Springer Transactions in Civil

and Environmental Engineering

Bradley Ladewig
Muayad Nadhim Zemam Al-Shaeli

Fundamentals
of Membrane
Bioreactors
Materials, Systems and Membrane
Fouling
Springer Transactions in Civil
and Environmental Engineering
Springer Transactions in Civil and Environmental Engineering (STICEE) publishes
the latest developments in Civil and Environmental Engineering. The intent is to
cover all the main branches of Civil and Environmental Engineering, both
theoretical and applied, including, but not limited to: Structural Mechanics Steel
Structures Concrete Structures Reinforced Cement Concrete Civil Engineering
Materials Soil Mechanics Ground Improvement Geotechnical Engineering
Foundation Engineering Earthquake Engineering Structural Health and
Monitoring Water Resources Engineering Hydrology Solid Waste Engineering
Environmental Engineering Wastewater Management Transportation Engineering
Sustainable Civil Infrastructure Fluid mechanics Pavement engineering Soil
dynamics Rock mechanics Timber engineering Hazardous waste disposal
Instrumentation and monitoring Construction management Civil engineering
construction Surveying and GIS Strength of Materials (Mechanics of Materials)
Environmental geotechnics Concrete engineering timber structures Within the
scopes of the series are monographs, professional books or graduate textbooks,
edited volumes as well as outstanding PhD theses and books purposely devoted to
support education in mechanical engineering at undergraduate and graduate levels.

More information about this series at [Link]

Bradley Ladewig
•

Muayad Nadhim Zemam Al-Shaeli

Fundamentals of Membrane
Bioreactors
Materials, Systems and Membrane Fouling

123
Bradley Ladewig Muayad Nadhim Zemam Al-Shaeli
Department of Chemical Engineering Department of Chemical Engineering
Imperial College London Monash University
London Melbourne, VIC
UK Australia

ISSN 2363-7633 ISSN 2363-7641 (electronic)

Springer Transactions in Civil and Environmental Engineering
ISBN 978-981-10-2013-1 ISBN 978-981-10-2014-8 (eBook)
DOI 10.1007/978-981-10-2014-8
Library of Congress Control Number: 2016949616

© Springer Nature Singapore Pte Ltd. 2017

By mistake this work was announced with the copyright holder being the authors. The correct copyright
holder is Springer SBM Singapore Private Ltd., SG
This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt from
the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authors or the editors give a warranty, express or implied, with respect to the material contained herein or
for any errors or omissions that may have been made.

Printed on acid-free paper

This Springer imprint is published by Springer Nature

The registered company is Springer Nature Singapore Pte Ltd.
The registered company address is: 152 Beach Road, #22-06/08 Gateway East, Singapore 189721, Singapore
Acknowledgements

First, I would like to thank God for blessing me with faith, strength and helping me
understand myself by looking at his manifestations.
Second, it is my genuine pleasure to express my deep sense of thanks to my
main supervisor Prof. Bradley Ladewig for guiding me through my writing this
book. This book would never have been completed without his virtuous guidance.
His timely recommendation, meticulous scrutiny, scholarly advice and scientific
approach have helped me significantly to accomplish this book. I really appreciate
his support, recommendation and encouragement.
I would like to acknowledge the financial support from Iraqi Government/
Ministry of Higher Education and Scientific Research in Iraq for their support by
granting me a Ph.D. scholarship.
I would like to extend my sincerest thanks and appreciation to my parents, my
brothers and my sisters for giving me encouragement and support.
Lastly and most importantly, my deepest appreciation to my wife (Soorah) for
her endless love without expecting any gifts and providing me with her constant
support and recommendation by standing shoulder to shoulder with me to get
though all the difficulties I faced as an international student. This work is dedicated
to her and our lovely daughter (Mariam).

v
Contents

1 Introduction to Membrane Bioreactors . . . . . . . . . . . . . . . . . . . . . . . . 1

1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 History of Membrane Bioreactors . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Membrane Bioreactor Configurations . . . . . . . . . . . . . . . . . . . . . . 5
1.4 Advantages and Limitations of Membrane Bioreactors . . . . . . . . . 7
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2 Fundamentals of Membrane Processes . . . . . . . . . . . . . . . . . . . . . . . . 13
2.1 Membrane Classification by Membrane Structure . . . . . . . . . . . . . 13
2.2 Membrane Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.1 Inorganic Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.2 Polymeric Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.3 Composite Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.4 Formation of Membranes by Phase Inversion
Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.3 Membrane Fabrication Techniques . . . . . . . . . . . . . . . . . . . . . . . . 27
2.3.1 Flat Sheet Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.3.2 Hollow Fibre Membranes . . . . . . . . . . . . . . . . . . . . . . . . . 29
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3 Fouling in Membrane Bioreactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.1 Membrane Fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.1.1 Causes of Fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.1.2 Effects of Fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.1.3 Techniques for the Control of Membrane Fouling
in Membrane Bioreactors . . . . . . . . . . . . . . . . . . . . . .... 59
3.2 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 71
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 72

vii
viii Contents

4 Surface Modification of Polyethersulfone Membranes . . . . . . . . . . . . 87

4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.2 Surface Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.3 Bulk Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
4.4 Physical Modification of PES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.4.1 Blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.4.2 Plasma Treatment and Plasma-Induced Grafting
Polymerisation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 107
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 115
5 Membrane Characterization Techniques . . . . . . . . . . . . . . . . . . . . . . . 131
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
5.2 Composition Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
5.3 Fourier Transform Infrared Spectroscopy (FTIR) . . . . . . . . . . . . . 132
5.4 Nuclear Magnetic Resonance (NMR) . . . . . . . . . . . . . . . . . . . . . . 134
5.5 X-ray Photoelectron Spectroscopy (XPS) . . . . . . . . . . . . . . . . . . . 134
5.6 Thermal Gravitational Analysis (TGA) . . . . . . . . . . . . . . . . . . . . . 135
5.7 Differential Scanning Calorimetry (DSC) . . . . . . . . . . . . . . . . . . . 135
5.8 Energy-Dispersive X-ray Spectroscopy (EDS) . . . . . . . . . . . . . . . 136
5.9 Scanning Electron Microscopy (SEM) . . . . . . . . . . . . . . . . . . . . . 136
5.10 Atomic Force Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
5.11 Characterization of Membrane Performance . . . . . . . . . . . . . . . . . 140
5.12 Hydrophilicity/Hydrophobicity of Membranes . . . . . . . . . . . . . . . 140
5.13 Permeability and Selectivity of Membranes . . . . . . . . . . . . . . . . . 141
5.14 Antifouling Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.15 Anticoagulation Properties of Membranes . . . . . . . . . . . . . . . . . . 142
5.16 Membrane Stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5.17 Stability After Physical Modification of PES Membrane . . . . . . . 143
5.18 Stability After Chemical Modification of PES Membrane. . . . . . . 146
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
Chapter 1
Introduction to Membrane Bioreactors

This chapter gives a general introduction to membrane science and technology, and
begins with the definition of terms and provides a description of membrane pro-
cesses currently implemented in different fields. Specifically, the Membrane
Bioreactor (MBR) technology is introduced and followed by a short overview of
the historical development and different configuration of MBRs. Finally, the
advantages and disadvantages of membrane bioreactors are discussed. To sum up,
MBR acts an efficient, reliable and cost-effective technology that deals excellently
with the growing demands for treating wastewater, which can then be returned to
the hydrological cycle without any adverse effects.

1.1 Introduction

A membrane is defined as a thin selective barrier between two phases (gas or

liquid), which is impermeable to the transfer of specific particles, molecules or
substances, colloidal, and dissolved chemical species other than water or solvent
(Mulder 1997). A material of reasonable mechanical strength that maintains a high
throughput of a desired permeates with a high degree of selectivity is ideal for the
production of membranes. Usually, a thin layer of material with a narrow range or
domain of pore size and a high surface porosity affect the physical structure of the
membrane. The physical structure of a thin layer membrane leads to the separation
of dissolved solutes in liquid streams and the separation of gas mixtures for
membrane filtration (Visvanathan et al. 2000).
Membrane processes or productions are categorised based on (1) the driving
force which is used for separation of impurities such as pressure (DP) temperature
(DP), concentration gradient (DC), partial pressure (Dp), or electrical potential
(DE), (2) the mechanism of separation, (3) the particular application of membrane,
(4) the size of the retained material, and (5) the type of membrane (Baker 2004).

© Springer Nature Singapore Pte Ltd. 2017 1

B. Ladewig and M.N.Z. Al-Shaeli, Fundamentals of Membrane Bioreactors,
Springer Transactions in Civil and Environmental Engineering,
DOI 10.1007/978-981-10-2014-8_1
2 1 Introduction to Membrane Bioreactors

Considering the categorization based on the pore size or size of retained mate-
rial, membranes can be classified as ultrafiltration (UF), microfiltration (MF),
nanofiltration (NF) and reverse osmosis (RO) membranes, dialysis, electrodialysis
(ED), where the first four processes produce permeate and concentrate (Radjenović
et al. 2008). As illustrated in Table 1.1, UF and MF are low pressure-driven pro-
cesses in which feed water is driven through a synthetic micro-porous membrane
and then divided into permeate (which passes through the membranes) and retentate
(which includes nonpermeating species). These membrane processes are known to
be more efficient in removing microorganisms and particles from wastewater. In
comparison to UF and MF, RO is a high pressure-driven process used to remove
dissolved constituents such as salts, low molecular organic and inorganic pollutants
from waste water remaining after advanced treatment with MF. NF operates at a
pressure range between RO and UF, targeting removal of divalent ion impurities
(Visvanathan et al. 2000).

Table 1.1 Characteristics of membrane processes (Nath 2008; Perry and Green 1997; Koros et al.
1996)
Type of Size of Driving Type of Application
process materials force membrane
retained
Ultrafiltration 1–100 nm (ΔP) Micro-porous – Separation of proteins
macromolecules (1–10 bar) and virus
– Concentration of oil in
water emulsions
Microfiltration 0.1–10 µm (ΔP) Porous Separation of bacteria
microparticles (0.5–2 bar) and cells from solutions
Nanofiltration 0.5–5 nm (ΔP) Micro-porous – Separation of dye
molecules (10–70 bar) and sugar
– Water softening
Reverse <1 nm (ΔP) Nanoporous – Desalination of sea
osmosis molecules (10–100 bar) and brackish water
– Process of water
purification
Dialysis <1 nm (ΔC) Micro-porous – Purification of blood
molecules or nanoporous
Electrodialysis <1 nm (ΔE) Micro-porous Separation of electrolytes
molecules or nanoporous from nonelectrolyates
Pervaporation – (ΔC) Nanoporous Dehydration of ethanol
and organic solvents
Gas separation – Partial Nanoporous Hydrogen recovery from
pressure process gas streams,
difference dehydration and
(1–100 bar) separation of air
Membrane – (ΔT) Micro-porous Water purification
distillation and desalination
1.1 Introduction 3

A more recently developed membrane process is MBR, which combines MF or

UF, and a bioreactor for biological treatment. This process is an emerging tech-
nology increasingly used for both municipal and industrial waste water treatment
and has led to significant advances in knowledge and experience related to their
design and operation (Crawford et al. 2000; Drews 2010; Hong et al. 2002; Hwang
et al. 2010; Judd 2006; Judd and Judd 2010; Meng et al. 2009; Stephenson et al.
2000; Thomas et al. 2000; Visvanathan et al. 2000). It represents a good innovative
process in which gravity settling or clarifiers of the conventional activated sludge
system (CAS) is replaced by membrane separation module (Bella et al. 2007; Hong
et al. 2002; Le-Clech et al. 2006). Such a module reproduces MF or UF processes
with pore sizes ranging from 0.05 to 0.4 µm (Bouhabila et al. 2001). This enables
the separation of solid–liquid and act as an advanced treatment unit for specific
pollution agents (e.g. coliform bacteria or suspended solids). It must be kept in
mind that these agents cannot be completely eliminated by conventional waste
water treatment processes (Bella et al. 2007; Le-Clech et al. 2006)
As seen schematically in Fig. 1.1, in a conventional activated sludge (CAS)
process, the microorganisms accumulate into flocs and these flocs are suspended in
wastewater to facilitate treatment. Once the waste water is treated, the flocculated
microorganisms must be eliminated from clean water (Hussain et al. 2010).
Conventionally, a clarifier is used for liquid–solid separation; therefore, a successful
treatment in CAS process relies on the development of flocs that settle well.
Furthermore, conventional activated sludge process (CASP) does not cope well
with fluctuations of wastewater flow rate or composition.
Conversely, in MBR, the membrane component eliminates the need for a clar-
ifier and is performed using low-pressure MF, UF or NF membranes. Additionally,
MBR systems allow the complete physical retention of bacterial flocs and almost all
suspended solids (individual microorganisms, large biological flocs and inert par-
ticles) within the bioreactor and therefore can offer excellent disinfection capacity

Fig. 1.1 a Typical process schematic for conventional activated sludge processes (CAS) and
b membrane bioreactor processes in wastewater treatment. Adapted from Leiknes (2010)
4 1 Introduction to Membrane Bioreactors

(Le-Clech et al. 2006; Li and Chu 2003). As a result, the total coliform bacteria
reduction can reach an average of log 7 (Hirani et al. 2010). Due to its advantages,
MBR has been demonstrated to be highly effective for the treatment of polluted
surface water supplies to produce potable water (Smith et al. 1969). Thus, in
comparison to other membrane processes, MBR has the potential for the treatment
of many types of wastewater; this does not solely lie in its application to biological
degradation and nitrification, but also because it could replace other conventional
treatment units such as flocculation, sedimentation, filtration and disinfection. In
industry, MBR is used as secondary treatment in order to reduce biodegradable and
non-biodegradable matter in the end product (because the presence of oxygen) or as
MBR can be used as an advanced treatment to remove residual nutrients which are
not fully removed during secondary treatment (Tchobanoglous et al. 2004).

