Contents

Cover

Title page

Copyright page

Preface

Chapter 1: Processing and Characterizations: State-of-the-Art and New Challenges

1.1 Membrane: Technology and Chemistry
1.2 Characterization of Membranes
1.3 Ceramic and Inorganic Polymer Membranes: Preparation, Characterization and Applications
1.4 Supramolecular Membranes: Synthesis and Characterizations
1.5 Organic Membranes and Polymers to Remove Pollutants
1.6 Membranes for CO₂ Separation
1.7 Polymer Nanomembranes
1.8 Liquid Membranes
1.9 Recent Progress in Separation Technology Based on Ionic Liquid Membranes
1.10 Membrane Distillation
1.11 Alginate-based Films and Membranes: Preparation, Characterization and Applications
References

Chapter 2: Membrane Technology and Chemistry

2.1 Introduction
2.2 Membrane Technology: Fundamental Concepts
2.3 Separation Mechanisms
2.4 Chemical Nature of Membrane
2.5 Surface Treatment of Membranes
2.6 Conclusions
References

Chapter 3: Characterization of Membranes

3.1 Introduction
3.2 Physical Methods for Characterizing Pore Size of Membrane
3.3 Membrane Chemical Structure
3.4 Conclusions
References

Chapter 4: Ceramic and Inorganic Polymer Membranes: Preparation, Characterization and Applications

4.1 Introduction
4.2 Recent Developments in Filler-doped Polymer Electrolytes
4.3 Methodology
4.4 Results and Discussion
4.5 Conclusions
Acknowledgment
References

Chapter 5: Supramolecular Membranes: Synthesis and Characterizations

5.1 Overview
5.2 Supramolecular Materials
5.3 Supramolecular Membranes
5.4 Membrane Fabrication Using Supramolecular Chemistry
5.5 Conclusions
References

Chapter 6: Organic Membranes and Polymers for the Removal of Pollutants

6.1 Membranes: Fundamental Aspects
6.2 Liquid-phase Polymer-based Retention (LPR)
6.3 Applications for Removal of Specific Pollutants
6.4 Future Perspectives
6.5 Conclusions
Acknowledgments
References

Chapter 7: Membranes for CO₂ Separation

7.1 Introduction
7.2 Fundamentals of Membrane Gas Separation
7.3 Polymeric Membranes for CO₂ Separation
7.4 Mixed Matrix Membranes
7.5 Supported Ionic Liquid Membranes (SILMs) for CO₂ Separation
7.6 Conclusion
7.7 Overall Comparison and Future Outlook
Abbreviations
References

Chapter 8: Polymer Nanomembranes

8.1 Introduction
8.2 Materials
8.3 Nanomembrane Fabrication
8.4 Characterization
8.5 Applications
References

Chapter 9: Liquid Membranes

9.1 Introduction
9.2 Most Recent Developments
9.3 Liquid Membranes Based Separation Processes
9.4 Conclusion
References

Chapter 10: Recent Progress in Separation Technology Based on Ionic Liquid Membranes

10.1 Introduction
10.2 Ionic Liquid Properties
10.3 Bulk Ionic Liquid Membranes
10.4 Emulsified Ionic Liquid Membranes
10.5 Immobilized Ionic Liquid Membranes
10.6 Green Aspect of Ionic Liquids
10.7 Conclusions
Acknowledgments
References

Chapter 11: Membrane Distillation

11.1 Introduction
11.2 Applications of Membrane Distillation Technology
11.3 Different Kinds of Membrane Distillation Configurations
11.4 Distillation Membranes
11.5 Transport Phenomena in MD
11.6 Conclusion
References

Chapter 12: Alginate-based Films and Membranes: Preparation, Characterization and Applications

12.1 Introduction
12.2 Recent Development
12.3 Applications
12.4 Conclusion
References

Index

End User License Agreement

List of Tables

Chapter 1

Table 3.1 Normalized adhesion forces for a range of colloid probes at a PSU/SPEEK membrane. (Reprinted from [46] with permission from Elsevier)

Chapter 4

Table 4.1 Activation energy, Ea, and pre-exponential constant, A, of polymer electrolytes obtained from Arrhenius plots.
Table 4.2 Heat of fusion and relative crystallinity of polymer electrolytes obtained from melting endotherm.
Table 4.3 The specific capacitance, coulombic efficiency, energy density and power density of NCPE-based EDLCs.

Chapter 5

Table 5.1 Gas permeabilities of PDMS [130], silicon-based glassy polymers [131], and PTMGP [132].
Table 5.2 Comparison of gas permeability coefficients of indan-containing poly(diphenylacetylenes) with PTMSP. The gas permeability coefficients were measured at 25 °C and are in the units of Barrer 10^–1⁰ cm³ (STP)-cm/cm² sec cm Hg.
Table 5.3 Gas diffusivity (D), solubility (S) and permeability (P) coefficients of PIM-1 and PIM-7 at 30 °C. Diffusivity coefficients are measured in 10^–⁸ cm² s^–¹, solubility coefficients are measured in 10^–³ cm³ cm^–³ cmHg^–¹, and permeability coefficients are measured in 10–10 cm³ [STP] cm cm^–² s^–¹ cmHg^–¹.

