functionalized surfaces for 15 min with a pH 2 solution (HCl), a pH 12 solution
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(NaOH), or a 0.6 M NaCl solution approximating the ionic strength of typical seawater, followed
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41 by a thorough rinse with deionized water. Physical stress was exerted by immersing the
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43 membranes in a sonicating water bath (Fisher Scientific F60) for 7 min. XPS spectra and SEM
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45 images were also re-evaluated after each of these steps to confirm the presence and extent of
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particle functionalization and assess the irreversibility of the functionalization.
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49 Additional measurements of contact angles of glycerol (≥99%) and diiodomethane (≥99%)
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51 were used to calculate the Lifshitz-van der Waals (γLW), electron donor (γ-), and electron acceptor
52 (γ+) components of the membrane surface tension before and after functionalization.36-38 In these
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54 calculations, the excess surface area due to roughness is accounted for by incorporation of the
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56 roughness area ratio, r, which was defined earlier. The total surface energy of the membrane
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surfaces is defined as the sum of the surface tension due to Lifshitz-van der Waals and Lewis
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6 acid-base components, γ TOT
= γ LW + γ AB , where γ AB = 2 γ +γ − .36, 37 From the membrane and the
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8 water components of the surface tension, it is possible to calculate the total interfacial free
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10 energy of cohesion of membrane interfaces immersed in water, ΔGMLM(TOT), which is often
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termed “hydrophilicity”.36-38 A higher value of the free energy is obtained if the membrane is
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13 non-cohesive, or more hydrophilic, when immersed in water.
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The zeta potential of the membrane surface before and after functionalization was measured
17 in an asymmetric clamping cell using a streaming potential analyzer (EKA, Brookhaven
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19 Instruments, Holtsville, NY). Measurements were performed while alternating flow direction of
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21 a 1 mM KCl solution, and by varying the pH of the solution by adding appropriate amounts of
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23 HCl or KOH. Four separately cast and functionalized membranes were evaluated. A detailed
24 experimental procedure and the method used to calculate the zeta potential from the measured
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26 streaming potential are given elsewhere.39
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29 AFM Interaction Forces. Atomic force microscopy (AFM) was used to measure the
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31 adhesive force between representative foulants in the bulk solution and the membrane by
32 adapting the procedures described by Li and Elimelech.40 The force measurements were
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34 performed in a fluid cell utilizing a particle probe, modified from a commercialized SiN AFM
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36 probe (Veeco Metrology Group, Santa Barbara, CA). A carboxylate modified latex (CML)
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38 particle (Interfacial Dynamics Corp., Portland, OR) with a diameter of 4.0 µm was attached to
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40 the tipless SiN cantilever using Norland Optical adhesive (Norland Products, Inc., Cranbury,
41 NJ). The particle probe was cured under UV light for 30 min. The CML-modified probe was
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43 immersed in 2000 mg/L model organic foulant solution, namely alginate or bovine serum
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45 albumin (BSA), for at least 16 hr at 4 °C to prevent organic degradation. The AFM adhesion
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47 force measurements were performed in a fluid cell. The ionic composition of the test solutions
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injected into the fluid cell was representative of a typical wastewater effluent (0.45 mM KH2PO4,
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50 9.20 mM NaCl, 0.61 mM MgSO4, 0.5 NaHCO3, 0.5 mM CaCl2, and 0.935 mM NH4Cl).13 The
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52 pH of the test solution was adjusted to 7.4 prior to injection. The membrane was equilibrated
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54 with the test solution for 30 to 45 min before force measurements were performed. The force
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measurements were conducted at five different locations, and at least 25 measurements were
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taken at each location. Data obtained from the retracting force curves were processed and
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5 converted to obtain the force versus surface-to-surface separation curves.
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8 RESULTS AND DISCUSSION
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10 Properties of the Nanoparticles are Fine-Tuned for Membrane Functionalization.
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12 Silica nanoparticles were used because their surface chemistry can be readily fine-tuned, thereby
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14 facilitating the attainment of target hydrophilic properties and enabling control of the interaction
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with the membrane surface. Two different ligands were employed to functionalize the
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17 nanoparticle surface. Nanoparticles treated with N-trimethoxysilylpropyl-N,N,N-
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19 trimethylammonium chloride carry quaternary ammonium groups and are hereafter designated as
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21 —N(CH3)3+ nanoparticles. The second treatment using (3-aminopropyl)trimethoxysilane
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23 produced nanoparticles with amine surface functionalities that are henceforth referred to as —
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NH2/NH3+ nanoparticles.
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27 Upon surface functionalization, the presence of ammonium or amine groups rendered the
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29 functionalized nanoparticles positively charged, as confirmed by measurements of their
30 electrophoretic mobility (Figure 1). The charge of—N(CH3)3+ nanoparticles is not significantly
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32 affected by solution pH, while the charging behavior of the—NH2/NH3+ nanoparticles is
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34 dependent on solution pH through protonation/deprotonation.
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36 The starting bare silica nanoparticles had a hydrodynamic radius of approximately 7 nm as
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38 observed by DLS measurements. The measured radius in deionized (DI) water increased to ~8
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40 and ~19 nm for the —N(CH3)3+ and —NH2/NH3+ functionalizations, respectively (Figure 1,
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42 table). While the small increase in diameter for the quarternary ammonium-functionalized
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44 nanoparticles is attributed to the presence of a hydration layer bound to the hydrophilic surface
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ligands, the increase in size of the amine nanoparticles was likely due to slight aggregation.