1.2 History of Membrane Bioreactors

Membrane bioreactors were initially developed in the 1960s when commercial scale
UF and MF membranes became available. The original process was introduced by
Dorr-Olivier Inc. (Milford, Connecticut) and combined a crossflow membrane fil-
tration loop with an activated sludge bioreactor (Enegess et al. 2003). Polymeric flat
sheet (FS) membranes with pore sizes ranging from 0.003 to 0.01 µm were used in
this process (Yamamoto et al. 1989). Replacing the settling tank of the conventional
activated sludge process seemed to be appealing. However it was difficult to val-
idate the use of such process due to the associated high costs of the membranes. The
low economic value of the product (tertiary effluent) and potential rapid loss of
performance due to fouling also impaired the process of membrane bioreactors.
And as such the focus was on attaining high fluxes. Nevertheless it was important to
deliver the mixed liquor suspended solids (MLSS) at a high cross flow velocity,
incurring a significant energy consumption (of the order 10 kWh/m3 product) to
reduce membrane fouling.
This first generation of MBRs suffered from a substandard economic perfor-
mance and as such their suitability was limited to a narrow range of applications
such as ski resorts, hotels or isolated trailers parks. The major breakthrough for
MBRs came in 1989 with the research conducted by Yamamoto et al. They
demonstrated for the first time the use of submerged membranes in bioreactor,
which was a major innovation, compared to the prior approach with the separation
device located externally to the reactor. Yamamoto et al. (1989) investigated the
feasibility of direct membrane separation using hollow fibre in an activated sludge
aeration tank, and identified the key parameters, which give a stable operation and
effective organic stabilisation and nitrogen removal. As a result, the number of
membrane bioreactors used to treat municipal wastewater increased significantly. In
2005, the market value of MBRs reached $217 million and continued to increase
reaching $360 million in the year 2010 (Judd 2006).
1.2 History of Membrane Bioreactors 5

The acceptance of modest fluxes (25 % or less of those in the first generation)
and the idea to use two-phase bubbly follow to limit membrane fouling has been
another aspect of recent development of MBR systems. Bubbling or air scouring is
used to deter clogging of the membrane modules from solid concentrations and as a
technique to control membrane fouling. According to Zhang et al. (2011b), two
types of bubbling can be used to control membrane fouling. The first one is a slug
bubble and the second one is a free bubble. They concluded that using slug bubbles
showed better antifouling performance than free bubbles in FS MBR under both
short-term and long-term operation. In short-term operation, a high flux operation
was achieved at 36 h with 40 L m−2 h−1. In contrast, moderate flux operation of
14 days was possible a flux of 24 L m−2 h−1.
From the mid-1990s there was an exponential increase in MBR plant installa-
tions as a result of lower operating cost with the submerged configuration and a
continual decrease in membrane cost. Further enhancement in the designs and
operation of MBRs has been achieved and these have been assimilated into larger
plants. Early MBRs operated at solid retention times (SRT) as high as 100 days
with MLSS up to 30 g L−1. Recently, the trend is to apply a lower SRT (around
10–20 days). This leads to more manageable MLSS levels (10–15 g L−1). Due to
these new operating conditions, the membrane-fouling tendency in MBR has begun
to decrease and overall maintenance has been simplified, as less frequent membrane
cleaning is necessary (Le-Clech et al. 2006). Currently a variety of MBR systems
are commercially available, mostly using submerged membranes. Although some
external modules are available, these external systems also use two-bubbly phase
flow for fouling mitigation.
Generally, for membrane configuration, hollow fibre and FS membrane sheets
are used in the applications of MBRs (Stephenson et al. 2000). The economic
feasibility of current generation MBRs depends on an attainable permeate flux,
predominantly controlled by appropriate fouling control strategy with a modest
energy input (usually 1 kWh/m3 product).
Effective fouling alleviation methods can be executed only when the phenomena
appearing at the membrane surface are fully understood. The plethora of publica-
tions dealing with membrane fouling and published within the last 5 years is
overwhelming and can confuse many readers. To simplify the situation, a com-
prehensive yet concise overview of MBR foulants parameters and fouling will be
presented in this book.

1.3 Membrane Bioreactor Configurations

Basically, there are two membrane configurations used in the membrane system.
The first configuration is side-stream (external) membrane bioreactors (see Fig. 1.2)
and the second one is submerged MBR (the membrane is immersed directly into
bioreactor) (see Fig. 1.3). The second one is more applicable in wastewater treat-
ment than the first one because it has many advantages such as lower energy
6 1 Introduction to Membrane Bioreactors

Fig. 1.2 Side-stream membrane bioreactor with external pressure-driven membrane unit. Adapted
from Radjenović et al. (2008)

Fig. 1.3 Submerged

Membrane Bioreactor with
internal vacuum
pressure-driven membrane
filtration. Adapted from
Radjenović et al. (2008)

consumption, higher hydraulic efficiency and simple design. However, side-stream

configuration is possibly used for wastewater treatment, with wastewater (feed) is
pumped into the membrane and part of the permeate is collected while the other part
is returned back to the MBR. Side-stream configuration has the capability to control
membrane fouling significantly; resulting in constant flux but the energy con-
sumption and complex design are the major limitations.
The configurations of MBR are based on geometry (either cylindrical or planar).
There are five major membrane configurations currently used in practice
(Radjenović et al. 2008)
1. Hollow fibre (HF)
2. Spiral-wound
3. Plate-and-frame (i.e. FS)
4. Pleated filter cartridge
5. Tubular.
1.3 Membrane Bioreactor Configurations 7

The first three membrane configurations are widely used in MBRs. In the first
membrane module, the large amounts of these membranes make a bundle and the
ends of the fibre are sealed properly in an epoxy block connected with the outside of
the housing. The water can flow from inside to outside of the membrane or vice
versa. These membranes operate under both pressure and vacuum. Due to the lower
energy cost and back-flushing capability, hollow fibre membranes are most popular
in MBRs.
Spiral-wound membrane configuration are mostly used for RO and NF pro-
cesses. The Spiral-wound membrane configuration are coiled through the perforated
tube in which permeate (effluent) goes out. The standard manufacturing of the
spiral-wound membrane configuration make their installation easier with less cost
in membrane production. The installation of these membrane configuration can be
performed in series or parallel in plants with higher capacity.
Currently, plate-and-frame membrane modules are widely used in water and
wastewater treatment industry. They are composed of FS membranes with sepa-
rators and/or support membranes. The pieces of these sheets are fastened onto a
plate. The water flows across the membrane and the permeate is extracted through
pipes which emerge from the interior of the membrane module in a process that
operates under vacuum (Radjenović et al. 2008).
The last two membrane configurations are pleated filter cartridge and tubular.
These membranes are not widely used in industrial scale. Obviously, tubular
membranes are wrapped in a pressure vessel (tube) and then mixed liquor is
pumped through them. They used specifically for side-stream MBR configurations.

1.4 Advantages and Limitations of Membrane Bioreactors

Membrane bioreactors have attracted extensive attention as a result of their

numerous advantages over CASP. The advantages of MBRs include excellent
treated water quality, high biodegradable efficiency, small footprint and reactor
requirements, absolute biomass retention and ease of stable operation. They can
also display high effluent quality, flexible operation, absolute removal of bacteria,
high volumetric loading up to 20 kg COD/m3 per day, excellent disinfection
capability and turbidity less than 0.5 NTU (number transfer unit), low sludge
production, compactness, enable high removal efficiency of biological oxygen
demand (BOD) and chemical oxygen demand (COD) (Judd 2006, 2008; Li and
Chu 2003; Liao et al. 2006; Pan et al. 2009; Wang et al. 2008; Yamato et al. 2006;
Yang et al. 2006; Bouhabila et al. 2001; Chang et al. 2006; Kimura et al. 2005;
Meng et al. 2009; Stephenson et al. 2000; Visvanathan et al. 2000; Zhang 2009).
As a result, the MBR process has now become a viable alternative for the
treatment and reuse of municipal and industrial wastewaters. MBRs are therefore
considered a promising tool for future waste water treatment (Rosenberger and
Kraume 2002; Rosenberger et al. 2002; Chu and Li 2005; Côté et al. 1998; Davis
et al. 1998; Gunder and Krauth 1998; Wu and Huang 2010; Zhang et al. 2011a).
8 1 Introduction to Membrane Bioreactors

However, alongside with these advantages, MBR technology is affected by crucial

issues that seriously hamper the performance and the widespread applications of
MBRs (Bouhabila et al. 2001; Li et al. 2013; Mannina and Cosenza 2013; Zhang
et al. 2011a). Membrane fouling, that is the undesirable deposition of retained
particles, colloids, macromolecules and salts on the membrane surface or on the
membrane pores, is the most critical disadvantage (Houari et al. 2010; Meng et al.
2009; Rana and Matsuura 2010; Kochkodan 2012). Specifically, membrane fouling
results in a reduction of separation process output, diminishes process productivity,
severe decline of the permeation flux or rapid transmembrane pressure increase
(TMP), leading to high energy consumption, frequent membrane cleaning or
replacement, which consequently leads to the increase in operating and mainte-
nance cost (Asatekin et al. 2007; Bouhabila et al. 2001; Huang et al. 2010, 2012;
Khan et al. 2009; Liao et al. 2004; Pan et al. 2009; Porcelli and Judd 2010; Rabie
et al. 2001; Tansel et al. 2000; Wang et al. 2009).
In MBR, fouling mechanism is strongly related to physical and chemical
interactions between the foulants and the membrane surface. Le-Clech et al. (2006)
stated that the mechanism of fouling in MBRs includes a mixture of pore closure,
cake layer and pore blocking, however, Zhang et al. (2006) argued that fouling
mechanism involves three stages: adsorption, pore closure followed by a period of
slow of TMP rise, and TMP jump. Chang et al. (2002) and Le-Clech et al. (2006)
reviewed membrane fouling by focusing on factors that affect MBR fouling. They
provided a very comprehensive study outlining numerous factors such as sludge
characteristics, operational parameters, membrane materials and feed water char-
acteristics which all interact in causing fouling in MBRs.

Fig. 1.4 Publications on MBR fouling (as reported in Scopus using the search term “membrane
AND bioreactor AND fouling” for title-abstract-keyword on 25 August 2015)
1.4 Advantages and Limitations of Membrane Bioreactors 9

Recently, numerous research studies have been conducted exploring fouling in

MBRs and techniques used to overcome fouling. As can be seen in Fig. 1.4, a
plethora of articles have been recently published on fouling and techniques to
reduce its impact on MBR. Despite the extensive research activity related to
MBR’s, the concept of fouling and techniques to overcome fouling in MBR’s is still
an active topic, which is extensively discussed in the literature.
Apart from membrane fouling, cost is another major limitation of MBR tech-
nology. This is because of the high cost of membranes, which leads to the increases
in both, operational and maintenance costs. Membrane cost covers replacing
severely fouled or corrupted membranes and membrane cleaning processes during
maintenance (Judd 2006; Le-Clech et al. 2006).
To sum up, various processes have been developed for water treatment using
membranes. Among these processes, MBR stands out as one of the most efficient
technologies. Its capability in treating wastewater cannot be disputed. However
alongside their advantages, MBR’s are limited by the concept of fouling. Membrane
fouling is a major issue in the membrane bioreactors that significantly impair their
practical applications. Therefore, this issue needs to be addressed to minimise the
need for chemical cleaning and physical cleaning, reducing operational and
maintenance costs that have a significant impact on MBRs. By minimising mem-
brane fouling, membrane bioreactors will be more widely applicable for a range of
wastewater treatment.

References

Asatekin A, Kang S, Elimelech M, Mayes AM (2007) Anti-fouling ultrafiltration membranes

containing polyacrylonitrile-graft-poly(ethylene oxide) comb copolymer additives. J Membr
Sci 298(1–2):136–146
Baker RW (2004) Membrane technology and applications, vol, 2nd edn. John Wiley Sons Ltd,
England
Bella D, Durante F, Torregrossa M, Viviani G, Mercurio P, Cicala A (2007) The role of fouling
mechanisms in a membrane bioreactor. Water Sci Technol 55(8–9):455–464
Bouhabila E, Ben R, Buisson H (2001) Fouling characterization in membrane bioreactors. Sep
Purif Technol 22–23:123–132
Chang IS, Clech PL, Jefferson B, Judd S (2002) Membrane fouling in membrane bioreactors for
wastewater treatment. J Environ Eng 128(11):1018–1029
Chang JS, Chang CY, Chen AC, Erdei L, Vigneswaran S (2006) Long-term operation of submerged
membrane bioreactor for the treatment of high strength acrylonitrile-butadiene-styrene (ABS)
wastewater: effect of hydraulic retention time. Desalination 191(1–3):45–51
Chu H, Li X (2005) Membrane fouling in a membrane bioreactor (MBR): sludge Cake formation
and fouling characteristics. Biotechnol Bioeng 90(3):323–331
Côté P, Buisson H, Praderie M (1998) Immersed membranes activated sludge process applied to
the treatment of municipal wastewater. Water Sci Technol 38(4-5-5 pt 4):437–442
Crawford G, Thompson D, Lozier J, Daigger G, Fleischer E (2000) Membrane bioreactors-
ADesigner’s perspective. In: Paper presented at the 73rd annual water environment federation
technical exposition and conference Anaheim, Oct 14–18
10 1 Introduction to Membrane Bioreactors

Davis W, Le M, Heath C (1998) Intensified membranes activated sludge process with submerged
membrane microfiltration. Water Sci 38(4–5):421–428
Drews A (2010) Membrane fouling in membrane bioreactors-characterisation, contradictions,
causes and cures. J Membr Sci 368:1–28
Enegess D, Togna A, Sutton P (2003) Membrane separation applications to biosystems for waste
water treatment. Filtr Sep 40:14–17
Gunder B, Krauth K (1998) Replacement of secondary clarification by membrane separation—
Results with plate and hollow fiber modules. Water Sci 38(4–5):383–393
Hirani ZM, DeCarolis JF, Adham SS, Jacangelo JG (2010) Peak flux performance and microbial
removal by selected membrane bioreactor systems. Water Res 44(8):2431–2440
Hong SP, Bae TH, Tak TM, Hong S, Randall A (2002) Fouling control in activated sludge
submerged hollow fiber membrane bioreactors. Desalination 143(3):219–228
Houari A, Seyer D, Couquard F, Kecili K, Démocrate C, Heim V, Di Martino P (2010)
Characterization of the biofouling and cleaning efficiency of nanofiltration membranes.
Biofouling 26(1):15–21
Huang X, Xiao K, Shen Y (2010) Recent advances in membrane bioreactor technology for
wastewater treatment in China. Front Environ Sci Eng China 4(3):245–271
Huang J, Zhang K, Wang K, Xie Z, Ladewig B, Wang H (2012) Fabrication of
polyethersulfone-mesoporous silica nanocomposite ultrafiltration membranes with antifouling
properties. J Membr Sci 423–424:362–370
Hussain A, Al-Rawajfeh AE, Alsaraierh H (2010) Membrane bio reactors (MBR) in waste water
treatment: a review of the recent patents. Recent Pat Biotechnol 4(1):65–80. doi:10.2174/
187220810790069505
Hwang BK, Kim JH, Ahn CH, Lee CH, Song JY, Ra YH (2010) Effect of disintegrated sludge
recycling on membrane permeability in a membrane bioreactor combined with a turbulent jet
flow ozone contactor. Water Res 44(6):1833–1840
Judd S (2006) Principles and applications of membrane bioreactors in water and waste water
treatment. Oxford, London
Judd S (2008) The status of membrane bioreactor technology. Trends Technol 26(2):109–116
Judd S, Judd C (2010) Principles and applications of membrane bioreactors for water and waste
water treatment, 2nd edn. Oxford, London
Khan SJ, Visvanathan C, Jegatheesan V (2009) Prediction of membrane fouling in MBR systems
using emerically estimated specific cake resistance. Bioresour Technol 100(23):6133–6136
Kimura K, Yamato N, Yamamura H, Watanabe Y (2005) Membrane fouling in pilot-scale
membrane bioreactors (MBRs) treating municipal wastewater. Environ Sci Technol 39(16):
6293–6299
Kochkodan, V, DJ. Johnson, N. Hilal (2014) Polymeric membranes: Surface modification for
minimizing (bio)colloidal fouling. Advances in Colloid and Interface Science 206:116-140
Koros WJ, Ma YH, Shimidzu T (1996) Terminology for membranes and membrane processes
(IUPAC Recommendations 1996). J Membr Sci 120:149–159
Le-Clech P, Chen V, Fane TAG (2006) Fouling in membrane bioreactors used in wastewater
treatment. J Membr Sci 284(1–2):17–53
Leiknes TO (2010) Membrane Bioreactors. In: Membrane technology. Wiley-VCH Verlag GmbH
& Co. KGaA, pp 193–227. doi:10.1002/9783527631407.ch7
Li X, Chu H (2003) Membrane bioreactor for the drinking water treatment of polluted surface
water supplies. Water Resour 37:4781–4791
Li Z, Tian Y, Ding Y, Chen L, Wang H (2013) Fouling potential evaluation of soluble microbial
products (SMP) with different membrane surfaces in a hybrid membrane bioreactor using
worm reactor for sludge reduction. Bioresour Technol 140:111–119
Liao BQ, Bagley DM, Kraemer HE, Leppard GG, Liss SN (2004) A review of biofouling and its
control in membrane separation bioreactors. Water Environ Res 76(5):425–436
Liao B, Kraemer J, Bagley D (2006) Anaerobic membrane bioreactors: applications and research
directions. Crit Rev Enivormen Sci Technol 36(6):489–530
References 11