Chapter 6

Table 6.1 Typical values of pore size and applied pressure for main pressure-driven membrane methods [1].
Table 6.2 Maximum retention capacity at pH 7 of Cu²⁺, Cd²⁺, and Co²⁺ of P(EI) 50% aqueous solution.

Chapter 7

Table 7.1 Values of the front factor k and the slope n of Robeson’s upper bound correlation [28].
Table 7.2 Chemical structure of some polymers used in CO₂ membrane separation [25, 31].
Table 7.3 CO₂ permeation properties for some polymers.
Table 7.4 Single gas CO₂ permeation properties of some polyimides.
Table 7.5 Mixed gas CO₂ permeation properties of some polyimides.
Table 7.6 Single gas CO₂ permeation properties of PSF-based membranes for CO₂/CH₄ and CO₂/N₂ separation.
Table 7.7 Single gas and mixed gas CO₂ permeation properties of PSF.
Table 7.8 CO₂ permeation properties of some polymer blend membranes in the literature. All measurements are for single gas except ‘b’ for mixed gas.
Table 7.9 Pure and mixed gas CO₂/CH₄ selectivity results for PSF incorporating 20% Matrimid [64].
Table 7.10 CO₂/N₂ and CO₂/CH₄ separation performance of mixed matrix membranes.
Table 7.11 Ideal (pure gas) CO₂/N₂ and CO₂/CH₄ selectivity values of commonly used ILs.
Table 7.12 List of the synthesized ionic liquids by Hojniak et al. [105].
Table 7.13 Mixed gas CO₂/N₂ and CO₂/CH₄ selectivity values of commonly used ILs.
Table 7.14 Ionic liquid losses as a function of pressure and pore size [116].

Chapter 9

Table 9.1 Application of emulsion liquid membranes.
Table 9.2 Emulsions used in LMs for heavy metals removal.
Table 9.3 Supported liquid membrane for VOCs separation.
Table 9.4 Molten salt membranes for gas separation.
Table 9.5 Glass transition temperature, T_g, of polymers [9].
Table 9.6 Materials, composition of hollow fiber liquid membranes.
Table 9.7 Supports for liquid membranes.
Table 9.8 Separation tasks, liquids and carriers of liquid membranes.

Chapter 10

Table 10.1 IL cations and anions most studied.
Table 10.2 Advantages and disadvantages of EIMs.

Chapter 11

Table 11.1 Comparison between MD and RO for desalination.
Table 11.2 Comparison between different MD configurations.
Table 11.3 Dominant mechanisms in mass transfer across the membrane in different MD configurations.
Table 11.4 Heat transfer in different regions of an MD configuration (if there is no resistance in cooling surface).

List of Illustrations

Chapter 2

Figure 2.1 Illustration of different membrane systems: (a) Supported liquid membrane, (b) hollow fiber membrane and (c) asymmetric membrane.
Figure 2.2 Illustration of a real membrane from SEM image (left) and Hagen-Poiseuille’s membrane (right); note that the shape of pores is not congruent with idealized cylindrical, perpendicular and parallel pores).
Figure 2.3 Membrane transport mechanism: size exclusion model (a) and solution-diffusion model (b).
Figure 2.4 Illustration of blocking pore models.
Figure 2.5 Solute concentration gradient and mass balance on the surface membrane according to film theory.
Figure 2.6 Scheme of concentration gradient according to the gel model.
Figure 2.7 Illustration of transport mechanisms in separation methods by liquid membranes.