47 TEM imaging confirmed that the size of both types of functionalized nanoparticles was
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49 comparable to that of the bare silica nanoparticles (not shown). This observation substantiates
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51 our hypothesis that the —NH2/NH3+ nanoparticles undergo aggregation in aqueous solution. No
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53 change in diameter was observed by DLS within 45 minutes of measurement for both
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functionalized nanoparticle types, suggesting that aggregation occurred immediately upon
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56 dispersion of the particle in solution. Overall, the positively-charged surface groups increased
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the electrostatic repulsion between functionalized nanoparticles, thwarting their aggregation in
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5 aqueous solution.
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In the presence of electrolytes in solution, DLS data demonstrated an increase in
9 hydrodynamic size for all nanoparticles (Figure 1, table). This phenomenon can be due to slight
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11 aggregation and/or to the adsorption of highly hydrated multivalent counterions onto the charged
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13 and hydrophilic particle surface. This mechanism could further enhance the structuring of the
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15 water molecules at the solid-liquid interface, resulting in a larger measured hydrodynamic
16 diameter by DLS.41-43
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19 The presence of organic ligands on the surface of the functionalized nanoparticles was
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confirmed by TGA measurement (Figure 1C-D-E). TGA data showed the appearance and
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22 amplification of two thermal degradation peaks (~250 and ~400 °C) for the functionalized
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24 nanoparticles. These peaks may be associated with thermo-oxidation of the alkyl chains of the
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26 surface ligands and possibly to the volatilization of some excess coupling agents used during
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particle functionalization. The production of a larger amount of volatile degradation products
29 translated into a smaller percentage of sample recovery at the end of the heating cycle compared
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31 to the bare silica nanoparticles.
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34 Nanoparticles are Irreversibly Bound to the Membrane Surface after
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Functionalization. All polyamide membranes fabricated via interfacial polymerization of
37 TMC and MPD inherently possess an outer layer of relatively high, negative fixed charges
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39 resulting from incomplete reaction and hydrolysis of the TMC acyl chlorides into carboxyls.32, 44
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41 The surface density of carboxylic groups of the membranes used in this study was measured by
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43 TBO 19 ± 4 charges/nm2 of planar area. The positively charged groups at the nanoparticle
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surface ensure durable adhesion to the membrane surface via strong interaction with the native
46 polyamide moieties, thus securing the nanoparticles at this interface. Specifically, the
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48 membrane−particle tethering occurred here primarily via electrostatic attraction.45 In addition,
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50 the functionalization with —NH2/NH3+ nanoparticles was performed in the presence of
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52 crosslinking agents EDC and NHS to facilitate the formation of covalent amide bonds between
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54 the nanoparticle amine groups and the membrane carboxyls.12 The functionalized membranes
55 are hereafter designated as —N(CH3)3+ or —NH2/NH3+ membranes.
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XPS data of the membrane surfaces evaluated before and after functionalization are
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5 presented in Figure 2. The energy peaks observed for the polyamide surface (black) are
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7 attributed to carbon, oxygen, and nitrogen (Figure 2A) among which carbon was the most
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9 abundant element (Figure 2B), consistent with the chemistry of the membrane active layer. The
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spectra related to the functionalized surfaces (blue and red) showed the appearance of energy
12 peaks associated with silicon (Figure 2A), which confirm the presence of the silica-based
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14 nanoparticles at these surfaces. Because XPS analyzes only the superficial portion of the
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16 membrane, oxygen was observed to be the predominant element, followed by carbon and silicon
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18 (Figure 2C-D), according to the composition of the functionalized silica nanomaterial. ATR-IR
19 spectra showed the emergence of a shoulder and an increase in absorbance around 1060 to 1100
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21 cm-1 (Supporting Information Figure S1), which is attributed to the stretching mode of Si-O-Si
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23 bonds.46 This observation further confirms the presence of silanized SiO2 nanoparticles at the
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25 membrane surface.
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27 Physicochemical Properties of the Membrane Surface. Figure 3 presents the
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29 pH−dependent zeta potential of the membrane surfaces before and after functionalization. The
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31 zeta potential was measured over the pH range of 4 to 9 for at least 4 separately cast and
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functionalized membrane samples. Knowledge of the membrane surface zeta potential and of
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34 the type and density of exposed charges is crucial because these parameters greatly influence the
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36 membrane fouling behavior.40, 47
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38 The results with the control membranes were in accordance with the protonation behavior of
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40 polyamide functional groups. At very low pH, the unreacted amine groups of MPD are
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42 protonated while carboxylic groups are uncharged, resulting in an overall positive potential
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44 (Figure 3A). As the pH increased above the pKa of the polyamide carboxyl groups,48 these
45 predominant acidic groups deprotonated, thus imparting a negative and largely constant zeta
46
47 potential to the surface.
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49
The zeta potential behavior of the functionalized membranes was consistent with the
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51 functionalities present at both the nanoparticle and the membrane surface. The —N(CH3)3+
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53 nanoparticles are positively charged at all pH values and interact with the membrane carboxylic
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55 moieties via electrostatic attraction. Therefore, the zeta potential of the membranes was highly
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positive at low pH, where carboxyl groups are uncharged, and became progressively more
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5 negative as the carboxylic groups deprotonated (Figure 3B). The overall zeta potential was close
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7 to zero around the pH range of 7 to 8, which is the characteristic pH of natural waters and
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9 wastewater effluents in membrane separation processes.