Mannina G, Cosenza A (2013) The fouling phenomenon in membrane bioreactors: assessment of

different strategies for energy saving. J Membr Sci 444:332–344
Meng F, Chae SR, Drews A, Kraume M, Shin HS, Yang F (2009) Recent advances in membrane
bioreactors (MBRs): membrane fouling and membrane material. Water Res 43(6):1489–1512
Mulder M (1997) Basic principles of membrane technology, 2nd edn. Kluwer Academic
publishers, Dordrecht
Nath K (2008) Membrane separation processes. Prentice Hall of India Private Limited, New Delhi
Pan J, Sun Y, Huang C (2009) Characteristics of soluble microbial products in membrane
bioreactor and its effect on membrane fouling. Desalination 250:778–780
Perry RH, Green DW (1997) Perry’s chemical engineers’ handbook, 7th edn. McGraw-Hill,
New York
Porcelli N, Judd S (2010) Chemical cleaning of potable water membranes: a review. Sep Purif
Technol 71(2):137–143
Rabie HR, Côté P, Adams N (2001) A method for assessing membrane fouling in pilot- and
full-scale systems. Desalination 141(3):237–243
Radjenović J, Matošić M, Mijatović I, Petrović M, Barceló D (2008) Membrane bioreactor
(MBR) as an advanced wastewater treatment technology. Handbook of environmental
chemistry. Water Pollut 5:S2. doi:10.1007/698_5_093
Rana D, Matsuura T (2010) Surface modifications for antifouling membranes. Chem Rev 110(4):
2448–2471
Rosenberger S, Kraume M (2002) Filterability of activated sludge in membrane bioreactors.
Desalination 146(1–3):373–379
Rosenberger S, Kubin K, Kraume M (2002) Rheology of activated sludge in membrane activation
reactors. Chemie-Ingenieur-Technik 74(4):487–494+373
Smith C, DiGregorio D, Talcott R (1969) The use of ultrafiltration membranes for activated sludge
separation. Paper presented at the 24th annual Purdue industrial waste conference
Stephenson T, Judd S, Jefferson B, Brindle K (2000) Membrane Bioreactors for waste water
treatment. IWA Publishing, London
Tansel B, Bao WY, Tansel IN (2000) Characterization of fouling kinetics in ultrafiltration systems
by resistances in series model. Desalination 129(1):7–14
Tchobanoglous G, Burton FL, Stensel HD (2004) Wastewater engineering treatment and reuse, 4th
edn. Mc-Graw Hill, New York
Thomas H, Judd S, Murrer J (2000) Fouling characteristics of membrane filtration in membrane
bioreactors. Membr Technol 122:10–13
Visvanathan C, Aim RB, Parameshwaran K (2000) Membrane separation bioreactors for waste
water treatment. Crit Rev Environ Sci Technol 30:1–48
Wang Z, Wu Z, Mai S, Yang C, Wang X, An Y, Zhou Z (2008) Research and applications of
membrane bioreactors in China: progress and prospect. Sep Purif Technol 62(2):249–263
Wang Z, Wu Z, Tang S (2009) Extracellular polymeric substances (EPS) properties and their
effects on membrane fouling in a submerged membrane bioreactor. Water Res 43(9):
2504–2512
Wu J, Huang X (2010) Use of azonation to mitigate fouling in a long-term membrane bioreactor.
Bioresour Technol 101:6019–6027
Yamamoto K, Hiasa M, Mohmood T, Matsuo T (1989) Direct solid-liquid separation using hollow
fiber membrane in an activated-sludge aeration tank. Water Sci Technol 21:43–54
Yamato N, Kimura K, Miyoshi T, Watanabe Y (2006) Difference in membrane fouling in
membran e bioreactors (MBRs) caused by membrane polymer materials. Membr Sci 280 (1–2):
911–919
Yang W, Cicek N, Ilg J (2006) State-of-the-art of membrane bioreactors: worldwide research and
commercial applications in North America. J Membr Sci 270(1–2):201–211
Zhang Q (2009) Performance evaluation and characterization of an innovative membrane
bioreactor in the treatment of waste water and removal of pharmaceuticals and pesticides.
Doctoral dissertation, University of Cincinnati
12 1 Introduction to Membrane Bioreactors

Zhang J, Chua HC, Zhou J, Fane AG (2006) Factors affecting the membrane performance in
submerged membrane bioreactors. J Membr Sci 284(1–2):54–66. doi:10.1016/[Link].2006.
06.022
Zhang H, Gao J, Jiang T, Gao D, Zhang S, Li H, Yang F (2011a) A novel approach to evaluate the
permeability of cake layer during cross-flow filtration in the flocculants added membrane
bioreactor. Bioresour Technol 102:11121–11131
Zhang K, Wei P, Yao M, Field R, Cui Z (2011b) Effect of the bubbling regimes on the
performance and energy cost of flat sheet MBRs. Desalination 283:221–226
Chapter 2
Fundamentals of Membrane Processes

In this chapter the common fundamentals of different membrane processes are

described. In the first part a general description of the different membrane struc-
tures, such as porous and dense homogeneous or symmetric and asymmetric
membranes, and their function is discussed. In the second part membrane materials
such as inorganic, organic, and composite materials and their function in membrane
bioreactors are described. Third, the preparation of synthetic membranes via the
phase inversion method is described in detail. Finally, alternative techniques of
membrane fabrication are presented.

2.1 Membrane Classification by Membrane Structure

Synthetic membranes display a broad range in their physical structure and the
material they are made from (Strathmann 2011). They can be classified according to
their morphology, as shown in Fig. 2.1.
The first group is dense homogeneous polymer membranes. Usually they are
prepared (i) from solution by solvent evaporation only or (ii) by extrusion of the
melted polymer (Nunes and Peinemann 2006). However, dense homogeneous
membranes only have a practical usefulness when they are made from a highly
permeable polymer such as silicone. Commonly, the permeate flow across the
membrane is quite low, since a minimal thickness is required to grant the membrane
mechanical stability. The majority of membranes currently are porous or consist of
a dense top layer on a porous structure (Mulder 1984, 1997; Nunes and Peinemann
2001; Strathmann et al. 2006).

© Springer Nature Singapore Pte Ltd. 2017 13

B. Ladewig and M.N.Z. Al-Shaeli, Fundamentals of Membrane Bioreactors,
Springer Transactions in Civil and Environmental Engineering,
DOI 10.1007/978-981-10-2014-8_2
14 2 Fundamentals of Membrane Processes

Fig. 2.1 Membrane

classifications according to
morphology. Adapted from
Nunes and Peinemann (2006)

The second category is porous membranes, which can also be divided into two
main groups. They are divided according to their pore diameter: microporous
(dp < 2 nm), mesoporous (2 nm < dp < 50 nm) and macroporous (dp > 50 nm)
(Gallucci et al. 2011b).
The first groups of membranes are referred to as symmetric (isotropic) and the
second type is referred to as asymmetric (anisotropic) membranes. Within the
asymmetric membranes, there are several distinctly different structures including
integrally skinned membranes (where the pore structure gradually changes from
very large pores to very fine pores, essentially forming a “skin” on top of the
membrane, giving rise to the name “integrally skinned”). Alternatively, the skin
may be nonporous. A third, and industrially very important type of asymmetric
membrane is the thin-film composite membrane, where a dense, selective, thin layer
is deposited or polymerised at the surface/interface of a porous substrate.
Symmetric membranes refer to the membranes with uniform structure (uniform
pore size or nonporous) throughout the entire membrane thickness (Buonomenna
et al. 2011). Symmetric membranes are used today mainly in dialysis, electro-
dialysis, and to some extent also in microfiltration (Strathmann 2000, 2011). The
thickness of symmetric membranes is usually between 30 and 500 µm. The total
resistance of the mass transfer relies on the total thickness of the membranes.
Hence, a decrease in membrane thickness results in an increased permeation rate.
2.1 Membrane Classification by Membrane Structure 15

Asymmetric membranes have a gradient in structure. They consist of a 0.1–5 µm

thick “skin” layer on a highly porous 100–300 µm thick structure (Strathmann
2011). The skin represents the actual selective barrier of the asymmetric sub-
structure. Its separation properties are thoroughly determined by the nature of the
material or the size of pores in the skin layer. The porous substrate layer serves as a
support for the mostly very thin top layer, or “skin” (relatively dense) and has little
effect on the separation properties of the membrane or the mass transfer rate of the
membrane (Strathmann 2011). The dense surface layer is considered to be
responsible for the membrane selectivity. Consequently, the controlled structure of
the dense surface layer has become a serious concern in the membrane design
(Zhenxin and Matsuura 1991). Also, the resistance to the mass transfer is mainly
determined by the top layer (Buonomenna et al. 2011; Nunes and Peinemann 2001).
Asymmetric membranes are primarily employed in pressure driven membrane
processes such as reverse osmosis, ultrafiltration, gas separation and sometimes in
microfiltration. High fluxes (high permeate flow per unit area), a reasonable
mechanical stability providing very thin selective layer are the unique properties of
asymmetric membranes (Strathmann 2011; Nunes and Peinemann 2006). Two
procedures are used to prepare asymmetric membranes: the first method is based on
phase inversion process which leads to integral structure (Kesting 1971), The
second method resembles a composite structure in a two-step process in which a
thin barrier layer is deposited on a microporous substructure (Cadotte and Petersen
1981; Strathmann 2011).

2.2 Membrane Materials

In general, there are three fundamentally different categories of membrane mate-

rials: Organic (polymeric), inorganic (ceramic) materials and biological materials.
Organic materials are either cellulose—based or composed of modified organic
polymers. By contrast, inorganic materials such as ceramics and metals are used in
niche industrial applications but are usually cost-prohibitive in wastewater treat-
ment. Biological membrane (bio membranes) is a selective barrier within or around
a cell in a living organism. The biomembrane is capable of recognising what is
necessary for the cell to receive or block for its survival. These membranes cannot
meet the industrial requirements due to thermomechanical stability and produc-
tivity. It should be pointed out that, a large majority of membranes in research and
commercial use are polymeric-based (organic membrane) as a result of their facile
processing into viable membrane structures and the diverse polymers available, as
well as the capability to synthesise novel polymer structures (Peyravi et al. 2012).
Recently, composite membranes and inorganic membranes have gained tremendous
attention owing to their potentially high performance, long lifetime and even their
availability that outweigh the benefits/advantages of using polymeric membranes.
16 2 Fundamentals of Membrane Processes

2.2.1 Inorganic Membranes

Inorganic membranes posses excellent thermal and chemical stability in comparison

to polymeric membranes and hive higher antifouling property due to the hydro-
philic nature of in organic material (Gallucci et al. 2011a; Mulder 1997).
Nevertheless, there has been some limitation in their use despite their wide use and
application. The main application of inorganic membranes in the past was
enrichment of uranium hexafluoride U235 via Knudsen flow through porous ceramic
membranes. Recently, many more applications are found in the field of ultrafil-
tration and microfiltration. Inorganic membranes are generally divided into four
groups: glass membranes, ceramic membranes, metallic membranes, carbon
membranes, and zeolitic membranes.
Metallic membranes can generally be obtained via the sintering of metal pow-
ders (e.g. stainless steel, molybdenum, or tungsten). According to (Gallucci et al.
2011a), the main materials for preparing metallic membranes are palladium and its
alloys due to their high solubility and permeability of hydrogen. These membranes
are employed for separation of hydrogen from gas mixtures and in the membrane
reactor area for producing pure hydrogen (Lin 2001). These membranes have both
advantages and disadvantages. The advantages are considerable mechanical
strength and higher permeating flux (Gallucci et al. 2011a). The limitations of
metallic membranes are (1) highly cost (very expensive) due to the low availability
of palladium in nature and (2) surface poisoning, which is significantly more for
thin metal membranes. There have been numerous studies reporting that the impact
of poisons such as CO or H2S on Pd-based membranes is a major problem. These
gases (H2S or CO) adsorb on the palladium surface that block the dissociation sites
for hydrogen. Therefore, these membranes have received limited attention today
because they do not relate to MBR technology (Judd 2006).
Ceramic membranes are of great importance in separation technology as they
have a higher chemical, thermal and mechanical stability compared to organic
membranes (Belfer et al. 2000). This stability makes these UF or MF membranes
suitable in different fields of industry such as (food, biotechnology and pharma-
ceutical applications). They have been proposed for gas separation and the appli-
cation of membrane reactor. Ceramic membranes are prepared through the
combination of a metal (e.g. aluminium, titanium, silicium or zirconium, zinc, tin,
and iron) with a non-metal in the form of oxide, nitride, or carbide to form a variety
of inorganic nanoparticles (fillers) such as carbon nanotubes, alumina, or aluminium
oxide (Al2O3), titanium oxide (TiO2), zirconium dioxide or zirconia (ZrO2), zinc
oxide (ZnO), Silver, tin oxide (SnO2), and Fe3O4. All these membranes have been
used to fabricate inorganic—polymer composite membranes (Arthanareeswaran
et al. 2008; Huang et al. 2006; Jian et al. 2006; Liang et al. 2012; Yang et al. 2007;
Zoppi and Soares 2002; Leo et al. 2013; Celik and Choi 2011; Celik et al. 2011a, b;
Bae and Tak 2005a, b; Maximous et al. 2010; Gallucci et al. 2011a; Leo et al. 2012;
Lu et al. 2005; Mulder 1997; Rahimpour et al. 2008, 2009; Razmjou et al. 2011a, b;
Sawada et al. 2012; Yu et al. 2009a, b; Livari et al. 2012; Moghimifar et al. 2014).
Sintering or sol–gel techniques are usually used to prepare ceramic membranes.
2.2 Membrane Materials 17