Chapter 3

Figure 3.1 SEM image of a PES flat sheet membrane. (Copyright 2015, with permission from MEM-TEK Research Center)
Figure 3.2 Schematic of applied forces in a membrane pore. (Copyright 2015, with permission from MEM-TEK research center)
Figure 3.3 Wet and dry run measurement of a flat sheet membrane. (Copyright 2015, with permission from MEM-TEK research center)
Figure 3.4 Pore number distrubution of a flat sheet membrane. (Copyright 2015, with permission from MEM-TEK research center)
Figure 3.5 DSC thermograms for a narrow pore size distribution (A) and for a broad pore size distribution (B). (Reprinted from [14] with permission from Elsevier)
Figure 3.6 Steps in the desorption process: (i) liquid-filled pore, at saturation pressure, (ii) just before desorption starts, pore is still filled, (iii) just after evaporation is complete, t-layer remains, (iv) after complete desorption. (Reprinted from [17], with permission from Elsevier)
Figure 3.7 An example of ATR-FTIR spectrum. Ar-SO₂-Ar typical frequencies are v(S = O asym) = 1325 cm^–1, v(S = O symm) = 1140 cm^–1. (Reprinted from [20] with permission from Elsevier)
Figure 3.8 Diagram of ATR-FTIR. (Reprinted from [20] with permission from Elsevier)
Figure 3.9 Schematic of Raman spectroscopy. (Adapted from [27] with permission from Elsevier)
Figure 3.10 The cross-section SEM-EDS images of nanocomposite membranes. (a) SEM image of 0.09 AgNP/PS membrane; (b) SEM image of 0.09 AgNP/PES membrane; (c) SEM image of 0.09 AgNP/CA membrane; (d) EDS mapping of PS/AgNP membrane; (e) EDS mapping of 0.09 AgNP/PES membrane; (f) EDS mapping of 0.09 AgNP/CA membrane. (Reprinted from [30] with permission from Elsevier)
Figure 3.11 Fouled membrane surface (al) and EDS spectrum of this surface (a2). (Reprinted from [34] with permission from Elsevier)
Figure 3.12 Auger transition illustration (a) excitation; (b) electron. (Reprinted from [37] with permission from Elsevier)
Figure 3.13 Basic schematic presentation of an AFM setup. (Reprinted from [6] with permission from Elsevier)
Figure 3.14 SEM image of a CaCO₃ particle probe. (Reprinted from [44] with permission from Elsevier)
Figure 3.15 SIMS spectra of unmodified PVDF membrane and the modified PVDF membrane (ETNA01PP). (Reprinted from [50] with permission from Elsevier)
Figure 3.16 Diagram of the sessile drop method to measure contact. (Reprinted from [51] with permission from Elsevier)
Figure 3.17 Diagram showing the captive bubble method to measure the contact angle between a liquid (water) and a membrane. (Reprinted from [51] with permission from Elsevier)
Figure 3.18 Zeta potential curve. (Reprinted from [51] with permission from Elsevier)

Chapter 4

Figure 4.1 Free-standing polymer film with addition of (a) SiO₂, (b) TiO₂, (c) ZrO₂ and (d) Al₂O₃.
Figure 4.2 The logarithm of ionic conductivity of polymer electrolyte at different mass fraction of nanosized SiO₂.
Figure 4.3 The logarithm of ionic conductivity of polymer electrolyte at different mass fraction of nanosized ZrO₂.
Figure 4.4 The logarithm of ionic conductivity of polymer electrolyte at different mass fraction of nanosized TiO₂.
Figure 4.5 The logarithm of ionic conductivity of polymer electrolyte at different mass fraction of nanosized Al₂O₃.
Figure 4.6 Formation of three-dimensional network between polymer backbone and the surface of SiO₂ nanoparticles.
Figure 4.7 Model representation of an effective ionic conducting pathway through the space charge layer of the neighboring SiO₂ grains at the boundaries.
Figure 4.8 Arrhenius plot of filler-free polymer electrolyte and filler-doped NCPEs.
Figure 4.9 Glass transition temperature (T_g) of polymer electrolytes.
Figure 4.10 Crystalline melting temperature (T_m) of polymer electrolytes.
Figure 4.11 Crystallization temperature (T_c) of polymer electrolytes.
Figure 4.12 LSV response of filler-free system.
Figure 4.13 LSV response of Si system.
Figure 4.14 LSV response of Zr system.
Figure 4.15 LSV response of Ti system.
Figure 4.16 LSV response of Al system.
Figure 4.17 Cyclic voltammogram of EDCL containing filler-free system.
Figure 4.18 Cyclic voltammogram of EDCL containing Si system.
Figure 4.19 Cyclic voltammogram of EDCL containing Zr system.
Figure 4.20 Cyclic voltammogram of EDCL containing Ti system.
Figure 4.21 Cyclic voltammogram of EDCL containing Al system.
Figure 4.22 Schematic diagrams of the formation of electrical double layer at the electrode-electrolyte interface.
Figure 4.23 Galvanostatic charge-discharge performances of EDLC containing Si system over first 5 cycles.
Figure 4.24 Galvanostatic charge-discharge performances of EDLC containing Zr system over first 5 cycles.
Figure 4.25 Galvanostatic charge-discharge performances of EDLC containing Ti system over first 5 cycles.
Figure 4.26 Galvanostatic charge-discharge performances of EDLC containing Al system over first 5 cycles.