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11 Nanoparticles functionalized with —NH2/NH3+ ligands are assumed to preferentially form
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13 amide bonds with the membrane carboxylic groups, thus effectively neutralizing many of the
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15 charges present on both reacting surfaces. As a result, the measured zeta potential values of the
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17
—NH2/NH3+ membranes were of lower magnitude compared to those of the —N(CH3)3+
18 membranes and exhibited a wider near-zero potential region, between approximately pH 6 and 8
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20 (Figure 3C). The zeta potential results provide indirect evidence for the presence of nanoparticles
21
22 at the surface of the functionalized membranes and for the type of particle−membrane
23
24 interaction.
25
26 The membrane surface morphology before and after functionalization was analyzed by SEM
27
28 and AFM (Figure 4). The representative topographic image (Figure 4G) and SEM surface
29
30 micrographs (Figure 4A-B) of a control polyamide membrane showed a uniform ridge-and-
31
valley morphology, which is typical of polyamide thin films formed by interfacial
32
33 condensation.1, 4
The characteristic surface roughness parameters of the membranes were
34
35 measured by tapping mode AFM. The untreated polyamide surfaces had a RMS of 129 ± 40 nm,
36
37 an average roughness, Ra, of 102 ± 39 nm, a maximum roughness, Rmax, of 850 ± 30 nm, and a
38
39 surface area difference, SAD, of 23 ± 10% (Figure 4H). These values are comparable to those
40
41
reported for similar materials.49
42
43 The high magnification SEM micrographs in Figures 4B-D-F, imaged at the surface of the
44
45 membranes after functionalization, showed that the ridge-and-valley features of the
46 functionalized surfaces were overlaid by a layer of nanoparticles. The nanoparticle size
47
48 correlates well with the radius measured by DLS experiments for each respective type of surface
49
50 functionality. The low magnification SEM micrographs presented in Figures 4A-C-E suggest
51
52 that the overall morphology of the membrane surface was not significantly affected after
53
functionalization, as the ridge-and-valley features were visible and comparable to those observed
54
55 for the control polyamide surface. This observation suggests that the nanoparticle coating
56
57
58 13
59
60
1
2
3
consisted of a mono- or multi-layer, with a total thickness small relative to the roughness of the
4
5 membrane active layer.
6
7
8
The surface roughness measurements of functionalized membranes (Figure 4H) indicated a
9 reduction in surface roughness due to the presence of nanoparticles, although it was not
10
11 sufficient to alter the overall surface morphology, consistent with SEM analysis. The
12
13 nanoparticles are likely to deposit preferentially within the valley-like regions of the polyamide
14
15 surface, thus flattening the overall surface. This flattening was more pronounced for the
16
relatively larger —NH2/NH3+ nanoparticles, which produced a more significant effect in
17
18 decreasing the membrane SAD (Figure 4H and Table 1).
19
20
21 Nanoparticles Render the Membrane Highly Hydrophilic. Figure 5 presents the
22
23 average contact angles of DI water at the surface of control (polyamide) and functionalized
24
membranes before (solid bar) and after (hollow bars) they were subjected to chemical and
25
26 physical stresses. The untreated polyamide membranes had a contact angle of 104 ± 16°, larger
27
28 than what typically observed for commercial polyamide membranes (Figure 5, Table 1). For
29
30 rough surfaces, such as those of our hand-cast samples, larger contact angles than expected from
31
32
the chemistry of the material might result from air trapped between the solid surface rugosities
33 and the liquid droplet.50 The digital picture (Figure 5A) shows a representative profile of a water
34
35 droplet on the hydrophobic polyamide surface. The presence of nanoparticles on the surface
36
37 functionalized membranes had a dramatic effect on the conformation of water droplets at the
38
39 solid-liquid interface, yielding contact angles of ~10° for the —N(CH3)3+ membranes and ~20°
40
for the —NH2/NH3+ membranes (Table 1), only in part attributable to the decrease in roughness
41
42 measured on the functionalized surfaces (Figure 4). Representative pictures of water droplet
43
44 profiles for the two functionalized surfaces are presented on the right of Figure 5B.
45
46 Contact angle measurements were also used as a proxy to appraise the reversibility of the
47
48 interaction between nanoparticles and membrane surfaces. Chemical or physical stresses
49
50 considerably harsher than typical operational conditions were applied to the functionalized
51
52 membranes and the conformation of water droplets was then re-evaluated. The contact angles
53 did not significantly change compared to membranes analyzed immediately after modification
54
55 (Figure 5A and B), suggesting that the nanoparticle-membrane bonds were sufficiently strong to
56
57
58 14
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1
2
3
render the surface functionalization irreversible. XPS and SEM analyses were also performed
4
5 subsequent to the stress protocol and showed no significant difference compared to the results
6
7 obtained on the functionalized membranes not subjected to stresses (Supporting Information
8
9 Figure S2). The confirmed strength of the nanoparticle-membrane interaction suggests minimal
10
11
detachment of the nanoparticles from the surface during typical membrane operational
12 conditions, thus ensuring long-term functionalization.