Glass membranes can be regarded as ceramic membranes. Issues associated with

ceramic membranes are the difficulties faced in proper sealing of the membranes in
modules operating at high temperature, extremely high sensitivity of membranes to
temperature gradient, leading to membrane cracking, and chemical instability of
some perovskite-type materials (Gallucci et al. 2011a). Glass membranes (silica,
SiO2) are generally prepared by leaching techniques.
Carbon membranes (also called carbon molecular sieve membranes CMS) have
been regarded as a promising candidate for applications of gas (Gallucci et al.
2011a). CMS are porous solids membranes, containing constricted holes that are
responsible for approaching the molecular dimensions of diffusing gas molecules.
Therefore, molecules with different size can be efficiently separated through
molecular sieving (Gallucci et al. 2008). CMS membranes can be prepared by
pyrolysis of thermosetting polymers such as poly acrylonitrile (PAN), cellulose
triacetate, phenol formaldehyde, and poly (furfural) alcohol.
Recently, a new class of membranes have been developed and studied, such as
the zeolitic membranes. These membranes have a very narrow pore size and can be
employed in gas separation, pervaporation and separation of ions from aqueous
solution by reverse osmosis. These membranes have some limitations; first the main
limitation is relatively low gas fluxes in comparison to other inorganic membranes.
Second, its thermal effect, as noted by Cejka et al. (2007), the zeolite layer exhibits
negative thermal expansion, in which the zeolite layer shrinks when the region
temperature is high, but the support layer expands continuously, causing thermal
stress issues for the attachment of the zeolite layer to the support and for the
connection of the individual microcrystals within the zeolite layer.
Inorganic membranes have both advantages and disadvantages as presented in
Table 2.1. The major advantages of inorganic membranes when compared with
polymeric membranes, is their high chemical, thermal, and mechanical stability and
wide tolerance to pH (Belfer et al. 2000; Gallucci et al. 2011a). They can operate at
high temperatures. As a fact of matter, inorganic membranes are stable at

Table 2.1 Advantages and disadvantages of inorganic membranes with respect to polymeric
membranes (Gallucci et al. 2011a)
Advantages Disadvantages
1. Long-term stability at high 1. High capital cost
temperatures
2. Resistance to harsh environments 2. Embrittlement phenomenon (in the case of dense
(e.g. chemical degradation, pH, etc.) Pd membranes)
3. Resistance to high pressure drops 3. Low membrane surface per module volume
4. Inertness to microbiological 4. Difficulty of achieving high selectivities in
degradation large-scale microporous membranes
5. Easy cleanability after fouling 5. Low permeability of the highly hydrogen
selective (dense) membranes at low temperatures
6. Easy catalytic activation 6. Difficult membrane to module sealing at high
temperature
18 2 Fundamentals of Membrane Processes

temperatures ranging from 300 to 800 °C and in some cases, ceramic membranes
usable over 1000 °C (van Veen et al. 1996). They also have a high resistance to
chemical degradation. Judd et al. (2004) stated that ceramic membranes did not foul
substantially at fluxes up to 60 L m−2 h−1, whilst polymeric membranes fouled at a
lower flux of 36 L m−2 h−1. Applicability of inorganic membranes is of great
interest in non—aqueous filtration due to stability in organic solvents (Tsuru et al.
2000a, b). Despite their potential in waste water treatment, certain limitations deter
membrane processes from large scale and continuous operation (Lee et al. 1999).
One of the major limitations arises from membrane fouling caused by different
inorganic salts (Bhattacharjee and Johnston 2002) which increases feed pressure,
reduces permeate flux, decreases product quality and finally shortens membrane
lifespan (Lee and Lee 2000; Seidel and Elimelech 2002).
Another limitation of inorganic membranes that probably hampers their appli-
cation is the high capital costs of both the manufacturing process and material
(Gallucci et al. 2011a). Therefore, the inorganic membranes might be used only in
some special applications such as anaerobic biodegradation (Fan et al. 1996) and
high temperature waste water treatment (e.g. high-strength industrial waste) (Luonsi
et al. 2002; Scott et al. 1998). Despite, the high expense of inorganic membranes
and their susceptibility to membrane fouling, they are still a competitive product in
many applications. It is expected that inorganic membranes will have more appli-
cations in the future. Table 2.1 summarises the advantages and disadvantages of
inorganic membranes over polymeric membranes.

2.2.2 Polymeric Membranes

Although polymer membranes are less resistance to high temperature and aggres-
sive chemicals than inorganic or metallic membranes, they are still the most widely
used materials in wastewater treatment applications. This is mainly owing to easy
preparation, reasonable expense (low cost), high efficiency for removing dispersed
oil, particles, and emulsified, small size, lower energy requirement, flexibility in
membrane configuration, and relatively low operating temperature which is also
associated with less stringent demands for the materials need in the construction of
module (Buonomenna et al. 2011; Nunes and Peinemann 2010). Among many
homopolymeric materials presented in Table 2.1, polyethersulfone (PES) is one of
the most vital polymeric materials and is widely used in producing microfiltration
(Li et al. 2008, 2009a, b; Ulbricht et al. 2007; Zhao et al. 2003a, b; Shin et al. 2005;
Liu and Kim 2011), ultrafiltration (Chaturvedi et al. 2001; Marchese et al. 2003; Xu
and Qusay 2004; Wang et al. 2006a, b, c) as well as nanofiltration membranes
(Boussu et al. 2006; Ismail and Hassan 2007), either on the laboratory or industrial
scale (Razali et al. 2013) Polyethersulfone (PES) has been recognised or
acknowledged as a high performance polyaromatic polymer possessing toughness
and thermal stability (Huang et al. 2012; Li et al. 2004; Shi et al. 2008; Shin et al.
2005; Zhao et al. 2013).
2.2 Membrane Materials 19

PES is a thermoplastic polymer and is typically amorphous in nature and shows

one prominent XRD peak at 2h = 19.9° (Nair et al. 2001; Kumar et al. 2006; Guan
et al. 2005). PES membranes show a high glass transition temperature
(Tg  503 K). PES structure has a harder benzene ring and a softer ether bond; so
crystalline properties can be expected (Barth et al. 2000; Ismail and Hassan 2007).
Additional properties include
• Good chemical resistance (inertness): PES exhibits excellent chemical resistance
to aliphatic hydrocarbons, alcohols, and acids. It is also soluble in some aprotic
polar solvents (Zhu et al. 2014).
• Blood compatibility.
• Outstanding oxidative stability.
• Outstandingly high mechanical strength.
• Easy processing and environmental endurance.
• Wide temperature and pH tolerance.
• Moderate good chlorine resistance.
• Easy to fabricate membranes in a wide variety of modules and configurations as
well as wide range of pore size available for UF and MF from 10 A to 0.2 lm.
• PES also shows other good qualities such as good membrane forming
properties.
• Commercially available and relatively inexpensive (Bolong et al. 2009).
Polyethersulfone has been affirmed as the membrane material in many processes
such as in biomedical fields for blood purification (haemodialysis and plasma
collection) (Barzin et al. 2004; Samtleben et al. 2003; Tullis et al. 2002; Werner
et al. 1995; Zhao et al. 2001; Unger et al. 2005), hollow fibres (Khulbe et al. 2003)
(Yang et al. 2007), stable substrate for the deposition and thermal processing of
semiconductor thin films (Nair et al. 2001), sensors applications (Gerlach et al.
1998), sterilisation and pharmaceutical (Baker 2012; Song et al. 2000), water
purification, beverage filtration, protein separation, and pre-treatment of reverse
osmosis (Bolong et al. 2009; Yu et al. 2011).
However, its main limitations is related to the relatively high hydrophobic
property, which can lead to severe membrane fouling (Kim et al. 1999; Van der
Bruggen et al. 2002a, b) owing to the adsorption of nonpolar solutes and
hydrophobic particles or bacteria onto its surface (Khulbe et al. 2000, 2010; Koh
et al. 2005; Rahimpour and Madaeni 2010). This would lead to the gradual
reduction of permeation flux, frequent membrane cleaning, impacting on the use-
able lifetime of the membrane and its applications (Daraei et al. 2013a, b, c; Luo
et al. 2005; Yamamura et al. 2007a, b; Zhao et al. 2013; Rahimpour et al. 2011).
Therefore, achieving the desired surface properties without modification of the
advantageous properties of PES membrane is a paramount goal for membrane
researchers and industry.
Regarding of the preparation of PES membranes, (Zhao et al. 2013) stated that
the structure of PES membranes is always symmetric and is prepared by phase
inversion methods. The structure of PES membrane is affected by the composition
20 2 Fundamentals of Membrane Processes

(e.g. concentration, solvent, and additives), temperature of PES solution, the non-
solvent or the mixture of nonsolvents, and the coagulation bath or even the envi-
ronment (Barth et al. 2000).
Many other polymeric materials can also be employed for fabricating mem-
branes as explained schematically in Table 2.2. This table illustrates some examples
of polymeric materials used for microfiltration, ultrafiltration, reverses osmosis, and
some membrane processes.
Recently, copolymer is another important polymeric material in the manufacture
of membranes. It is gaining more attention by a number of researchers. The
copolymers are composed of at least two different types of structural units with
different properties. The properties of copolymers rely on the properties of the units
that are connected in the polymer and their relative proportions. Hence, polymers
that are employed for the preparation of membrane and require different properties
can be copolymerised carefully by selecting various polymeric units. To date, many
membranes with high performance have been fabricated by different copolymers
with different molecular structures (for example, block copolymers: poly (ethylene
oxide)–polysulfone block copolymer (Hancock et al. 2000), graft copolymers: poly
(ethylene glycol)-graft-polyacrylonitrile copolymer (Su et al. 2009b), and so on.

2.2.3 Composite Membranes

Composite membranes are often referred to as thin-film composite

(TFC) membranes and they have received tremendous attention in recent years for
desalination of brackish and sea water, waste water reclamation, and the separation
and purification of chemical and biological products (Buch et al. 2008). TFC
membranes are composed of at least two layers (with different (polymeric) mate-
rials), with a very selective membrane material being deposited as a dense ultrathin
layer formed upon a more or less porous support layer (sublayer), which usually is
an ultrafiltration membrane and serves as support as shown in Fig. 2.2 (Strathmann
1989; Wu 2012). The advantage of TFC membranes is each layer (i.e. top selective
layer and bottom porous substrate) is thoroughly optimised and controlled inde-
pendently to achieve the desired selectivity and permeability while presenting
excellent compression resistance and mechanical strength (Jahanshahi et al. 2010;
Lau et al. 2012; Rahimpour 2011; Kosaraju and Sirkar 2008). The porous support
layer (bottom layer) is generally prepared through phase inversion method. On the
other hand the top selective layer is prepared from elastomer, which is hard to
prepare it through phase inversion method. The first generation TFC membranes
were prepared by pouring a thin layer of polymer solution on a liquid of water or
mercury (Mulder 1997). Numerous coating procedures have been used to prepare
TFC membranes, including plasma polymerisation, dip coating, in situ polymeri-
sation, and interfacial polymerisation. These techniques will be discussed in this
chapter.
Table 2.2 Overview of polymeric materials used for membranes, the type of membranes formed and the membrane processes they are used in Ulbricht
(2006)
Polymer Barrier type Morphology cross Barrier thickness Membrane processes
section (µm)
Cellulose acetates Nonporous Anisotropic *0.1 GS, RO
Mesoporous Anisotropic *0.1 UF
Macroporous Isotropic 50–300 MF
Cellulose Nitrites Macroporous Isotropic 100–500 MF
2.2 Membrane Materials

Cellulose regenerated Mesoporous Anisotropic *0.1 UF, D

Perfluorosulfonic acid polymer Nonporous Isotropic 50–500 ED, fuel cell
Polyacrylonitrile Mesoporous Anisotropic *0.1 UF
Polyetherimides Mesoporous Anisotropic *0.1 UF
Polyethersulfone Mesoporous Anisotropic *0.1 UF
Macroporous Isotropic 50–300 MF
Polyethylene terephthalate Macroporous Isotropic track-etched 6–35 MF
Polyphenylene oxide Nonporous Anisotropic *0.1 GS
Polytetrafluoroethylene Macroporous Isotropic 50–500 MF
Nonporous *0.1 GS
Polyamide, aliphatic Macroporous Isotropic 100–500 MF
Polyamide, aromatic Mesoporous Anisotropic *0.1 UF
Polyamide, aromatic. In situ synthesised Nonporous Anisotropic/composite *0.05 RO, NF
Polycarbonates, aromatic Nonporous Anisotropic *0.1 MF
Macroporous Isotropic track-etched 6–35 RO, NF
Polyether, aliphatic crosslinked, In situ synthesised Nonporous Anisotropic/composite *0.05 RO, NF
Polyethylene Macroporous Isotropic 50–500 MF
Polyimides Nonporous Anisotropic *0.1 GS, NF
Polypropylene Macroporous Isotropic 50-500 MF
(continued)
21
Table 2.2 (continued)
22

Polymer Barrier type Morphology cross Barrier thickness Membrane processes

section (µm)
Polysiloxanes Nonporous Anisotropic/composite *0.1 < 1–10 GS, PV, NF
(organophilic)
Polysulfone Nonporous Anisotropic *0.1 GS
Mesoporous Anisotropic *0.1 UF
Polyvinyl alcohol, crosslinked Nonporous Anisotropic/composite <1–10 PV (hydrophilic)
Polyvinylidene fluoride Mesoporous Anisotropic *0.1 UF
Macroporous Isotropic 50–300 MF
Poly(Styrene-co-divinylbenzene), sulfonated or Nonporous Isotropic 100–500 ED
terminated
RO reverse osmosis, NF nanofiltration, UF ultrafiltration, MF microfiltration, GS gas separation, ED electrodialysis, PV pervaporation
2 Fundamentals of Membrane Processes
2.2 Membrane Materials 23

Fig. 2.2 Examples of the preparation of composite membranes by interfacial polymerization

(Mulder 1997)

Another type of procedure used to prepare composite membranes, is the coating

layer, which plugs the pores in the sublayer. In this procedure, the unique char-
acteristics of the sublayer compared to those of the coating layer highlight the
overall properties. With other techniques like stretching, sintering, leaching out and
track-etching, porous membranes can be obtained. Porous membranes are mainly
used as sublayer for composite membranes. Using phase inversion method is fre-
quently possible to obtain open or dense structures. Various techniques have been
implemented to prepare the ultrathin barrier layer upon the supporting layer. These
techniques include (Lau et al. 2012; Mulder 1997; Seman et al. 2012).
(a) Interfacial polymerization (IP): It is a technique that is used for depositing the
thin selective layer onto the porous layer. Polymerisation reactions emerge
between two reactive monomers that react on the interface of two immiscible
phase (an aqueous phase and an organic solvent such as hexane) through
24 2 Fundamentals of Membrane Processes

interfacial polymerization, and form a denser polymeric top layer on the

supporting layer surface. The benefits of this technique are self-inhibiting
through passage of a limited supply of reactants through the already formed
layer, causing an extremely thin film of thickness in the range of 50 nm.
Figure 2.2 illustrates some examples of monomers and pre-polymers that can
be used to prepare composite membranes by interfacial polymerization.
(b) Dip coating: It is a straightforward and effective technique to prepare com-
posite membranes with a very thin structure but dense toplayer. Membranes
obtained by this technique can be used in gas separation, pervaporation and
reverse osmosis applications. The principle of this method is dip coating a
polymer solution onto the supporting layer’s surface and then drying the
coated layer (using oven).
(c) Lamination: In this technique, casting an ultrathin layer and then the micro-
porous layer is covered with the casted ultrathin layer.
(d) Plasma-initiated polymerization: This technique involves depositing the barrier
film directly on the microporous support layer by gaseous phase monomer
plasma using an electrical discharge at high frequencies up to 10 MHz (Mulder
1997).