Chapter 5

Figure 5.1 Schematic representation of the general classification of porous solids (top, an example is given in each case: polymers for the porous organic solids; zeolites for porous inorganic solids; and MOFs for the porous organic-inorganic hybrid solids). (Reproduced from [55])
Figure 5.2 Construction of the MOF-5 framework. Top, the Zn₄(O)(O₁₂C₆) cluster. Left, as a ball stick model (Zn, blue; O, green; C, grey). Middle, the same with the Zn₄(O) tetrahedron indicated in green. Right, the same but now with the ZnO₄ tetrahedra indicated in blue. Bottom, one of the cavities in the Zn₄(O)(BDC)₃, MOF-5 framework. Eight clusters (only seven visible) constitute a unit cell and enclose a large cavity, indicated by a yellow sphere of diameter 18.5 Å in contact with 72 C atoms (grey). (Reproduced with permission from [63])
Figure 5.3 A supramolecular cube can be constructed from a linear ditopic and 90° tritopic building blocks using a edge-directed method (left) or from six tetratopic panels joined by twelve 90° ditopic building blocks using a face- or panel-based approach (right). (Reproduced with permission from reference [67])
Figure 5.4 Paddlewheel dimetallic building blocks can be used to make 3D MOFs (a), 2D MOFs (b), 1D wires (c). (Reproduced with permission from [67])
Figure 5.5 [Cu₃(TMA)₂(H₂O)₃]n viewed along the cell body diagonal [111], showing a hexagonal shaped 18 Å window. (Reproduced with permission from [68])
Figure 5.6 Overview of synthesis methods, possible reaction temperatures, and final reaction products in MOF synthesis. (Reproduced with permission from [71])
Figure 5.7 The self-assembly of a square may proceed through incorrectly oriented intermediate species. As these fragments associate and dissociate in solution, they will eventually funnel to the thermodynamically favored square, automatically healing any defects. (Reproduced with permission from [67])
Figure 5.8 The step-by-step approach for the growth of the SURMOFs on a SAM-functionalized substrate. The approach involves repeated cycles of immersion in solutions of the metal precursor and solutions of organic ligand. Between steps the material is rinsed with solvent. (Reproduced with permission from [83])
Figure 5.9 (a) Diffusion cell for ZIF-8 film preparation and (b) the schematic formation of ZIF-8 films on both sides of the nylon support via contra-diffusion of Zn²⁺ and Hmim through the pores of the nylon support [88].
Figure 5.10 The single crystal X-ray structures of ZIFs. (Left and Center) In each row, the net is shown as a stick diagram (left) and as a tiling (center). (Right) The largest cage in each ZIF is shown with ZnN4 tetrahedra in blue. (Reproduced with permission from [91])
Figure 5.11 Fabrication process: phenyltriethoxysilane (PhTES) solution is drop-cast onto a silicon wafer (a) and heated until set (b). ZIF-9 powder is spread across the PhTES surface (c), heated to adhere the crystals (d) then repeated to achieve a dense coverage. The surface is then exposed to lithographic X-ray beam (e) and rinsed with ethanol, etching unexposed areas to leave behind the patterned surface (f). (Reproduced with permission from [52])
Figure 5.12 Condensation reaction of 1,4-benzenediboronic acid to produce COF-1 [95].
Figure 5.13 Schematic representation of the dynamic reactions for the preparation of COFs [98].
Figure 5.14 Co-condensation of boronic acids building locks to give 2D COFs (COF-6, COF-8, COF-10). (Reproduced with permission from [100])
Figure 5.15 Solvothermal condensation of HHTP and PBBA in the presence of a substrate-supported SLG surface provides COF-5 as both a film on the graphene surface, as well as a powder precipitated in the bottom of the reaction vessel. (Reproduced with permission from [108])
Figure 5.16 Schemes to describe extrinsic (left) and intrinsic (right) porous cage materials. (Scheme is modified from original diagrams from [112])
Figure 5.17 A space-filled representation diagram of the cage structure produced by Doonan and coworkers. (Reproduced from [6])
Figure 5.18 Structures for cages synthesized by the [4 + 6] condensation of 1,3,5-triformylbenzene with three different vicinal diamines. Hydrogen atoms are omitted for clarity, carbon and nitrogen atoms are colored grey and blue, respectively. Methyl and cyclohexyl groups on the vertices are shown in green and red respectively. (Reproduced with permission from [110])
Figure 5.19 Structures of (a) diamond shape framework; (b) Structure model of P1; C structure model of P2; d0 structure model of P3. P refers to phenyl rings. (Diagram reproduced with permission from [116])
Figure 5.20 The blue polyhedron represents the tetrahedral bonded carbon atom and the yellow spheres denote the pore sizes in the 3D PAFs; (a) one phenyl linker; (b) two phenyl linkers; (c) three phenyl linkers and (d) four phenyl linkers. (Reproduced from [120])
Figure 5.21 Chemical structures of common poly(dialkylacetylenes).
Figure 5.22 Pure gas permeability of poly(1-trimethylgermyl-2-pentyne) (PTMSP) containing different cis/trans contents.
Figure 5.23 Chemical structures of (a) PIM-1 and (b) PIM-7, common PIMs. PIM-1s are usually synthesized at 65 °C in the presence of K2CO3 and DMF.
Figure 5.24 The gas permeability and selectivity of PIMs exceed most other polymers and lie above Robeson’s upper bound line. ■ represents PIM-1 while ▲ represents PIM-7 [146].
Figure 5.25 Graphical representation of the membrane structure in PTMSP and PMP nanocomposites [129, 147].
Figure 5.26 CO₂ permeability of PIM-1 is increased by 160% with the incorporation of Ti-exchanged UiO-66 MOFs.
Figure 5.27 Schematic diagram of MOF-polyimide interactions: (a) MIL-53(al)/ polyimide, (b) MOF-5/polyimide and (c) Cu3(BTC)2/polyimide [157].
Figure 5.28 (a) PAF-1 particles are synthesized via a Yamamoto coupling reaction. (b) Schematic of super-glassy polymer/PAF-1 intermixing. Typically PTMSP, PMP and PIM-1 densify to give a non-permeable conformation (top right), but with the addition of PAF-1, the original permeable structure is maintained (bottom right). (c) TEM micrograph of 50 nm PTMSP/PAF-1 film shows that PAF-1 particles are surrounded by Si, indicating the fine dispersion of PAF-1 within the PTMSP matrix. The noisy Si X-ray signal within the PAF-1 particle could be due to stray scattering of exciting Si fluorescence. (d) TEM and EDX analysis of PAF-1 particles immersed in PTMSP solution show that Si is well-intercalated within the PAF-1 particles. These particles were washed thoroughly with chloroform prior to imaging.
Figure 5.29 The (a) relative and (b) absolute gas permeabilities of (i) PTMSP-based, (ii) PMP-based, and (iii) PIM-1-based nanocomposites. The solid and empty symbols represent CO₂, and N₂ permeabilities of membranes, respectively. Squares, circles, and triangles represent pristine super-glassy polymers, super-glassy polymers with PAF-1, and super-glassy polymers with metal organic frameworks, respectively. Lines are drawn to guide the eye. The deviation of these permeability measurements is within ±10%. (c) The CO₂ permeability and CO₂/N₂ selectivity of PTMSP- (red), PMP- (green), and PIM-1-based (blue) nanocomposites are plotted on Robeson’s upper bound. The squares represent pure super-glassy polymer films, circles represent super-glassy polymer/PAF-1 films, and triangles represent super-glassy polymer/metal organic framework films. Our model accurately predicts the aging trends in different systems. Ultimately, PAF-1-based nanocomposites perform better over time without any CO₂ permeability loss. The arrows provide a visual guide to show the relationship between CO₂ permeability and selectivity over time (aging is tracked from the bottom of each arrow).
Figure 5.30 (a) Isopropanol permeance and (b) dye rejection rate of PTMSP and PTMSP/PAF-1 membranes before and after polymer aging.
Figure 5.31 (a) Chemical structure of the ABA triblock copolymer used by Quemener et al. [216]. (b) During solvent evaporation, high concentration of block copolymer will assemble into micelles to form dynamically responsive membranes. (c) An SEM image of the membrane film.
Figure 5.32 (a–d) SEM images of membrane during the self-healing process in the presence of pressure over extended periods of time; (e) and (f) are false-color reconstruction of the SEM images in (a–d).
Figure 5.33 (a) Schematic representation of self-assembled supramolecular nanofibers (orange fibers) within a nonwoven microfiber substrate (blue fibers) [217]. (b) Average filtration efficiencies of microfiber-nanofiber nanocomposites of Schmidt et al. The filtration efficiency was measured using a test aerosol containing 6000 particles cm^–3 of ISO fine dust over a testing period of 30 seconds.
Figure 5.34 (a) Schematic diagram for the switch effect of the membrane. (1) The as-obtained macroscopic membrane. (2) The randomly arranged NWs. (3) A higher magnification of (2), by which innumerous nanopores were formed. (4) Water films formed in the nanopores based on H-bond. (5) Hydration surface of the NWs based on H-bond. (6) Intrinsic structure of the MnO₂ NWs. (7–10) The mechanism of the recycle process of the membrane between hydration and alcoholization. (7) The crystal structure of the MnO₂ showing a (110) plane on which a lot of oxygen atoms are exposed to the surface to provide binding sites of H-bond. (8) A hydration surface. (9) An alcoholization surface. (10) Water could pass through the membrane smoothly while oil could not when the ‘switch’ was closed. (11) Oil could pass through the membrane smoothly when the ‘switch’ was open. (b) The IR spectrum of the membrane. (c–d) The crystal structure of the V₂O₅ from different views. (Adapted from Wang et al. [219]).
Figure 5.35 A scheme showing the fabrication, use, and recycling of supramolecular membrane of Rybtchinski et al. [220].