13
14
15 The surface tensions and interfacial free energies of the membranes were calculated from
16 contact angle measurements with two polar liquids, water and glycerol, and an apolar liquid,
17
18 diiodomethane (Table 1). The polyamide control membrane had a relatively low surface energy
19
20 ( γ TOT = 37.8 mJ/m2), almost exclusively resulting from van der Waals forces. As a result, the
21
22 polyamide surface was found to be relatively wetting ( −∆GML = 57.9 mJ/m2), but hydrophobic
23
24 ( ∆GMLM =
−97.9 mJ/m2) when immersed in deionized water (Figure 6). These results are
25
26 consistent with data obtained from other polyamide membranes.38, 51
27
28
29 The surface properties of the membranes changed dramatically after functionalization with
30 superhydrophilic nanoparticles. Both the Lifshitz-van der Waals and the acid-base components
31
32 of surface tensions increased. In particular, the electron donor parameter was responsible for the
33
34 nearly monopolar functionality of the surface (Table 1), consistent with the properties of the
35
36 ligands coating the nanoparticle surface.52, 53
The high density of electron donor sites at the
37
38
surface of the functionalized membranes promotes hydrogen bonding interactions with water
39 molecules.54 This, in turn, resulted in a significant increase in calculated membrane wettability
40
41 and in a conversion of the surface interfacial free energy of cohesion to positive values, i.e.
42
43 hydrophilic properties (Figure 6A). The values of hydrophilicity estimated for our
44
45 functionalized membranes are the highest reported so far in the literature for similar materials.
46 The high interfacial free energy was accompanied by a relatively large value of surface energy
47
48 (Figure 6B). The strong hydration layer of the near superhydrophilic surface resists the
49
50 adsorption of molecules and particles to the membrane surface, thus increasing its anti-fouling
51
52 resistance.17
53
54 Hydrophilic Membranes Have Lower Interaction Forces with Organic Foulants.
55
56 The rationale for creating highly hydrophilic membranes for water separation technologies is to
57
58 15
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60
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2
3
impart fouling resistance. By maximizing the interfacial acid-base forces between surfaces and
4
5 the adherent water, we form a layer of tightly bonded water molecules that act as a short-range
6
7 barrier against the adhesion of foulants.20 Atomic force microscopy (AFM) has been applied in
8
9 membrane fouling/cleaning research to quantify intermolecular forces when foulants approach
10
11
the investigated surface within the contact limit.6, 20, 40, 55, 56 In this study, we investigated the
12 interaction forces between model foulants adsorbed on a colloidal probe, namely alginate and
13
14 BSA, and our membranes (Figure 7). Representative adhesion (pull-off) curves obtained during
15
16 the retraction of the fouled tip from the membrane surface are presented. We also report the
17
18 average, minimum, and maximum values of adhesion forces calculated from a statistically
19 significant number of retracting force-distance curves analyzed in 5 randomly selected spots on
20
21 each membrane sample.
22
23
24
AFM results showed that the attractive energy well between model foulants and control
25 polyamide membranes was deeper than that observed using functionalized, hydrophilic
26
27 membranes (Figure 7A and B). The resulting distribution of foulant-membrane intermolecular
28
29 forces was also statistically more negative (i.e. more attractive) for the control polyamide
30
31 membranes (Supporting Information Figure S3). Several force-distance curves measured on —
32
N(CH3)3+ membranes did not show an attractive energy well but only repulsive forces, indicating
33
34 no foulant adhesion to the membrane due to a barrier to adhesion.57 This behavior was not
35
36 observed for control polyamide membranes on which all AFM foulant probe engagements
37
38 resulted in an attractive force, often exceeding -3 mN/m for both foulant molecules. These
39
40
results are consistent with previous observations showing lower attractive forces on hydrophilic
41 surfaces,20 and indicate the attainment of highly hydrophilic surfaces with potentially lower
42
43 fouling propensity. The antifouling behavior and antifouling mechanisms of our highly
44
45 hydrophilic membranes were further confirmed in cross-flow experiments in forward osmosis
46
47 and reverse osmosis operation modes, using feed solutions of BSA or alginate as described in our
48
related publication.30
49
50
51
52 CONCLUSION
53
54 We fabricated forward osmosis membranes with near superhydrophilic surface properties that
55
56 could significantly reduce fouling. The surface of silica nanoparticles was functionalized with
57
58 16
59
60
1
2
3
superhydrophilic ligands possessing quaternary ammonium or amine moieties. A simple dip-
4
5 coating technique was utilized to irreversibly bind the nanoparticles to the native carboxylic
6
7 groups of polyamide forward osmosis membranes. The functionalization produced a uniform
8
9 layer of nanoparticles on the polyamide film rendering the membrane surface highly wettable
10
11
and hydrophilic. The post-fabrication route to functionalization ensures that the productivity and
12 the rejection performance of the membranes are maintained. Using atomic force microscopy, we
13
14 measured significantly lower adhesion forces between model organic foulants and the
15
16 hydrophilic surfaces compared to unmodified polyamide membranes. These observations are
17
18 significant because lower foulant-membrane adhesion has been shown to correlate well with
19 increased membrane fouling resistance.