2.2.4 Formation of Membranes by Phase Inversion Method

Generally, various techniques have been extensively used to prepare synthetic

membranes either inorganic membranes (e.g. ceramics, metals, glass, Zeolites) or
organic membranes that includes all sorts of polymers (Mulder 1997; Nunes and
Peinemann 2006; Strathmann et al. 2006). The purpose of preparation is to modify
the material using an appropriate technique to obtain a membrane structure with an
appropriate morphology for a specific separation. The preparation method is limited
by the materials used, the membrane morphology obtained and the separation
principle applied.
The techniques that are being employed for the preparation of synthetic mem-
brane are phase inversion, stretching of films, irradiation and etching of films,
sintering of powders, track-etching, sol–gel process, microfabrication vapour
deposition and coating (Hoek and Elimelech 2003; Hoek et al. 2002; Jeong et al.
2007; Mulder 1997; Tang et al. 2008; Ulbricht 2006). One of the most important
methods is phase inversion.
Phase inversion method is arguably one of the most common and versatile
technique used to prepare all sorts of morphologies (both symmetric and asym-
metric types) due to the significance of immersion precipitation (Boom et al. 1992;
Buonomenna et al. 2011; Madaeni and Rahimpour 2005a, b; Mulder 1997;
Rahimpour and Madaeni 2010; Rahimpour et al. 2007a, b, 2009, 2010a, b). It is a
process whereby a polymer is transformed in a controlled manner from a liquid
state to a solid state. Throughout this technique, a thermodynamically stable
2.2 Membrane Materials 25

polymer solution with a multiple components is subjected to a liquid–liquid

demixing whereby the cast polymer film separates into a polymer—rich phase
(membrane matrix) and a polymer—lean phase (membrane pores) (Buonomenna
et al. 2011). The mechanism of phase inversion during membrane formation can be
concisely described by a polymer/solvent/nonsolvent system, as explained typically
by a ternary phase diagram shown in Fig. 2.3 (Buonomenna et al. 2011).
The corners of the triangle act the three components (polymer, solvent, non-
solvent), whilst at any point within the triangle represents a mixture of three
components (starting compositions of the casting solution); the binodal curve
divides the triangle into two phase regions; a one-phase region where all compo-
nents are miscible to and a two-phase region where the system is separated into a
polymer-rich, generally a solid phase and a polymer-poor which is generally liquid
phase (although the one-phase region in the phase diagram is continuous
thermodynamically).
For practical purposes it can conveniently be divided into a liquid and a solid
region. The tie lines within the two-phase region connect two equilibrium states on
the binodal curve, which also represent the compositions of two coexisting phases
generated during the phase separation. The region between the spinodal and the
binodal curves is called metastable region, where phase separation appears under
certain initiation (nucleation). The region within the spinodal curve corresponds to
unstable composition where immediate demixing occurs after entering this region.

Fig. 2.3 Ternary phase diagram (solvent/polymer/nonsolvent) for membrane formation via phase
inversion process (Machado et al. 1999)
26 2 Fundamentals of Membrane Processes

By immersing a thin layer casting solution into a coagulation bath, the solvent of
the casting solution is exchanged with a nonsolvent (Rahimpour and Madaeni
2007). The composition of the coagulation and casting solution are the most con-
siderable factor, as it determines the phase inversion path of a membrane forming
system (Albrecht et al. 2001).
The filled square represents the initial state of casting solution. The exchange
between solvent and nonsolvent changes the composition in the casting film. Once
demixing polymer solution arrives in the metastable region between the binodal and
the spinodal, the region is referred to “binodal demixing” and therefore represents
path A (Fig. 2.3). In this region, the polymer solution is separate into a
polymer-lean phase and a polymer-rich phase (Buonomenna et al. 2011). Another
pathway towards miscibility gap (path B) is called “spinodal decomposition”. In
this pathway, the composition path passed through the thermodynamically unstable
zone (critical point), in which the binodal and spinodal curve converge, and two
co-continuous phases formed. This process yields asymmetric membranes with a
dense top layer and porous sublayer containing macrovoids, pores, and micropores
(Rahimpour and Madaeni 2007).
The general concept of phase inversion method covers a variety of different
techniques, including:
(a) Precipitation by solvent evaporation: Precipitation by solvent evaporation is a
straightforward technique used to prepare phase inversion membranes. The
polymer is dissolved in a solvent and form homogenous solution (casting or
dope solution). Then, the dope solution is casted on a suitable support (e.g.
glass plate) or another type of support that may be nonporous (polymer) or
porous (non-woven fabric). Later, the solvent is allowed to evaporate in an
inert gas (e.g. nitrogen) to exclude water vapour, allowing a dense homoge-
nous membrane to be obtained (Mulder 1997).
(b) Precipitation by controlled evaporation: In the early years this technique has
been used. In this method, the polymer is dissolved in a mixture of solvent and
nonsolvent. Even though, the solvent is more volatile than the nonsolvent, the
evaporation step leads to polymer precipitation own to higher nonsolvent
content. The structure of membrane prepared by this technique is skinned
membranes.
(c) Thermal precipitation: Polymeric solution in a mixed or single solvent is cooled
to allow phase separation to occur. Evaporation of the solvent usually allows the
formation of a skinned membrane (Cheryan 1998; Oh et al. 2009; Su et al.
2009a, b). This method is thoroughly used to prepare microfiltration membranes.
(d) Precipitation from the vapour phase: In this method, a dope solution, which
consists of a polymer and a solvent, is placed in a vapour atmosphere whereas
vapour phase consists of a nonsolvent saturated with the same solvent. The
high solvent concentration in the vapour phase prohibits the evaporation of
solvent from the cast film. As a result of diffusion of nonsolvent into the cast
film, the membrane formation appears. This leads to formation of porous
membrane without a toplayer.
2.2 Membrane Materials 27

(e) Immersion precipitation or nonsolvent induced phase inversion: This is one of

the most common methods in the preparation of the most polymeric micro-
filtration and ultrafiltration and some of nanofiltration which is used for sep-
aration processes (Ismail and Hassan 2007). In this procedure, a film of
homogenous polymeric solution is cast on a suitable substrate after preparing it
by dissolving polymer into solvent. Then the cast film is immersed in a
coagulation bath containing deionised water or methanol. Precipitation occurs
as a consequence of the exchange between the solvent and nonsolvent. The
membrane structure essentially is obtained from a combination of mass
transfer and phase separation method (Rahimpour et al. 2010a). Keeping in
mind, that thermodynamic behaviour of a polymer solution is attributed to
immersion—precipitation and is represented by polymer/solvent/nonsolvent
systems (Buonomenna et al. 2011). This precipitation is also called dry/wet
method (Zhao et al. 2008; Oh et al. 2009).

2.3 Membrane Fabrication Techniques

Membranes of different arrangements are formed in order to meet different indus-

trial and domestic demands; thus, various casting techniques have been imple-
mented to obtain different types of the membrane such as flat sheet membrane
(casting), hollow fibre membrane (spinning) and composite membrane (dip coat-
ing). The first two, will be discussed in this chapter. The third one is discussed
previously.

2.3.1 Flat Sheet Membranes

For research purposes, flat sheet membrane is a relatively simple method used to
fabricate/prepare membranes. In industrial scale, the casting method employed is
usually a continuous mode as shown below in Fig. 2.4 (Mulder 1997).
The principle of this method is the polymer is initially dissolved in an appro-
priate solvent mixture (which may include additives) and forms a homogeneous
(dope) solution. Molecular weight of a polymer, concentration of the polymer and
the kind of solvent used (mixture) are three factors (parameters) affect the viscosity
of the dope solution. Afterward, the polymer solution is spread (poured) and cast
directly to a thin film of a homogenous polymer solution using one of the sup-
porting layer (for example, clean glass plate, or polyethylene non-woven fabric,
polyester, metal, and Teflon) by means of steel casting knife and adjusting the
thickness of the membranes. The casting thickness can roughly vary from 50 to
500 µm. The thin film of a homogenous polymer solution (protomembrane) is
immediately immersed in a second liquid, which is a nonsolvent for the polymer;
28 2 Fundamentals of Membrane Processes

Fig. 2.4 Schematic of continuous flat sheet membrane preparation. Adapted from Mulder (1984,
1997)

however, it is miscible with the polymer solvent. Exchange between the solvent and
nonsolvent occurs and ultimately introduces phase separation in polymer film and
would lead to the formation of membranes (Rahimpour and Madaeni 2010;
Rahimpour et al. 2010a, b; Mulder 1997). Water is used as a nonsolvent (second
liquid), as it is a powerful nonsolvent. Organic solvents (e.g. methanol) can be used
for the same purpose as well. Since the solvent/nonsolvent pair is a very important
characteristic in obtaining the desired structure, the nonsolvent cannot be chosen at
will.
A non-continuous mode is usually employed in a laboratory scale. The
three-component polymer solution (polymer/solvent/additive) is prepared and stir-
red under particular temperatures in order to ensure complete dissolution of the
polymer. After the polymer solution is placed for some time and the complete
release of bubbles is confirmed, the homogenous solution is cast on glass plates
using a casting knife with a specific thickness (for example, filmographe Dr. Blade
150 µm; Erichsen blade 150 µm). This is immediately moved to the coagulation
bath (which is usually deionised water) for immersion at room temperature without
any evaporation. Then, the membranes are peeled off the glass and subsequently
rinsed with deionised water and stored in fresh deionised water for at least one day
to leach out all residual solvents (Rahimpour and Madaeni 2010; Rahimpour et al.
2009, 2010a, b). At the final stage, membrane is sandwiched by placing between
two sheets of filter paper or placing in air for 24 h at room temperature.
In Summary, flat sheet membranes are relatively straightforward to prepare, as
they are very effective for characterising on laboratory scale. A dead end cell station
is usually used for measuring water flux of membranes.
For very small membrane surface area (less than 1000 cm2), the membranes are
mostly cast by hand or semi-automatically using glass plate, not on non-woven
polyester.
2.3 Membrane Fabrication Techniques 29

2.3.2 Hollow Fibre Membranes

Spinning is another technique used to prepare hollow fibre membranes. For

industrial applications, hollow fibre membranes are more applicable, more effective
and cheaper than flat sheet membranes because hollow fibre membranes have
relatively higher (surface/volume) ratio compared to flat sheet membranes, which
can have a greater resistance to pressure. Additionally very few manufactures
supply flat sheet membranes (Zhao et al. 2013). Hollow fibre membranes have a
minimum dead space; therefore it can be physically cleaned by frequent backwash,
yielding longer life to the membranes. It has been designed with specific dimen-
sions that are suitable to minimise membrane fouling in a given application. Many
scholars believe that hollow fibre membranes and flat membranes can exhibit
similar performance. But, the procedures for their preparation are thoroughly dif-
ferent, considering hollow fibre membranes are self-supporting. The fibre dimen-
sions are a paramount aspect and should be taken into account when preparing
hollow fibre membranes.
In general, hollow fibre membranes can be prepared by three methods:
(a) Wet spinning method: possible but rarely used to prepare hollow fibre
membranes,
(b) Melt spinning, and
(c) Dry spinning (dry-wet spinning): this method is more applicable to prepare
hollow fibre membranes and is based on the phase inversion method (Khayet
and García-Payo 2009).
A schematic drawing illustrating the preparation of hollow fibre membranes is
displayed in Fig. 2.5. The polymer solution is prepared and stored in a thermostated
tank. Then, the solution is pumped and extruded through a tube–in-orifice spin-
neret; the polymer solution (being filtered before it) enters the spinneret. The vis-
cosity of the polymer solution should be high (more than 100 poise). The bore
injection liquid (nonsolvent liquid or gas) is also delivered or passed through the
inner tube of the spinneret. The primary function (goal) of the bore liquid is to keep
the fibre open and to assist in controlling the interior surface morphology of the
hollow fibre through phase inversion.
After a short residence time in air or atmosphere, the fibre is immersed in a
coagulation bath where precipitation appears outside the liquid filament due to
solvent evaporation. After immediate coagulation, asymmetric hollow fibre are
formed with density gradient along the radial direction (Machado et al. 1999). The
fibres are then rinsed and cut with the desired length and collected upon a godet.
Cutting the fibre is favourable in the hollow fibre process to assist in promoting the
flow of bore liquid inside the hollow. The main parameters in the spinning tech-
nique are (Mulder 1997):
(a) The extrusion rate of the polymer solution,
(b) The bore fluid rate,
(c) The tearing rate,
30 2 Fundamentals of Membrane Processes

Fig. 2.5 Hollow fibre spinning apparatus. Adapted from Machado et al. (1999), Mulder (1997)

(d) The residence time in the air gap (between spinneret and coagulation bath), and
(e) The dimensions of the spinneret.
These parameters strongly interact with the membrane forming parameters such
as the composition of the polymer solution, the composition of the coagulation bath
and its temperature.
In summary, the configurations of flat sheet and hollow fibre membrane can be
used as membrane bioreactors (MBRs) for applications of wastewater treatment,
and both have their advantages and disadvantages.