Chapter 6

Figure 6.1 Membrane transport mechanism: (a) size exclusion model and (b) solution-diffusion model.
Figure 6.2 (a) Steps for the separation mechanism by LPR, (b) scheme of the principle of LPR technique and (c) stages of LPR visualized as separation process.
Figure 6.3 (a) Illustration of washing method and (b) typical experimental results (retention profile); (c) Illustration of enrichment method and (d) typical experimental results (enrichment curve).
Figure 6.4 Illustration of Manning’s zone distribution model.
Figure 6.5 Structures of the water-soluble polymers: (a) P(EI) and (b) P(EIE).
Figure 6.6 Retention profiles of metal ions as a function of Z using P(EI) 50% aqueous solution at (a) pH 3, (b) pH 5 and (c) pH 7 and using P(EIE) 17% aqueous solution at (d) pH 3, (e) pH 5 and (f) pH 7.
Figure 6.7 The sorption-desorption process of Cu²⁺ in P(EI) 50% aqueous solution using basic-acidic pH solutions from the reservoir. (C) denotes charge or sorption, and (D) denotes discharge or desorption. R(%) denotes the retention capacity and E(%) denotes de elution capacity.
Figure 6.8 Structure of cationic water-soluble polymer P(BrVMP).
Figure 6.9 Retention profiles of As(V) using P(BrVMP) as a polymer and regenerated cellulose membrane at different pH; with 20:1 molar ratio and 1 bar pressure.
Figure 6.10 Retention profiles of As(V) using different polymers and regenerated cellulose membrane at pH 9, with 20:1 molar ratio and 1 bar pressure.
Figure 6.11 The sorption-desorption processes. (a) first sorption process of P(BrVMP) through enrichment method at pH 9; (b) first desorption process of P(BrVMP) using washing method at pH 3; (c) second sorption of P(BrVMP) through enrichment method at pH 9; (d) second desorption process of polymers using washing method at pH 3; (e) third sorption of P(BrVMP) through enrichment method at pH 9.