20
21
22
23
24 ASSOCIATED CONTENT
25
26
27 Supporting Information. ATR-IR analysis of the membrane surfaces confirming presence
28
29 of silica nanoparticles after membrane functionalization (Figure S1); XPS and SEM analyses of
30
the membrane surface performed after subjecting the membrane surface to stress, confirming the
31
32 irreversibility of surface functionalization (Figure S2); statistics of foulant-membrane interaction
33
34 forces measured by AFM (Figure S3); summary of forward osmosis performance testing
35
36 conditions and results (Table S4).
37
38
39
40
41 AUTHOR INFORMATION
42
43
44 Corresponding Author. *Email: menachem.elimelech@yale.edu; phone: (203) 432-2789
45
46
47
48
49
50
ACKNOWLEDGMENTS
51
52 This publication is based on work supported by Award No. KUS-C1-018-02, made by King
53
54 Abdullah University of Science and Technology (KAUST). We also acknowledge the NWRI-
55 AMTA Fellowship for Membrane Technology, awarded to Alberto Tiraferri.
56
57
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5 REFERENCES
6
7
8 (1) Elimelech, M.; Phillip, W. A., Science 2011, 333 (6043), 712.
9 (2) McGinnis, R. L.; Elimelech, M., Environ. Sci. Technol. 2008, 42 (23), 8625.
10 (3) McGinnis, R. L.; Elimelech, M., Desalination 2007, 207 (1-3), 370.
11
(4) Petersen, R. J., J. Membr. Sci. 1993, 83 (1), 81.
12
13 (5) Geise, G. M.; Park, H. B.; Sagle, A. C.; Freeman, B. D.; McGrath, J. E., J. Membr. Sci.
14 2011, 369 (1-2), 130.
15 (6) Ang, W. S.; Tiraferri, A.; Chen, K. L.; Elimelech, M., J. Membr. Sci. 2011, 376 (1-2),
16 196.
17 (7) Mi, B. X.; Elimelech, M., J. Membr. Sci. 2010, 348 (1-2), 337.
18
19
(8) Rana, D.; Matsuura, T., Chem. Rev. 2010, 110 (4), 2448.
20 (9) Kang, G. D.; Cao, Y. M., Water Res. 2012, 46 (3), 584.
21 (10) Kim, S. H.; Kwak, S. Y.; Sohn, B. H.; Park, T. H., J. Membr. Sci. 2003, 211 (1), 157.
22 (11) Mo, J.; Son, S. H.; Jegal, J.; Kim, J.; Lee, Y. H., J. Appl. Polym. Sci. 2007, 105 (3),
23 1267.
24
(12) Tiraferri, A.; Vecitis, C. D.; Elimelech, M., Acs Applied Materials & Interfaces 2011, 3
25
26 (8), 2869.
27 (13) Herzberg, M.; Elimelech, M., J. Membr. Sci. 2007, 295 (1-2), 11.
28 (14) De Kwaadsteniet, M.; Botes, M.; Cloete, T. E., Nano 2011, 6 (5), 395.
29 (15) Upadhyayula, V. K. K.; Gadhamshetty, V., Biotechnol. Adv. 2010, 28 (6), 802.
30 (16) Stanley, M. S.; Callow, M. E.; Callow, J. A., Planta 1999, 210 (1), 61.
31
32
(17) Callow, J. A.; Callow, M. E., Nature Communications 2011, 2.
33 (18) Herzberg, M.; Kang, S.; Elimelech, M., Environ. Sci. Technol. 2009, 43 (12), 4393.
34 (19) Shannon, M. A.; Bohn, P. W.; Elimelech, M.; Georgiadis, J. G.; Marinas, B. J.; Mayes,
35 A. M., Nature 2008, 452 (7185), 301.
36 (20) Morra, M., Journal of Biomaterials Science-Polymer Edition 2000, 11 (6), 547.
37
(21) Finlay, J. A.; Callow, M. E.; Ista, L. K.; Lopez, G. P.; Callow, J. A., Integr. Comp. Biol.
38
39 2002, 42 (6), 1116.
40 (22) Wavhal, D. S.; Fisher, E. R., Langmuir 2003, 19 (1), 79.
41 (23) Gudipati, C. S.; Finlay, J. A.; Callow, J. A.; Callow, M. E.; Wooley, K. L., Langmuir
42 2005, 21 (7), 3044.
43 (24) Ostuni, E.; Chapman, R. G.; Holmlin, R. E.; Takayama, S.; Whitesides, G. M.,
44
45
Langmuir 2001, 17 (18), 5605.
46 (25) Brant, J. A.; Childress, A. E., J. Membr. Sci. 2004, 241 (2), 235.
47 (26) Ang, W. S.; Lee, S. Y.; Elimelech, M., J. Membr. Sci. 2006, 272 (1-2), 198.
48 (27) Tiraferri, A.; Yip, N. Y.; Phillip, W. A.; Schiffman, J. D.; Elimelech, M., J. Membr. Sci.
49 2011, 367 (1-2), 340.
50
(28) Yip, N. Y.; Tiraferri, A.; Phillip, W. A.; Schiffman, J. D.; Elimelech, M., Environ. Sci.
51
52 Technol. 2010, 44 (10), 3812.
53 (29) Yip, N. Y.; Tiraferri, A.; Phillip, W. A.; Schiffrnan, J. D.; Hoover, L. A.; Kim, Y. C.;
54 Elimelech, M., Environ. Sci. Technol. 2011, 45 (10), 4360.
55 (30) Tiraferri, A.; Kang, Y.; Giannelis, E.; Elimelech, M., Environ. Sci. Technol. 2012,
56 Under review.
57
58 19
59
60
1
2
3
(31) Tiraferri, A.; Chen, K. L.; Sethi, R.; Elimelech, M., J. Colloid Interface Sci. 2008, 324
4
5 (1-2), 71.