References

Albrecht W, Weigel T, Schossig-Tiedemann M, Kneifel K, Peinemann KV, Paul D (2001)

Formation of hollow fiber membranes from poly(ether imide) at wet phase inversion using
binary mixtures of solvents for the preparation of the dope. J Membr Sci 192(1–2):217–230.
doi:10.1016/S0376-7388(01)00504-X
Arthanareeswaran G, Sriyamuna Devi TK, Raajenthiren M (2008) Effect of silica particles on
cellulose acetate blend ultrafiltration membranes: Part I. Sep Purif Technol 64(1):38–47
Bae TH, Tak TM (2005a) Effect of TiO2 nanoparticles on fouling mitigation of ultrafiltration
membranes for activated sludge filtration. J Membr Sci 249(1–2):1–8
Bae TH, Tak TM (2005b) Interpretation of fouling characteristics of ultrafiltration membranes
during the filtration of membrane bioreactor mixed liquor. J Membr Sci 264(1–2):151–160
Baker R (2012) Membrane technology and application, 3rd edn. Wiley, United Kingdom
Barth C, Gonçalves MC, Pires ATN, Roeder J, Wolf BA (2000) Asymmetric polysulfone and
polyethersulfone membranes: effects of thermodynamic conditions during formation on their
performance. J Membr Sci 169(2):287–299
References 31

Barzin J, Feng C, Khulbe KC, Matsuura T, Madaeni SS, Mirzadeh H (2004) Characterization of
polyethersulfone hemodialysis membrane by ultrafiltration and atomic force microscopy.
J Membr Sci 237(1–2):77–85
Belfer S, Fainchtain R, Purinson Y, Kedem O (2000) Surface characterization by FTIR-ATR
spectroscopy of polyethersulfone membranes-unmodified, modified and protein fouled.
J Membr Sci 172(1–2):113–124
Bhattacharjee S, Johnston GM (2002) A model of membrane fouling by salt precipitation from
multicomponent ionic mixtures in crossflow nanofiltration. Environ Eng Sci 19(6):399–412
Bolong N, Ismail AF, Salim MR, Rana D, Matsuura T (2009) Development and characterization of
novel charged surface modification macromolecule to polyethersulfone hollow fiber membrane
with polyvinylpyrrolidone and water. J Membr Sci 331(1–2):40–49
Boom RM, Wienk IM, Den Van, Boomgaard T, Smolders CA (1992) Microstructures in phase
inversion membranes. Part 2. The role of a polymeric additive. J Membr Sci 73(2–3):277–292
Boussu K, Van der Bruggen B, Volodin A, Van Haesendonck C, Delcour JA, Van der Meeren P,
Vandecasteele C (2006) Characterization of commercial nanofiltration membranes and
comparison with self-made polyethersulfone membranes. Desalination 191(1–3):245–253
Buch PR, Jagan Mohan D, Reddy AVR (2008) Preparation, characterization and chlorine stability
of aromatic-cycloaliphatic polyamide thin film composite membranes. J Membr Sci 309(1–
2):36–44
Buonomenna M, Choi S, Galiano F, Drioli E (2011) Membranes prepared via phase inversion. In:
Basile A, Gallucci F (eds) Membranes for membrane reactors, preparation, optimization and
selection, 1st edn. Wiley, UK, pp 475–490
Cadotte J, Petersen R (1981) Thin film reverse osmosis membranes: origin, development, and
recent advances. In: Synthetic membranes, ACS symposium series 153, vol 1, pp 305–325
Cejka J, Corna HV, Corma A, Schuth F (2007) Introduction to zeolite science and practise, studies
in surface science and catalysis. Elsevier
Celik E, Choi H (2011) Carbon nanotube/polyethersulfone composite membranes for water
filtration. In: ACS Symposium Series, vol 1078
Celik E, Liu L, Choi H (2011a) Protein fouling behavior of carbon nanotube/polyethersulfone
composite membranes during water filtration. Water Res 45(16):5287–5294
Celik E, Park H, Choi H, Choi H (2011b) Carbon nanotube blended polyethersulfone membranes
for fouling control in water treatment. Water Res 45(1):274–282
Chaturvedi BK, Ghosh AK, Ramachandhran V, Trivedi MK, Hanra MS, Misra BM (2001)
Preparation, characterization and performance of polyethersulfone ultrafiltration membranes.
Desalination 133(1):31–40
Cheryan M (1998) Ultrafiltration and microfiltration handbook. Technomic Publishing Company
Inc, USA
Daraei P, Madaeni SS, Ghaemi N, Khadivi MA, Astinchap B, Moradian R (2013a) Enhancing
antifouling capability of PES membrane via mixing with various types of polymer modified
multi-walled carbon nanotube. J Membr Sci 444:184–191
Daraei P, Madaeni SS, Ghaemi N, Khadivi MA, Astinchap B, Moradian R (2013b) Fouling
resistant mixed matrix polyethersulfone membranes blended with magnetic nanoparticles:
study of magnetic field induced casting. Sep Purif Technol 109:111–121
Daraei P, Madaeni SS, Ghaemi N, Khadivi MA, Rajabi L, Derakhshan AA, Seyedpour F (2013c)
PAA grafting onto new acrylate-alumoxane/PES mixed matrix nano-enhanced membrane:
preparation, characterization and performance in dye removal. Chem Eng J 221:111–123
Fan XJ, Urbain V, Qian Y, Manem J (1996) Nitrification and mass balance with a membrane
bioreactor for municipal wastewater treatment. Water Sci Technol 34. doi:10.1016/0273-1223
(96)00502-1
Gallucci F, Basile A, Hai F (2011a) Membranes for membrane reactors: preparation, optimization
and selection, 1st edn. Wiley, UK
Gallucci F, Basile A, Hai FI (2011b) Introduction—a review of membrane reactors. In:
Membranes for membrane reactors: preparation, optimization and selection. Wiley, Chichester,
pp 1–61. doi:10.1002/[Link]
32 2 Fundamentals of Membrane Processes

Gallucci F, Tosti S, Basile A (2008) Pd-Ag tubular membrane reactors for methane dry reforming:
a reactive method for CO2 consumption and H2 production. J Membr Sci 317(1–2):96–105.
doi:10.1016/[Link].2007.03.058
Gerlach G, Baumann K, Buchhold R, Naklal A (1998) German Patent D E 19853732
Guan R, Zou H, Lu D, Gong C, Liu Y (2005) Polyethersulfone sulfonated by chlorosulfonic acid
and its membrane characteristics. Eur Polym J 41(7):1554–1560
Hancock LF, Fagan SM, Ziolo MS (2000) Hydrophilic, semipermeable membranes fabricated with
poly(ethylene oxide)-polysulfone block copolymer. Biomaterials 21(7):725–733
Hoek EMV, Elimelech M (2003) Cake-enhanced concentration polarization: a new fouling
mechanism for salt-rejecting membranes. Environ Sci Technol 37(24):5581–5588
Hoek EMV, Kim AS, Elimelech M (2002) Influence of crossflow membrane filter geometry and
shear rate on colloidal fouling in reverse osmosis and nanofiltration separations. Environ Eng
Sci 19(6):357–372
Huang J, Zhang K, Wang K, Xie Z, Ladewig B, Wang H (2012) Fabrication of
polyethersulfone-mesoporous silica nanocomposite ultrafiltration membranes with antifouling
properties. J Membr Sci 423–424:362–370
Huang ZQ, Chen ZY, Guo XP, Zhang Z, Guo CL (2006) Structures and separation properties of
PAN-Fe3O4 ultrafiltration membranes prepared under an orthogonal magnetic field. Ind Eng
Chem Res 45(23):7905–7912
Ismail AF, Hassan AR (2007) Effect of additive contents on the performances and structural
properties of asymmetric polyethersulfone (PES) nanofiltration membranes. Sep Purif Technol
55(1):98–109
Jahanshahi M, Rahimpour A, Peyravi M (2010) Developing thin film composite poly
(piperazine-amide) and poly(vinyl-alcohol) nanofiltration membranes. Desalination 257(1–
3):129–136
Jeong BH, Hoek EMV, Yan Y, Subramani A, Huang X, Hurwitz G, Ghosh AK, Jawor A (2007)
Interfacial polymerization of thin film nanocomposites: a new concept for reverse osmosis
membranes. J Membr Sci 294(1–2):1–7
Jian P, Yahui H, Yang W, Linlin L (2006) Preparation of polysulfone-Fe3O4 composite
ultrafiltration membrane and its behavior in magnetic field. J Membr Sci 284(1–2):9–16
Judd S (2006) Principles and applications of membrane bioreactors in water and waste water
treatment, 1st edn. Elsevier, UK
Judd S, Robinson R, Holdner J, Vazquez HA, Jefferson B (2004) Impact of membrane material on
membrane bioreactor permeability. In: Proceedings of the water environment-membrane
technology conference, Seoul, Korea
Kesting R (1971) Synthetic polymeric membranes. McGraw-Hill, New York
Khayet M, García-Payo MC (2009) X-Ray diffraction study of polyethersulfone polymer,
flat-sheet and hollow fibers prepared from the same under different gas-gaps. Desalination 245
(1–3):494–500
Khulbe KC, Feng C, Matsuura T, Kapantaidakis GC, Wessling M, Koops GH (2003)
Characterization of polyethersulfone-polyimide hollow fiber membranes by atomic force
microscopy and contact angle goniometery. J Membr Sci 226(1–2):63–73. doi:10.1016/j.
memsci.2003.08.011
Khulbe KC, Feng CY, Matsuura T (2010) Surface modification of synthetic polymeric membranes
for filtration and gas separation. Recent Pat Chem Eng 3(1):1–16
Khulbe KC, Matsuura T, Singh S, Lamarche G, Noh SH (2000) Study on fouling of ultrafiltration
membrane by electron spin resonance. J Membr Sci 167(2):263–273
Kim IC, Choi JG, Tak TM (1999) Sulfonated polyethersulfone by heterogeneous method and its
membrane performances. J Appl Polym Sci 74(8):2046–2055
Koh M, Clark MM, Howe KJ (2005) Filtration of lake natural organic matter: adsorption capacity
of a polypropylene microfilter. J Membr Sci 256(1–2):169–175
Kosaraju P, Sirkar K (2008) Interfacially polymerized thin film comopsite membranes on
microporous polypropylene supports for solvent-resistant nanofiltration. Membr Sci
321:155–161
References 33

Kumar R et al (2006) Nucl Instr Meth Phys Res 248B: 279–283

Lau WJ, Ismail AF, Misdan N, Kassim MA (2012) A recent progress in thin film composite
membrane: a review. Desalination 287:190–199
Lee S, Kim J, Lee CH (1999) Analysis of CaSO4 scale formation mechanism in various
nanofiltration modules. J Membr Sci 163(1):63–74
Lee S, Lee CH (2000) Effect of operating conditions on CaSO4 scale formation mechanism in
nanofiltration for water softening. Water Res 34(15):3854–3866
Leo CP, Ahmad Kamil NH, Junaidi MUM, Kamal SNM, Ahmad AL (2013) The potential of
SAPO-44 zeolite filler in fouling mitigation of polysulfone ultrafiltration membrane. Sep Purif
Technol 103:84–91
Leo CP, Cathie Lee WP, Ahmad AL, Mohammad AW (2012) Polysulfone membranes blended
with ZnO nanoparticles for reducing fouling by oleic acid. Sep Purif Technol 89:51–56
Li B, Zhao W, Su Y, Jiang Z, Dong X, Liu W (2009a) Enhanced desulfurization performance and
swelling resistance of asymmetric hydrophilic pervaporation membrane prepared through
surface segregation technique. J Membr Sci 326(2):556–563
Li JF, Xu ZL, Yang H, Yu LY, Liu M (2009b) Effect of TiO2 nanoparticles on the surface
morphology and performance of microporous PES membrane. Appl Surf Sci 255(9):
4725–4732
Li Y, Cao C, Chung TS, Pramoda KP (2004) Fabrication of dual-layer polyethersulfone
(PES) hollow fiber membranes with an ultrathin dense-selective layer for gas separation.
J Membr Sci 245(1–2):53–60
Li Y, Chung TS, Xiao Y (2008) Superior gas separation performance of dual-layer hollow fiber
membranes with an ultrathin dense-selective layer. J Membr Sci 325(1):23–27
Liang S, Xiao K, Mo Y, Huang X (2012) A novel ZnO nanoparticle blended polyvinylidene
fluoride membrane for anti-irreversible fouling. J Membr Sci 394–395:184–192
Lin YS (2001) Microporous and dense inorganic membranes: current status and prospective. Sep
Purif Technol 25(1–3):39–55. doi:10.1016/S1383-5866(01)00089-2
Liu SX, Kim JT (2011) Characterization of surface modification of polyethersulfone membrane.
J Adhes Sci Technol 25(1–3):193–212
Livari AE, Aroujalian A, Raisi A, Fathizadeh M (2012) The effect of TiO2 nanoparticles on
PES UF membrane fouling in water oil separation. Process Eng 44:1783–1785
Lu Y, Yu S, Chai B (2005) Preparation of PVDF ultrafiltration membrane modified by nano-sized
alumina(Al2O3) and its antifouling research. Polymer 46:7701–7706
Luo ML, Zhao JQ, Tang W, Pu CS (2005) Hydrophilic modification of poly(ether sulfone)
ultrafiltration membrane surface by self-assembly of TiO2 nanoparticles. Appl Surf Sci 249(1–
4):76–84
Luonsi A, Laitinen N, Beyer K, Levänen E, Poussade Y, Nyström M (2002) Separation of CTMP
mill-activated sludge with ceramic membranes. Desalination 146(1–3):399–404
Machado PST, Habert AC, Borges CP (1999) Membrane formation mechanism based on
precipitation kinetics and membrane morphology: Flat and hollow fiber polysulfone
membranes. J Membr Sci 155(2):171–183
Madaeni SS, Rahimpour A (2005a) Effect of type of solvent and non-solvents on morphology and
performance of polysulfone and polyethersulfone ultrafiltration membranes for milk concen-
tration. Polym Adv Technol 16(10):717–724
Madaeni SS, Rahimpour A (2005b) Preparation of polyethersulfone ultrafiltration membranes for
milk concentration and effects of additives on their morphology and performance. Chin J
Polym Sci (English Edition) 23(5):539–548
Marchese J, Ponce M, Ochoa NA, Prádanos P, Palacio L, Hernández A (2003) Fouling behaviour
of polyethersulfone UF membranes made with different PVP. J Membr Sci 211(1):1–11
Maximous N, Nakhla G, Wan W, Wong K (2010) Performance of a novel ZrO2/PES membrane
for wastewater filtration. J Membr Sci 352(1–2):222–230
Moghimifar V, Raisi A, Aroujalian A (2014) Surface modification of polyethersulfone
ultrafiltration membranes by corona plasma-assisted coating TiO2 nanoparticles. J Membr
Sci 461:69–80
34 2 Fundamentals of Membrane Processes