Chapter 7

Figure 7.1 Gas separation through pure polymeric and functionalized membranes.
Figure 7.2 Membrane gas permeation mechanisms through porous and nonporous membranes.
Figure 7.3 Robeson’s upper bound correlation for CO₂/N₂ separation [28].
Figure 7.4 Robeson’s upper bound correlation for CO₂/CH₄ separation [28].
Figure 7.5 Robeson’s upper bound correlation for H₂/CO₂ separation [28].
Figure 7.6 Robeson’s upper bound correlation for H_e/CO₂ separation [28].
Figure 7.7 Synthesis process of dense polymeric membranes.
Figure 7.8 Commonly used dianhydrides in polyimide synthesis [25, 36].
Figure 7.9 Chemical structure of Matrimid^® 5218 [44].
Figure 7.10 Comparison of permeation properties of Matrimid^® 5218 at single gas and mixed gas conditions [37].
Figure 7.11 Comparison of permeation properties of Matrimid^® 5218 at single gas and mixed gas conditions [38].
Figure 7.12 PSF and some PSF-based polymer structures [25].
Figure 7.13 Effect of PTMEG incorporation on CO₂ permeation properties of Pebax 1657 (4 bars and 25 °C) [67].
Figure 7.14 CO₂/CH₄ and CO₂/N₂ selectivities of PIM-1/Matrimid dense films (35 °C and 3.5 atm) [63].
Figure 7.15 CO₂ permeability as a function of PIM-1 composition in Matrimid (35 °C and 3.5 atm) [63].
Figure 7.16 Comparison between the permeation properties of pure PU and PU/PVAc (80/20) blend membrane (10 bars) [34].
Figure 7.17 CO₂ permeability as a function of PANI composition in PBI (30 °C and 1.5 bar).
Figure 7.18 CO₂ permeation properties of PANI/PBI blend membrane (30 °C and 1.5 bar) [60].
Figure 7.19 Schematic illustration of MMM incorporating different components of the inorganic filler [68].
Figure 7.20 Effect of ZIF-7 loading on CO₂ permeability and CO₂/CH₄ and CO₂/N₂ selectvities of Pebax^® 1657 [73].
Figure 7.21 Effect of CANs content on gas separation performance of pristine Pebax and Pebax-CANs MMMs for: (a) CO₂/CH₄ separation and (b) CO₂/N₂ separation (2 bars and 25 °C) [74].
Figure 7.22 Effect of Co(II)–NaY particle loadings on (a) CO₂ permeability, and (b) CO₂/N₂ selectivity of CA membranes (25 °C) [75].
Figure 7.23 Single gas versus mixed gas CO₂ permeability obtained with MMMs by Jomekian et al. [76].
Figure 7.24 Single gas versus mixed gas CO₂/CH₄ selectivity results obtained with MMMs by Jomekian et al. [76].
Figure 7.25 Pure and mixed gas CO₂/CH₄ selectivity results for PSF/PI blend incorporating 15.2 wt% silica nanoparticles (10 bars and 25 °C) [64].
Figure 7.26 Single gas versus mixed gas CO₂/N₂ selectivities for different SILMs reported by Neves et al. [103].
Figure 7.27 Single gas versus mixed gas CO₂/CH₄ selectivities for different SILMs reported by Neves et al. [103].
Figure 7.28 Single gas versus mixed gas CO₂/N₂ selectivities for different SILMs reported by Scovazzo et al. [104].
Figure 7.29 Single gas versus mixed gas CO₂/CH₄ selectivities for different SILMs reported by Scovazzo et al. [104].
Figure 7.30 Ionic liquid loss of SILMs prepared with pressure and vacuum immobilization reported by Hernández-Fernándeza et al. [115].
Figure 7.31 Weight of SILMs based on (a) hydrophilic, and (b) hydrophobic membranes immobilized with different ILs as a function of time (pressure difference: 1 bar) [103].
Figure 7.32 Comparison of CO₂/N₂ separation properties of membranes in the literature.
Figure 7.33 Comparison of CO₂/CH₄ separation properties of membranes in the literature.