6 (32) Tiraferri, A.; Elimelech, M., J. Membr. Sci. 2012, 389, 499.
7 (33) Staros, J. V.; Wright, R. W.; Swingle, D. M., Anal. Biochem. 1986, 156 (1), 220.
8 (34) Ghosh, A. K.; Jeong, B. H.; Huang, X. F.; Hoek, E. M. V., J. Membr. Sci. 2008, 311 (1-
9 2), 34.
10
11
(35) Wenzel, R. N., Journal of Physical and Colloid Chemistry 1949, 53 (9), 1466.
12 (36) Van Oss, C. J., J. Adhes. Sci. Technol. 2002, 16 (6), 669.
13 (37) van Oss, C. J.; Wu, W.; Docoslis, A.; Giese, R. F., Colloid Surface B 2001, 20 (1), 87.
14 (38) Hurwitz, G.; Guillen, G. R.; Hoek, E. M. V., J. Membr. Sci. 2010, 349 (1-2), 349.
15 (39) Walker, S. L.; Bhattacharjee, S.; Hoek, E. M. V.; Elimelech, M., Langmuir 2002, 18
16
(6), 2193.
17
18 (40) Li, Q. L.; Elimelech, M., Environ. Sci. Technol. 2004, 38 (17), 4683.
19 (41) Butkus, M. A.; Grasso, D., J. Colloid Interface Sci. 1998, 200 (1), 172.
20 (42) Derjaguin, B. V.; Churaev, N. V., Langmuir 1987, 3 (5), 607.
21 (43) Leberman, R.; Soper, A. K., Nature 1995, 378 (6555), 364.
22 (44) Freger, V., Langmuir 2003, 19 (11), 4791.
23
24
(45) Fang, J.; Kelarakis, A.; Estevez, L.; Wang, Y.; Rodriguez, R.; Giannelis, E. P., J.
25 Mater. Chem. 2010, 20 (9), 1651.
26 (46) Mawhinney, D. B.; Glass, J. A.; Yates, J. T., J. Phys. Chem. B 1997, 101 (7), 1202.
27 (47) Wiesner, M. R.; Chellam, S., Environ. Sci. Technol. 1999, 33 (17), 360A.
28 (48) Vrijenhoek, E. M.; Hong, S.; Elimelech, M., J. Membr. Sci. 2001, 188 (1), 115.
29
(49) Tang, C. Y. Y.; Kwon, Y. N.; Leckie, J. O., Desalination 2009, 242 (1-3), 168.
30
31 (50) van Oss, C. J.; Giese, R. F.; Docoslis, A., J. Dispersion Sci. Technol. 2005, 26 (5), 585.
32 (51) Brant, J. A.; Childress, A. E., J. Membr. Sci. 2002, 203 (1-2), 257.
33 (52) Chatterjee, A.; Balaji, T.; Matsunaga, H.; Mizukami, F., Journal of Molecular Graphics
34 & Modelling 2006, 25 (2), 208.
35 (53) He, T.; Ding, H. J.; Peor, N.; Lu, M.; Corley, D. A.; Chen, B.; Ofir, Y.; Gao, Y. L.;
36
37 Yitzchaik, S.; Tour, J. M., J. Am. Chem. Soc. 2008, 130 (5), 1699.
38 (54) Vanoss, C. J.; Chaudhury, M. K.; Good, R. J., Adv. Colloid Interface Sci. 1987, 28 (1),
39 35.
40 (55) Tang, C. Y.; Kwon, Y. N.; Leckie, J. O., J. Membr. Sci. 2009, 326 (2), 526.
41 (56) Lee, S.; Ang, W. S.; Elimelech, M., Desalination 2006, 187 (1-3), 313.
42
43
(57) Adout, A.; Kang, S.; Asatekin, A.; Mayes, A. M.; Elimelech, M., Environ. Sci. Technol.
44 2010, 44 (7), 2406.
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43 Scheme 1. Schematic of the functionalized nanoparticles and of the protocol to functionalize the thin-
44
45 film composite polyamide forward osmosis membranes used in this study. Polyamide membranes
46
47 possess native carboxylic groups at their surfaces that can be exploited as binding sites for
48 functionalization with tailored nanoparticles. Two different ligands were used to tailor the surface of
49
50 nanoparticles rendering them highly hydrophilic and optimizing their interaction with the membrane
51
surface.