Mulder M (1984) Basic principles of membrane technology, 1st edn. Kluwer Academic
Publishers, Dordrecht
Mulder M (1997) Basic principles of membrane technology, 2nd edn. Kluwer Academic
Publishers, Dordrecht
Nair PK, Cardoso J, Gomez Daza O, Nair MTS (2001) Polyethersulfone foils as stable transparent
substrates for conductive copper sulfide thin film coatings. Thin Solid Films 401(1–2):243–250
Nunes S, Peinemann K (2001) Membrane technology. Wiley, Weinheim
Nunes S, Peinemann K (2006) Membrane technology. Wiley, Weinheim
Nunes S, Peinemann K (2010) Membranes for water treatment, 4th edn. Wiley, Weinheim
Oh SJ, Kim N, Lee YT (2009) Preparation and characterization of PVDF/TiO2 organic-inorganic
composite membranes for fouling resistance improvement. J Membr Sci 345(1–2):13–20
Peyravi M, Rahimpour A, Jahanshahi M (2012) Thin film composite membranes with modified
polysulfone supports for organic solvent nanofiltration. J Membr Sci 423–424:225–237
Rahimpour A (2011) Preparation and modification of nano-porous polyimide (PI) membranes by
UV photo-grafting process: ultrafiltration and nanofiltration performance. Korean J Chem Eng
28(1):261–266
Rahimpour A, Jahanshahi M, Peyravi M, Khalili S (2011) Interlaboratory study of highly
permeable thin film composite polyamide nanofiltration membrane. Polym Adv Technol
23:884–893
Rahimpour A, Madaeni SS (2007) Polyethersulfone (PES)/cellulose acetate phthalate (CAP) blend
ultrafiltration membranes: preparation, morphology, performance and antifouling properties.
J Membr Sci 305(1–2):299–312
Rahimpour A, Madaeni SS (2010) Improvement of performance and surface properties of
nano-porous polyethersulfone (PES) membrane using hydrophilic monomers as additives in
the casting solution. J Membr Sci 360(1–2):371–379
Rahimpour A, Madaeni SS, Mansourpanah Y (2007a) The effect of anionic, non-ionic and cationic
surfactants on morphology and performance of polyethersulfone ultrafiltration membranes for
milk concentration. J Membr Sci 296(1–2):110–121
Rahimpour A, Madaeni SS, Mansourpanah Y (2007b) High performance polyethersulfone UF
membrane for manufacturing spiral wound module: preparation, morphology, performance,
and chemical cleaning. Polym Adv Technol 18(5):403–410
Rahimpour A, Madaeni SS, Mansourpanah Y (2010a) Fabrication of polyethersulfone
(PES) membranes with nano-porous surface using potassium perchlorate (KClO4) as an
additive in the casting solution. Desalination 258(1–3):79–86
Rahimpour A, Madaeni SS, Mansourpanah Y (2010b) Nano-porous polyethersulfone
(PES) membranes modified by acrylic acid (AA) and 2-hydroxyethylmethacrylate (HEMA)
as additives in the gelation media. J Membr Sci 364(1–2):380–388
Rahimpour A, Madaeni SS, Taheri AH, Mansourpanah Y (2008) Coupling TiO2 nanoparticles
with UV irradiation for modification of polyethersulfone ultrafiltration membranes. J Membr
Sci 313(1–2):158–169
Rahimpour A, Madaeni SS, Zereshki S, Mansourpanah Y (2009) Preparation and characterization
of modified nano-porous PVDF membrane with high antifouling property using UV
photo-grafting. Appl Surf Sci 255(16):7455–7461
Razali NF, Mohammad AW, Hilal N, Leo CP, Alam J (2013) Optimisation of polyethersulfone/
polyaniline blended membranes using response surface methodology approach. Desalination
311:182–191
Razmjou A, Mansouri J, Chen V (2011a) The effects of mechanical and chemical modification of
TiO2 nanoparticles on the surface chemistry, structure and fouling performance of PES
ultrafiltration membranes. J Membr Sci 378(1–2):73–84
Razmjou A, Mansouri J, Chen V, Lim M, Amal R (2011b) Titania nanocomposite polyether-
sulfone ultrafiltration membranes fabricated using a low temperature hydrothermal coating
process. J Membr Sci 380(1–2):98–113
References 35

Samtleben W, Dengler C, Reinhardt B, Nothdurft A, Lemke HD (2003) Comparison of the new

polyethersulfone high-flux membrane DIAPES® HF800 with conventional high-flux mem-
branes during on-line haemodiafiltration. Nephrol Dial Transplant 18(11):2382–2386
Sawada I, Fachrul R, Ito T, Ohmukai Y, Maruyama T, Matsuyama H (2012) Development of a
hydrophilic polymer membrane containing silver nanoparticles with both organic antifouling
and antibacterial properties. J Membr Sci 387–388(1):1–6
Scott JA, Neilson DJ, Liu W, Boon PN (1998) A dual function membrane bioreactor system for
enhanced aerobic remediation of high-strength industrial waste. Water Sci Technol 38(4–
5):413–420
Seidel A, Elimelech M (2002) Coupling between chemical and physical interactions in natural
organic matter (NOM) fouling of nanofiltration membranes: implications for fouling control.
J Membr Sci 203(1–2):245–255
Seman MA, Khayet M, Hilal N (2012) Development of anti-fouling properties and performance of
nanofiltration membranes by interfacial polymerization and photografting In: Hilal N,
Khayet M, Wright B (eds) Membrane modification technology and applications. Boca
Raton, Taylor & Francis Group: CRC press, pp 119–153
Shi Q, Su Y, Zhao W, Li C, Hu Y, Jiang Z, Zhu S (2008) Zwitterionic polyethersulfone
ultrafiltration membrane with superior antifouling property. J Membr Sci 319(1–2):271–278
Shin SJ, Kim JP, Kim HJ, Jeon JH, Min BR (2005) Preparation and characterization of
polyethersulfone microfiltration membranes by a 2-methoxyethanol additive. Desalination 186
(1–3):1–10
Song YQ, Sheng J, Wei M, Yuan XB (2000) Surface modification of polysulfone membranes by
lowtemperature plasma-graft poly(ethylene glycol) onto polysulfone membranes. J Appl
Polym Sci 78(5):979–985
Strathmann, H (1989) Economical evaluation of membrane technology In: Cecille L, Toussaint JC
(eds) Future industrial prospects of membrane processes. Elsevier, London & New York,
pp 41–55
Strathmann H (2000) Introduction to membrane science and technology. Wiley-VCH, Weinheim
Strathmann H (2011) Introduction to membrane science and technology. Wiley-VCH, Weinheim
Strathmann H, Giorno L, Drioli E (2006) An introduction to membrane science and technology.
In: Consiglio Nazionale delle Ricerche, Rome
Su Y, Mu C, Li C, Jiang Z (2009a) Antifouling property of a weak polyelectrolyte membrane
based on poly(acrylonitrile) during protein ultrafiltration. Ind Eng Chem Res 48(6):3136–3141
Su YL, Cheng W, Li C, Jiang Z (2009b) Preparation of antifouling ultrafiltration membranes with
poly(ethylene glycol)-graft-polyacrylonitrile copolymers. J Membr Sci 329(1–2):246–252
Tang B, Huo Z, Wu P (2008) Study on a novel polyester composite nanofiltration membrane by
interfacial polymerization of triethanolamine (TEOA) and trimesoyl chloride (TMC).
I. Preparation, characterization and nanofiltration properties test of membrane. J Membr Sci
320(1–2):198–205
Tsuru T, Izumi S, Yoshioka T, Asaeda M (2000a) Temperature effect on transport performance by
inorganic nanofiltration membranes. AIChE J 46(3):565–574
Tsuru T, Sudou T, Kawahara SI, Yoshioka T, Asaeda M (2000b) Permeation of liquids through
inorganic nanofiltration membranes. J Colloid Interface Sci 228(2):292–296
Tullis RH, Duffin RP, Zech M, Ambrus JL Jr (2002) Affinity hemodialysis for antiviral therapy.
I. Removal of HIV-1 from cell culture supernatants, plasma, and blood. Ther Apheresis
6(3):213–220
Ulbricht M (2006) Advanced functional polymer membranes. Polymer 47(7):2217–2262
Ulbricht M, Schuster O, Ansorge W, Ruetering M, Steiger P (2007) Influence of the strongly
anisotropic cross-section morphology of a novel polyethersulfone microfiltration membrane on
filtration performance. Sep Purif Technol 57(1):63–73
36 2 Fundamentals of Membrane Processes

Unger RE, Peters K, Huang Q, Funk A, Paul D, Kirkpatrick CJ (2005) Vascularization and gene
regulation of human endothelial cells growing on porous polyethersulfone (PES) hollow fiber
membranes. Biomaterials 26(17):3461–3469. doi:10.1016/[Link].2004.09.047
Van der Bruggen B, Braeken L, Vandecasteele C (2002a) Evaluation of parameters describing flux
decline in nanofiltration of aqueous solutions containing organic compounds. Desalination 147
(1–3):281–288
Van der Bruggen B, Braeken L, Vandecasteele C (2002b) Flux decline in nanofiltration due to
adsorption of organic compounds. Sep Purif Technol 29(1):23–31
van Veen HM, Bracht M, Hamoen E, Alderliesten PT (1996) Chapter 14 Feasibility of the
application of porous inorganic gas separation membranes in some large-scale chemical
processes. Membr Sci Technol 4
Wang Y, Su Y, Sun Q, Ma X, Ma X, Jiang Z (2006a) Improved permeation performance of
Pluronic F127-polyethersulfone blend ultrafiltration membranes. J Membr Sci 282(1–2):44–51
Wang YQ, Su YL, Ma XL, Sun Q, Jiang ZY (2006b) Pluronic polymers and polyethersulfone
blend membranes with improved fouling-resistant ability and ultrafiltration performance.
J Membr Sci 283(1–2):440–447
Wang YQ, Wang T, Su YL, Peng FB, Wu H, Jiang ZY (2006c) Protein-adsorption-resistance and
permeation property of polyethersulfone and soybean phosphatidylcholine blend ultrafiltration
membranes. J Membr Sci 270(1–2):108–114
Werner C, Jacobasch HJ, Reichelt G (1995) Surface characterization of hemodialysis membranes
based on streaming potential measurements. J Biomater Sci Polym Ed 7(1):61–76
Wu H (2012) Improving the anti-fouling and fouling release of PVDF UF membrane by
chemically modified SiO2 nanoparticles. New South Wales, Sydney, Australia
Xu ZL, Qusay FA (2004) Polyethersulfone (PES) hollow fiber ultrafiltration membranes prepared
by PES/non-solvent/NMP solution. J Membr Sci 233(1–2):101–111
Yamamura H, Kimura K, Watanabe Y (2007a) Mechanism involved in the evolution of physically
irreversible fouling in microfiltration and ultrafiltration membranes used for drinking water
treatment. Environ Sci Technol 41(19):6789–6794
Yamamura H, Okimoto K, Kimura K, Watanabe Y (2007b) Influence of calcium on the evolution
of irreversible fouling in microfiltration/ultrafiltration membranes. J Water Supply Res Technol
—AQUA 56(6–7):425–434
Yang Y, Zhang H, Wang P, Zheng Q, Li J (2007) The influence of nano-sized TiO2 fillers on the
morphologies and properties of PSF UF membrane. J Membr Sci 288(1–2):231–238
Yu LY, Shen HM, Xu ZL (2009a) PVDF-TiO2 composite hollow fiber ultrafiltration membranes
prepared by TiO2 sol-gel method and blending method. J Appl Polym Sci 113(3):1763–1772
Yu LY, Xu ZL, Shen HM, Yang H (2009b) Preparation and characterization of PVDF-SiO2
composite hollow fiber UF membrane by sol-gel method. J Membr Sci 337(1–2):257–265
Yu Y, Seo S, Kim IC, Lee S (2011) Nanoporous polyethersulfone (PES) membrane with enhanced
flux applied in forward osmosis process. J Membr Sci 375(1–2):63–68. doi:10.1016/[Link].
2011.02.019
Zhao C, Liu T, Lu Z, Cheng L, Huang J (2001) An evaluation of a polyethersulfone hollow fiber
plasma separator by animal experiment. Artif Organs 25:3–60
Zhao C, Liu X, Rikimaru S, Nomizu M, Nishi N (2003a) Surface characterization of polysulfone
membranes modified by DNA immobilization. J Membr Sci 214(2):179–189
Zhao C, Xue J, Ran F, Sun S (2013) Modification of polyethersulfone membranes—A review of
methods. Prog Mater Sci 58(1):76–150
Zhao Q, Qian J, An Q, Zhu Z, Zhang P, Bai Y (2008) Studies on pervaporation characteristics of
polyacrylonitrile-b-poly(ethylene glycol)-b-polyacrylonitrile block copolymer membrane for
dehydration of aqueous acetone solutions. J Membr Sci 311(1–2):284–293
Zhao ZP, Wang Z, Wang SC (2003b) Formation, charged characteristic and BSA adsorption
behavior of carboxymethyl chitosan/PES composite MF membrane. J Membr Sci 217(1–
2):151–158
References 37

Zhenxin Z, Matsuura T (1991) Discussions on the formation mechanism of surface pores in

reverse osmosis, ultrafiltration, and microfiltration membranes prepared by phase inversion
process. J Colloid Interface Sci 147(2):307–315
Zhu J, Guo N, Zhang Y, Yu L, Liu J (2014) Preparation and characterization of negatively charged
PES nanofiltration membrane by blending with halloysite nanotubes grafted with poly (sodium
4-styrenesulfonate) via surface-initiated ATRP. J Membr Sci 465:91–99
Zoppi RA, Soares CGA (2002) Hybrids of poly(ethylene oxide-b-amide-6) and ZrO2 sol-gel:
Preparation, characterization, and application in processes of membranes separation. Adv
Polym Technol 21(1):2–16
Chapter 3
Fouling in Membrane Bioreactors

Membrane fouling is a stubborn problem in all membrane filtration processes, in

particular membrane bioreactors because it leads to higher operating pressure, more
frequent chemical cleaning, shortened membrane life and compromised product
water quality. This chapter presents an exhaustive overview of membrane fouling in
membrane bioreactors. It commences by giving a concise definition of membrane
fouling and its diverse implication in the development of membrane bioreactor
technology. This chapter highlights the underlying causes of membrane fouling and
its effects are also indicated. The types of membrane fouling in membrane biore-
actors are elucidated in detail. Thereafter, methods used to control or limit mem-
brane fouling are also outlined in this chapter. To sum up, membrane fouling is
highly complex physico-chemical problem.

3.1 Membrane Fouling

Generally, membrane fouling is considered as a bottleneck in membrane filtration

processes (Huang et al. 2012b). It is inevitable problem in which the retained
particles, colloids, macromolecules and salts are undesirably deposited and accu-
mulated on the membrane surface or in the membrane pores (Houari et al. 2010;
Meng et al. 2009; Rana and Matsuura 2010; Kochkodan and Hilal 2015).
Membrane fouling is a very common hindrance to the advancement of water
treatment membrane technologies, including microfiltration (Xiao et al. 2011);
ultrafiltration (Bai and Leow 2002a, b; Le-Clech et al. 2006a, b), nanofiltration (Mo
et al. 2012; Simon et al. 2013) and osmosis processes (Li et al. 2007; Phuntsho et al.
2012). Therefore, membrane fouling decreases the permeate flux significantly,
affects the quantity and quality of products, raises operating costs, and eventually
shortens membrane lifespan (Wang et al. 2011a, b; Porcelli and Judd 2010).