Chapter 8

Figure 8.1 Spin coating machine. The substrate of the polymeric membrane is placed on the rotating disc and kept in contact with the holder at high rotational speed by creating vacuum at the bottom of the substrate. The solution with the polymer is dispensed on the substrate by pipette in static or dynamic condition of the substrate, depending on the application. The parameters of the process, rotational speed, acceleration, and duration time are programmable by the keyboard.
Figure 8.2 Illustration of the layer-by-layer nanomembrane assembly technique. Left: assembly of the first layer; middle: assembly of the second layer; right: final structure. (© 2009; Reprinted with permission from J. Matovic and Z. Jakšić)
Figure 8.3 oCVD and iCVD processes. (a) Reactor configuration for oxidative chemical vapor deposition (oCVD). Evaporated oxidant and vapor-phase monomer(s) adsorb onto a cooled substrate and step-growth polymerization occurs. (b) Initiated chemical vapor deposition (iCVD) process. Vapor-phase vinyl monomer(s) and thermally labile initiator flow through an array of heated filaments. The initiator is decomposed into radicals; these radicals and the monomer(s) adsorb on a cooled substrate and film growth occurs via free radical polymerization. (Reprinted with permission from John Wiley and Sons)
Figure 8.4 Permeance vs thickness. The blue line represents the dependence of the permeance P on thickness membrane L considering equilibrium at the surfaces. The red line represents the same dependence but abandoning the hypothesis of equilibrium at the surfaces.
Figure 8.5 Bulging experiment. (a) Experimental setup, (b–d) lateral views of various deflected nanomembranes under overpressure. (Reprinted with permission from The Chemical Society of Japan)
Figure 8.6 Surface modification of PDMS with PEG-DOPA-K. Wettability and gross morphology of (a, c, e) bare and (b, d, f) PEG-DOPA-K modified PDMS surfaces by (a, b) contact angle, (c, d) optical microscopy, and (e, f) atomic force microscopy (AFM). (Reprinted with permission from John Wiley and Sons)

Chapter 9

Figure 9.1 Flow diagram of batch mixer-settler process of ELM.
Figure 9.2 Liquid membrane configurations.
Figure 9.3 ILM for liquid phase separations.
Figure 9.4 Mechanism for the facilitated transport of oxygen through an immobilized alkali metal nitrate/nitrite molten.
Figure 9.5 Schematic transport models of a bulk organic hybrid liquid membrane (BOHLM) system with (a, c) hydrophobic membranes and (b, d) hydrophilic or ion exchange membranes.
Figure 9.6 Schematic concentration profile of each Ti(IV) chemical species, transported through the BOHLM system with hydrophobic membranes.
Figure 9.7 Schematic concentration profile of each Ti(IV) chemical species, transported through the BHLM with hydrophilic or ion-exchange membranes.
Figure 9.8 Scheme of conventional agitated bulk liquid membrane (a), multi-membrane hybrid system, and respective concentration profiles (b).
Figure 9.9 Electrodialysis cell with liquid membrane (1 – platinum electrodes; 2 – sulphuric acid solutions; 3 – solid anion-exchange membranes; 4 – feed solution; 5 – cellophane films; 6 – liquid membrane; 7 – strip solution).
Figure 9.10 Schematic diagram of the three-aqueous phase (BAHLM) module: F, E, and R are the compartments of the feed, LM, and receiving (strip) solutions, respectively; M1 and M2 are the ion-exchange membranes; 1 and 2 are the inlet and outlet of the feed, LM, and strip solutions, respectively.
Figure 9.11 Simulation of the BAHLM transport: (a) concentration profiles in a regular scheme and (b) concentration profiles in a simplified scheme.
Figure 9.12 Facilitated transport ILM.
Figure 9.13 ILM with simultaneous gas or vapor separation and catalytic reaction.

Chapter 10

Figure 10.1 Main classification of ionic liquid cations.
Figure 10.2 U-shape liquid membrane configuration.
Figure 10.3 Scheme of emulsion liquid membranes.
Figure 10.4 Transport of organic compounds through SILMs (C: concentration of species).
Figure 10.5 Scheme of a non-dispersive solvent extraction ionic liquid membrane process using two hollow fiber contactors.

Chapter 11

Figure 11.1 Direct contact membrane distillation (DCMD) [4].
Figure 11.2 Air gap membrane distillation (AGMD) [4].
Figure 11.3 Memstill configuration [4, 24].
Figure 11.4 Permeate gap membrane distillation (PGMD).
Figure 11.5 Sweep gap membrane distillation (SGMD) [4].
Figure 11.6 Vacuum membrane distillation (VMD) [4].
Figure 11.7 Vacuum gap membrane distillation (VGMD).
Figure 11.8 Memsys configuration [4, 33].
Figure 11.9 (a) Pervaporation (PV), (b) Vacuum Membrane Distillation (VMD), modified according to Khayet and Matsuura [34].
Figure 11.10 (a) Plate and frame module; (b) Supported flat sheet membrane [4].
Figure 11.11 (a) Hollow fiber module; (b) Hollow fiber membrane [4].