52
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58 21
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4 Hydrodynamic radius using dynamic light Electrophoretic
5 scattering (nm)* mobility (µm·cm V -1s-1)
6 Deionized water Salt solution Unadjusted pH
7 Bare silica 6.98 ± 0.11 8.15 ± 0.15
8
9 -N(CH3)3+ 8.02 ± 0.16 11.55 ± 0.25 2.48 ± 0.09
10 -NH2/NH3+ 18.99 ± 0.35 20.52 ± 0.45 2.30 ± 0.19
11 *No aggregation observed within 45 minutes
12 0.40
Normalized DTG (% / min)

13 100
Bare silica
C 0.35
Normalized TG (%)
14 99 0.30
15 -N(CH3)3+ 98 0.25
16 0.20
17 A 97
0.15
18 96 0.10
19 95 0.05
20 0.00
21 94
0 100 200 300 400 500 600
22 0.40

23 100 D 0.35
Normalized TG (%)
24 99 0.30
25
98 0.25
26
0.20
27 97
0.15
28
96 0.10
29 -NH2/NH3+ 95 0.05
30 -N(CH3)3+
31 B 94
0 100 200 300 400 500 600
0.00
32
33 0.40

34 100
-NH2/NH3+ E 0.35
Normalized TG (%)
35 99 0.30
36 98 0.25
37 0.20
38 97
0.15
39 96 0.10
40 95 0.05
41 0.00
42 94
0 100 200 300 400 500 600
43
Temperature
44
45
46
47 Figure 1. Size, electrophoretic mobility, and thermogravimetric analysis of the functionalized silica
48 nanoparticles. The measured size and electrophoretic mobility of the nanoparticles in deionized water
49 and in an electrolyte solution representative of a typical wastewater effluent (0.45 mM KH2PO4, 9.20 mM
50 NaCl, 0.61 mM MgSO4, 0.5 mM NaHCO3, 0.5 mM CaCl2, and 0.935 mM NH4Cl) are presented in the
51 table. A) and B) show TEM images of silica nanoparticles silanized with –N(CH3)3+-terminated chains
52 and –NH2-terminated chains, respectively. The plots on the right present TGA data for the C) bare silica
53 nanoparticles as well as for the D-E) functionalized nanoparticles. The thermogravimetric plot (line)
54
refers to the left axis and the differential thermogravimetric plot (hollow circles) refers to the right axis.
55
56
Both data sets were normalized by the initial sample mass.
57
58 22
59
60
1
2
3
4
5
6
7
A Polyamide O
8
CPS (a.u.)
9
-N(CH3)3+
10 -NH3+/NH2 C
11
12
13 N
14 Si 2s Si 2p
15
16
17 1200 1000 800 600 400 200 0
18 Electron Binding Energy (eV)
19
20 Polyamide
21
22 70 B 70 C 70 D
Area Fraction (%)
23 60 60
-N(CH3)3+ 60
-NH3+/NH2
24 50 50 50
25 40 40 40
26
30 30 30
27
28 20 20 20
29 10 10 10
30 0 0 0
31 O C N O C N Si O C N Si
Element Element Element
32
33
34
35
36
37
38
39
40
41
42 Figure 2. XPS analysis of the surface of the membranes. A) XPS survey scan of control polyamide
43 membranes (black), and of membranes functionalized with silica nanoparticles silanized with –N(CH3)3+-
44
45 terminated chains (red) and –NH2-terminated chains (blue), B-C-D) fractions of oxygen (O, purple),
46
47
carbon (C, green), nitrogen (N, black), and silica (Si, orange) relative to the sum of these elements present
48 at the surface of the three different membranes. The elemental fraction was calculated using software
49
50 CasaXPS from the scans of Figure 2A. The two functionalized membranes show the presence of
51
significant amount of silica at their surface.
52
53
54
55
56
57
58 23
59
60
1
2
3
4
40
5
Polyamide
Zeta Potential (mV)

6 30
7 20
8 10
9
10 0
11 -10
12 -20
13
-30 A
14
15 4 5 6 7 8 9
16 40
17
-N(CH3)+3
Zeta Potential (mV)
18 30
19 20
20 10
21
0
22
23 -10
24 -20
25 -30 B
26
4 5 6 7 8 9
27
28 40
29 30 -NH+3/NH2
Zeta Potential (mV)
30 20
31
10
32
33 0
34 -10
35 -20
36
37 -30 C
38 4 5 6 7 8 9
39 pH
40
41
42
43
44 Figure 3. Zeta potential of the surface of the membranes as a function of solution pH. A) Zeta potentials
45 of polyamide control membranes, and B-C) zeta potentials of membranes functionalized with silica
46
47 nanoparticles silanized with (red) –N(CH3)3+-terminated chains and (blue) –NH2-terminated chains,
48
49 respectively. Zeta potential values were measured and calculated for at least 4 separately cast and
50 functionalized samples for each membrane type, across a pH range from approximately 4 to 9. The data
51
52 related to different samples were placed in the same plot and represented by different symbols.
53
Measurements were taken at room temperature (23 °C), in solution of 1 mM KCl, and by adjusting the pH
54
55 with appropriate amounts of HCl or KOH.
56
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43 Figure 4. Surface morphology and roughness of the membranes from SEM and AFM analyses. Surface
44 SEM micrographs of A-B) polyamide control membranes, C-D) membranes functionalized with silica
45
46
nanoparticles silanized with –N(CH3)3+-terminated chains, and E-F) membranes functionalized with silica
47 nanoparticles silanized with –NH2-terminated chains. Panels A, C, and E are low magnification
48 micrographs, while panels B, D, and F are higher magnification surface images. G) representative AFM
49 images of a control polyamide membrane. H) roughness parameters measured by AFM tapping mode
50
51
analysis. Here, RMS is root mean square of roughness, Rmax/10 is maximum roughness divided by a
52 factor of 10, Ra is average roughness, and SAD is percentage surface area difference. Black, red, and blue
53 bars refer to polyamide membranes, and membranes functionalized with –N(CH3)3+- and –NH2-coated
54 nanoparticles, respectively. Roughness values are the average of measurements taken from a total of 12
55
56
random spots on 3 separately cast and functionalized sample surfaces.
57
58 25
59
60
1
2
3
4
5
A
Contact Angle (degrees)
120 Polyamide
6
7 -N(CH3)3+
8 100
9
Subjected to stress
10 80 Polyamide
11
12 60
on )
.S H
th aO
13
Cl
.
40
Na
pH Cl)
Ba 2 (N
14
(H
M
15
1
2
6
20
0.
pH
16
17
18 0
19
-N(CH3)3+
B
20
Contact Angle (degrees)
21 120 Polyamide
22 -NH2/NH3+
23 100
24 Subjected to stress
25 80
26 -NH2/NH3+
. S H)
O
27 60
12 l)
2 l
pH NaC
.
pH (HC
Ba (Na
on
28
M
29
th
40
6
0.
30
31
32
20
33
34 0
35
36
37
38
39 Figure 5. Contact angles of deionized water on the surface of the membranes for A) membranes
40
41 functionalized with silica nanoparticles silanized with –N(CH3)3+-terminated chains (red), and B)
42 membranes functionalized with silica nanoparticles silanized with –NH2-terminated chains (blue). The
43
44 contact angle of DI water on control polyamide membranes is shown in both plots as a patterned black
45
bar. The plots show values of the membranes as functionalized (solid bars), and after the surface was
46
47 subjected to stress (hollow bars), as briefly labeled in the graphs on each bar and as described in the
48
49 discussion. Values are averages of at least 8 random spots from each sample. Measurements were
50 carried out at room temperature (23 °C), without addition of ionic strength, and at unadjusted pH. When
51
52 contact angles were too low to be accurately measured, a value of 10 degrees was assumed for the
53
54 calculations. Representative pictures of DI water droplets are included on the right for illustration
55 purposes.
56
57
58 26
59
60
1
2
3
4
5 -∆G13 (Wettability)
6
Specific Energy (mJ/m2)

7 Polyamide
8
120 -N(CH3)3+
9 -NH2/NH3+
10
80
11
12
40
13 0
14
15 -40
16
17
18
-80 A
19
20 -∆G131 (Hydrophilicity)
21
22
23 60
Surface Energy (mJ/m2)
24
25 50
B
26
27 40
28
29 30
30
31
32
20
33
34 10
35
36 0
37
38
39
40
41
42
43 Figure 6. Wettability, hydrophilicity, and surface energy of the surface of the membranes. A) wettability
44 with DI water, -ΔGML, and of hydrophilicity, ΔGTOTMLM, and B) calculated values of surface energy, γTOT.
45
46 Data for polyamide control membranes are presented as black patterned bars. Values for membranes
47
functionalized with silica nanoparticles silanized with –N(CH3)3+-terminated chains or with –NH2-
48
49 terminated chains are shown as red and blue bars, respectively. The surface energy parameters were
50
51 calculated from average contact angles measured with DI water, glycerol, and diiodomethane at room
52 temperature (23 °C), without addition of ionic strength, and at unadjusted pH. At least 25 contact angles
53
54 on at least 3 separately cast and functionalized samples were measured for each liquid and for each
55
56 membrane type.
57
58 27
59
60
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41 Figure 7. Representative AFM retraction curves for foulant-membrane interaction using a A) BSA-
42
43 fouled tip, and B) alginate-fouled tip. Data for control polyamide and for membranes functionalized with
44
45 –N(CH3)3+-terminated nanoparticles are shown as black squares and red circles, respectively. The
46 average, minimum, and maximum values of the minimum energy wells measured for 125 separate
47
48 retracting curves are reported for each foulant. The ‘No’ label stands for measurements where no
49
adhesion force was observed. The test solution for the measurements is synthetic wastewater as described
50
51 in the experimental section. Measurements were carried out at room temperature (23 °C).
52
53
54
55
56
57
58 28
59
60
1
2
3
Table 1. Summary of the contact angle and surface energy data of the different membranes
4
5 analyzed in this study. Average contact angles of the water, glycerol, and diiodomethane are
6
7 reported (degrees), along with the different components of the surface energy of the membrane
8
9 surface, expressed in mJ/m2
10
11
12
13
14
15
Membrane θwat θgly θdiod SAD LW ΔGMLM
16 γ γ+ γ- γAB γTOT -ΔGML
17 (%) (TOT)
18
19 Polyamide 105 76.5 27.2 23.0 37.7 0.06 0.03 0.09 37.8 57.9 -97.9
20
21
22 -N(CH3)3+ <10 17.6 18.3 19.3 41.0 1.10 38.3 13.0 54.0 133 +12.3
23
24
25 -NH3+/NH2 19.9 23.7 25.7 9.9 42.1 1.2 39.4 13.9 55.9 135 +12.7
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 29
59
60

Highly Hydrophilic Thin-Film Composite Forward Osmosis Membranes Functionalized With Surface-Tailored Nanoparticles

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Highly Hydrophilic Thin-Film Composite Forward Osmosis Membranes Functionalized With Surface-Tailored Nanoparticles

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Normalized DTG (% / min)

Normalized DTG (% / min)

Normalized DTG (% / min)

Zeta Potential (mV)

Specific Energy (mJ/m2)

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