Chapter 12

Figure 12.1 Chemical structures of G-block, M-block, and alternating block in alginate [1].
Figure 12.2 Formation of an alginate gel by calcium cations, resulting in “egg-box” calcium linked junctions [10].
Figure 12.3 Schematic of preparation for calcium alginate films and a schematic illustration for the swelling state of the films cross-linked in different systems [11].
Figure 12.4 Design of the Alg/Chs bi-layer composite membrane [152].

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ISBN 978-1-118-83173-1

Preface

Many recent research accomplishments in the area of polymer nanocomposite membrane materials are summarized in this book, Nanostructured Polymer Membranes: Processing and Characterizations. State-of-the-art on membrane technology and chemistry and new challenges being faced in the field are discussed. Among the topics reviewed are characterization of membranes; current techniques for the processing and characterization of ceramic and inorganic polymer membranes; supramolecular membranes; organic membranes and polymers for removal of pollutants; membranes for CO₂ separation; polymer nanomembranes; liquid membranes; separation technology based on ionic liquid membranes; membrane distillation; and alginate-based membranes and films.

This book is intended to serve as a “one-stop” reference resource for important research accomplishments in the area of nanostructured polymer membranes and their processing and characterizations. It will be a very valuable reference source for university and college faculties, professionals, post-doctoral research fellows, senior graduate students, and researchers from R&D laboratories working in the area of polymer nanobased membranes. The various chapters are contributed by prominent researchers from industry, academia and government/private research laboratories across the globe and comprise an up-to-date record on the major findings and observations in the field.

Chapter 1 provides an overview of the techniques and processes detailed in later chapters, along with the state of art, new challenges and opportunities in the field. In chapter 2, principles and fundamentals of membrane separation are presented in addition to a description of different types of membrane processes (pressure-driven membrane methods and liquid membranes) and the chemical and physical methods for membrane modification. Chapter 3 provides fundamental ideas about all types of characterization techniques for polymer-based nanomembranes such as FTIR, Raman spectroscopy, X-ray spectroscopy, electron spectroscopy, atomic force microscopy mass spectrometry and surface hydrophilicity. The next chapter mainly concentrates on the preparation, characterization and applications of ceramic and inorganic polymer membranes. Chapter 5 gives an overview of supramolecular membranes, primarily focusing on polymeric membranes and mixed matrix membranes for gas separation applications. Other topics discussed in this chapter are membranes synthesized from self-assembly, hydrogen bonding, π-π stacking of block copolymer systems, small molecules, and nanoparticles; and a summary of recent research into gas membrane separations.

Chapter 6 explains organic membranes and polymers to remove pollutants. It provides fundamental aspects of membranes as well as processes, including membranes as electro-ultrafiltration, ultrafiltration coupled to ultrasound, flotation coupled to microfiltration, liquid-phase polymer-based retention and liquid surfactant membrane. The next chapter is essential for tracking the progress in membrane development. It is a comprehensive review of recent studies in CO₂ separation using different technologies, CO₂ permeation properties, and breakthroughs and challenges in developing efficient CO₂ separation membranes. Chapter 8 reports the state-of-the-art on fabrication methods of polymeric nanomembranes according to their specific needs and illustrates the most useful materials, employing mostly glassy and rubbery polymers. Often, to enhance membrane properties or to prevent undesired behavior, the fabrication is followed by different kinds of surface treatments. The authors discuss recent investigations on mechanical, thermal and gas transport properties of nanomembranes that frequently reveal a different behavior with respect to the polymeric membranes of greater thickness. The next chapter presents an introduction to liquid membrane separation techniques such as emulsion liquid membranes, immobilized liquid membranes, salts liquid membranes, hollow fiber contained liquid membranes, bulk hybrid liquid membranes and bulk aqueous hybrid liquid membranes. The author of this chapter also discusses the theory behind liquid membranes, along with their material design, preparation, performance and stability, and their applications in the separation and removal of metal cations from a range of diverse matrices, gas separation, etc.

Chapter 10 provides an overview of the recent progress in separation technology based on ionic liquid membranes; moreover, it covers issues relevant to this technology such as methods of preparation, mechanisms of transport, stability and fields of application. Chapter 11 on membrane distillation provides comprehensive coverage of both the fundamentals and recent developments associated with the application, process design, and membrane fabrication in this field. The final chapter provides a comprehensive overview of general properties, recent developments, and applications of alginate-based films and membranes. Sodium alginate is water-soluble, nontoxic, biocompatible, biodegradable, reproducible, and can yield coherent films or membranes upon casting or solvent evaporation.

In conclusion, the editors would like to express their sincere gratitude to all the contributors of this book, whose excellent support made the successful completion of this venture possible. We are grateful to them for the commitment and sincerity they showed towards their contributions. Without their enthusiasm and support, the compilation of a book would not have been possible. We would like to thank all the reviewers who have taken their valuable time to make critical comments on each chapter. We also thank the publisher, John Wiley and Sons Ltd. and Scrivener Publishing, for recognizing the demand for a book on the increasingly important area of Nanostructured Polymer Membranes Processing and Characterization and handling such a new project, which many other publishers have yet to address.

Visakh. P. M.
Olga Nazarenko
September 2016