© Springer Nature Singapore Pte Ltd. 2017 39

B. Ladewig and M.N.Z. Al-Shaeli, Fundamentals of Membrane Bioreactors,
Springer Transactions in Civil and Environmental Engineering,
DOI 10.1007/978-981-10-2014-8_3
40 3 Fouling in Membrane Bioreactors

(a) (b)

Fig. 3.1 Membrane fouling process in membrane bioreactors, via a pore blocking and b cake
layer formation. Adapted from Meng et al. (2009)

With respect to MBR, membrane fouling is one of the most stubborn problems,
hindering its widespread practical applications and also reduces its performance
(Hilal et al. 2005; Huang et al. 2010; Kang et al. 2003; Kimura et al. 2005;
Le-Clech et al. 2006a, b; Meng et al. 2009; Zularisam et al. 2006; Miura et al. 2007;
Wang et al. 2011a, b).
Membrane fouling can be ascribed to both pore clogging and sludge cake
deposition which are regarded as the main fouling components as shown
schematically in Fig. 3.1 (Hilal et al. 2005; Lee et al. 2001a), whilst other
adsorption of solutes on membranes, deposition of particle within the membrane
pores and alterations to the cake layer affect membrane fouling via the modification
of either or both components (Bai and Leow 2002a, b; Ma et al. 2001a, b; Wiesner
et al. 1992; Ahmed 1997; Wakeman and Williams 2002a). Pore blocking and
adsorption in internal pore surfaces occur if the foulants (colloids) are smaller than
the membrane pores (i.e. solutes). However, if the foulants (colloids and sludge
flocs) are much larger than the membrane pores, they tend to form cake layer on the
surface of membrane. In fact, pore blocking increases the membrane resistance
whereas cake layer can create an additional layer of resistance to permeation flow
(Bai and Leow 2002a; Wiesner et al. 1992).
During the past few decades, there have been numerous research studies con-
ducted to grasp the complex mechanisms of membrane fouling and strategies that
can be implemented to keep the filterability of membranes which in turn controls
fouling (Tardieu et al. 1998; Xiao et al. 2011; Ang et al. 2011; Chon et al. 2013;
Lee et al. 2004; Asatekin et al. 2007; Hilal et al. 2005; Hong et al. 2002; Le-Clech
et al. 2006a, b, c). However, there are still research gaps on how to counteract
fouling successfully (Wu and Huang 2010a; Wang et al. 2011; Tiraferri et al. 2012;
Diagne et al. 2012; Cui and Choo 2013).
Fouling has been a problematic phenomenon the industry has been battling for a
while, and extensive research must be conducted on this issue. This can broaden our
understanding of fouling which can result in finding an effective and efficient
technique to control and even minimise it. Once a feasible solution for membrane
fouling is implemented, membrane bioreactors will become a more promising
technology for a wider range of wastewater treatment.
3.1 Membrane Fouling 41

3.1.1 Causes of Fouling

Huang et al. (2012b), Le-Clech et al. (2006b), Rana and Matsuura (2010) and Zhou
et al. (2014) state that fouling is caused by the interaction between the foulants
which may be particulate, colloidal particles or matters or biomacromolecules in
separation solutions and the membrane surface which includes: organic, inorganic
and biological substances in numerous forms. The foulants interact physically and
chemically with the membrane surface, however chemically it degrades the mem-
brane material. Consequently, non-specific adhesion of microorganisms and
biomacromolecules occurs on the membrane surface, resulting in blocked or
decreased greatly membrane pores and then a significant decrease in permeation
flux or separation efficiency.
Previous studies have indicated that the factors which affect membrane fouling
in membrane bioreactors are: the type of wastewater (Li and Yang 2007), sludge
age (Chang and Lee 1998), sludge loading rate (Chang et al. 2002), permeate flux
(Tradieu et al. 1998; Fan et al. 2000), aeration intensity (Bouhabila et al. 1998;
Howell et al. 2004), mixed liquor suspended solid concentration (MLSS) (Hong
et al. 2002; Le-Clech et al. 2003; Yamamoto et al. 1989), mechanical stress (Zeng
2007), solid retention time (SRT) (Shin and Kang 2003; Lee et al. 2003), food to
microorganism ratio (F/M), and hydraulic retention time (HRT) (Rosenberger and
Kraume 2002; Rosenberger et al. 2002a, b). Table 3.1 gives the relationship
between these factors and membrane fouling on the basis of recent research studies.
In addition to the factors above, the properties of mixed liquor have also been
thought to impact membrane fouling in MBRs. These properties include soluble
compounds (Wisniewski and Grasmick 1998), soluble microbial products
(SMP) (Huang et al. 2000; Lesjean et al. 2005; Liu et al. 2005), extracellular
polymeric substances (EPS) (Chang and Lee 1998), particle size distribution(Cicek
et al. 1999) and viscosity of mixed liquor (Ueda et al. 1996). Furthermore, the
research studies also illustrate that carbohydrate/protein has a solid relationship with
the evolution of membrane fouling in membrane bioreactor systems. However, a
clear relationship between carbohydrate/protein and membrane fouling in MBRs
was not apparently found in recent research studies in which pilot-scale experiments
were implemented by Kimura et al. (2005). Other investigators, for example
(Evenblij and van der Graaf 2004; Nuengjamnong et al. 2005; Drews et al. 2006a;
Geng and Hall 2007; Nagaoka et al. 1996; Ng et al. 2006) have concluded that EPS
and SMP are currently regarded as the major foulants of membranes in MBRs. The
deposition of EPS and SMP towards membranes can clog membrane pores and
form a fouling layer on the membrane surface, gradually increasing the filtration
resistance (Tansel et al. 2006; Brindle and Stephenson 1996; Chang and Lee 1998;
Cho and Fane 2002; Drews et al. 2007; Rosenberger and Kraume 2002). Zhang
et al. (2011a) vividly outlines the factors impacting membrane fouling in membrane
bioreactors (MBRs). The authors state that the primary cause of fouling originates
from three main parameters including membrane properties, sludge characteristics
and operating parameters; this can be seen in Fig. 3.2. The operating parameters
42 3 Fouling in Membrane Bioreactors

Table 3.1 Summary of the relationship between various fouling factors and membrane fouling
(Meng et al. 2009)
Sludge Effect on membrane fouling Reference
condition
MLSS – High MLSS leads to normalised lower permeability Trussell et al.
– High MLSS leads to higher fouling potential (2007)
– High MLSS leads to lower cake resistance, lower specific cake Psoch and
resistance Schiewer (2006)
Chang and Kim
(2005)
Viscosity – High viscosity leads to low membrane permeability Li et al. (2007)
– High MLSS/Viscosity leads to membrane permeability Trussell et al.
– High viscosity leads to high membrane resistance (2007)
Chae et al. (2006)
F/M – High F/M ratio leads to high fouling rates Trussell et al.
– MLSS (2–3 g/L): high F/M leads to high irremovable fouling (2006)
– MLSS (8–12 g/L): high F/M leads to higher removable fouling Watanabe et al.
– High F/M leads to high protein in foulants (2006)
Kimura et al.
(2005)
EPS – Increased polysaccharide concentration leads to increased Drews et al.
fouling rate (2006b)
– Bound EPS influences on specific cake resistance Cho et al.
– Increased polysaccharide concentration leads to increased (2005b)
fouling rate Lesjean et al.
– Increased bound EPS leads to membrane resistance (2005)
– The loosely bound EPS contributes to most of the filtration Chae et al. (2006)
resistance of the whole sludge Ramesh et al.
(2007)
SMP – SMP is more important than MLSS Zhang et al.
– Colloidal TOC relates with permeate flux (2006b)
– Filtration resistance is determined by SMP Fan et al. (2006)
– SMP is probably responsible for fouling Jeong et al.
– Polysaccharide is a possible indicator of fouling (2007)
– Low SMP leads to low fouling index Sperandio et al.
– Fouling rates correlate with SMP (2005)
Le-Clech et al.
(2005b)
Jang et al. (2006)
Trussell et al.
(2006)
Filamentous – High filamentous bacteria concentration leads to high sludge Meng et al.
bacteria viscosity (2007)
– Bulking sludge could cause a severe fouling Sun et al. (2007)
– Low filamentous bacteria concentration leads to cake Kim and Jang
resistance (2006)
Operating – Decreased SRT from 100 to 20 d leads to high TMP Ahmad (2007)
condition – Decreased SRT from 30 to 10 d leads to high fouling Zhang et al.
SRT – Decreased SRTs leads to high fouling potentials of SMP (2006b)
– Decreased SRT from 5 to 3 d leads to high fouling Liang et al.
(2007)
Cho et al.
(2005a)
(continued)
3.1 Membrane Fouling 43

Table 3.1 (continued)

Sludge Effect on membrane fouling Reference
condition
HRT – High HRT leads to high membrane fouling Meng et al.
– Lower HRT leads to high membrane fouling (2007a)
– Lower HRT leads to high membrane fouling Chae et al. (2006)
Cho et al. (2005)
Aeration – High aeration intensity leads to (high) permeability Trussell et al.
– Air sparging improves membrane flux (2007)
– Larger bubbles for fouling control are preferable Psoch and
– Air backwashing for fouling control is preferable Schiewer (2006)
– Bubble-induced shear reduces fouling significantly Phattaranawik
– Air scouring can prolong membrane operation et al. (2007)
Chae et al. (2006)
Wicaksana et al.
(2006)
Sofia et al. (2004)
Permeate flux – Subcritical flux mitigates irremovable fouling Lebegue et al.
– Subcritical flux mitigates fouling (2008)
Guo et al. (2007)

Fig. 3.2 Factors influencing membrane fouling in membrane bioreactors. Adapted from Meng
et al. (2009)
44 3 Fouling in Membrane Bioreactors

[e.g. dissolved oxygen (DO), solid retention time (SRT), hydraulic retention time
(HRT) and food to microorganism ratio (F/M)] have directly no impact on mem-
brane fouling but they determine the sludge characteristics. The optimisation of the
operating parameters can modify activated sludge. In terms of sludge characteris-
tics, their effects on membrane fouling are very complicated. Therefore, numerous
investigators recently add coagulant or adsorbent into membrane bioreactor systems
artificially to modify activated sludge. Their results were very effective in reducing
membrane fouling (Ji et al. 2008, 2010; Hwang et al. 2007; Koseoglu et al. 2008;
Teychene et al. 2011). Although all these research studies have been performed on
membrane fouling, they are still insufficient and many questions remain unan-
swered to date.

3.1.2 Effects of Fouling

Membrane fouling has a number of effects. First of all, it reduces the membrane
permeate flux either permanently or temporarily. If the fouling is temporary, then
the initial flux can usually be recovered by cleaning the membrane or by applying
backpressures to the temporarily fouled membrane. Membranes cannot be restored
when they are permanently fouled (Rana and Matsuura 2010). Second, it can
significantly reduce membrane performance, reduce separation efficiency, increase
maintenance and operating costs and rapid increase in transmembrane pressure
(TMP), shorten membrane lifespan, lead to more membrane cleaning or replace-
ment (HT et al. 2010; Yang et al. 2006b; Mansouri et al. 2010; Le-Clech et al.
2006b; Shirazi et al. 2010; Wu and Huang 2010b; Wu et al. 2010; Zhang et al.
2011b). It should be noted that although flux decrease is also associated with the
phenomenon of concentration polarisation, this is not considered as fouling because
it disappears when the filtration process is stopped.

[Link] Models of Membrane Fouling

Membrane fouling can be mainly described either by external fouling or internal

fouling. Internal fouling occurs when particles deposit inside the membrane
structure, leading to blocked pores partially or completely, reducing the effective
pore diameter and even reducing flow through the membrane (Baker 2012; Ma et al.
2007). The standard blocking model (SBM), the complete blocking model
(CBM) and the intermediate blocking model (IBM) are three models used to
describe internal fouling. By contrast, at the early stage of filtration, external fouling
refers to surface fouling and occurs thoroughly on the membrane surface when the
colloids accumulate; the accumulation of aggregated colloids may lead to blocking
pores and finally form a cake layer/film on the membrane surface. External fouling
can be removed a certain extent via cleaning procedure. The cake filtration model
(CFM) is usually used to describe external fouling.
3.1 Membrane Fouling 45

Fig. 3.3 Illustration of several membrane fouling mechanisms. Adapted from Leiknes (2012)

Furthermore, during membrane filtration there have been four fouling models
employed to describe the mechanisms of membrane fouling as shown schematically
in Fig. 3.3 (Oh et al. 2009).
1. Cake filtration—A uniform cake layer formed upon the entire membrane surface
as a consequence of the deposition and accumulation of particles with a larger
diameter than the membrane pore size. Cake fouling is generally reversible by
water flushing or backwashing (Baker 2012).
2. Complete pore blocking or plugging—this can be caused by occlusion of pores
with particles. Superimposition is impossible.
3. Intermediate pore blocking—Similar to complete pore blockage, though the
particles have the capability to deposit on the top of other deposited particles.
This can only occur under these conditions, superimposition is possible.
4. Standard blocking—Particles with a smaller pore size enter the pores and
deposit on the internal pore surfaces with their whole length, causing the nar-
rowing of the pore size.
These fouling models supply a visible picture of the relative position of particles
towards membranes. Additionally, they provide a mathematical model of the flux
filtration behaviours under constant pressure filtration mode, which can be char-
acterised by a significant plummet in the flux at the beginning of the process,
followed by decreasing curve slope until the steady state is achieved. Moreover,
developments and extensions make these fouling models applicable for constant
flux filtration and spread out some combined models.
46 3 Fouling in Membrane Bioreactors

[Link] Types of Fouling

Generally, according to the chemical nature of foulants, membrane process and the
types of foulants and their interaction with membrane surface, several types of
membrane fouling have been identified in membrane bioreactors (Kochkodan and
Hilal 2015; Pan et al. 2010; Flemming 1997; Flemming et al. 1997; Kimura et al.
2004) as shown below:
1. Removable and irremovable fouling.
2. Organic fouling or scaling.
3. Inorganic fouling.
4. Biofouling.
5. Reversible and irreversible fouling.
6. Colloidal fouling.

Removable and irremovable fouling

The control and investigation of both irremovable membrane and removable
fouling in MBRs is of significant importance for long-term membrane operation
and sustainable operations of MBRs. During initial filtration, solutes, colloids and
microbial cells pass through the membrane and precipitate progressively inside the
membrane pores. Whilst for long-term operation of MBRs, the deposited cells
aggregate in MBRs and form EPS, which is considered as one of the major foulants
of membrane in MBRs. EPS is a complex mixture of carbohydrates, proteins,
humic compounds, uronic acids and DNA. EPS form a strongly attached fouling
layer on the membrane surface and clog the membrane pores partially or com-
pletely. Meantime, some inorganic substances might stick progressively on the
membrane surface or in the membrane pores (Meng et al. 2009).
Irremovable fouling can be caused by pore blocking and strongly attached
foulants during filtration, whilst removal fouling is caused by foulants that loosely
attach and is associated by the cake layer formation above the membrane surface.
Therefore, to counteract removable and irremovable fouling propensities, many
researchers stated that operation below the critical flux is the best approach to
control membrane fouling, particularly removable and irreversible fouling within a
specified filtration system. For example, (Field et al. 1995) introduced the concept
of critical flux. This flux is called subcritical flux or non-fouling operation if the
operation is below the critical flux and is expected to cause less irremovable
fouling. For a short-term membrane operation, when the permeate flux or mem-
brane permeation is less than the critical flux filtration conditions, the transmem-
brane pressure (TMP) remains constant and fouling was removable. By contrast,
when the permeate flux exceeds the critical flux, the TMP increases and is expected
to increase significantly. Indeed, for long-term membrane operation, irremovable
fouling can appear if the process is operated below the critical flux. Ognier et al.
(2004) stated that with the choice of subcritical flux filtration conditions, a slight
3.1 Membrane Fouling 47

membrane fouling was still seen to develop, which proved to be hydraulically

irremovable after long-term operation. The critical flux value relies on operating
conditions (i.e. aeration intensity, temperature), membrane characteristics and
sludge characteristics. The principle of critical flux has gained popularity in the
study of MBR fouling (Guglielmi et al. 2007a, b; Lebegue et al. 2008; Wang et al.
2008). However, most of the research studies on the determination of critical flux
are based on ex situ measuring which cannot provide reliable information about
MBRs fouling. Therefore, in recent years, De La Torre et al. (2008) developed an
in situ measuring method in which more reliable information can provide about
critical flux in comparison to ex situ measuring method. This method is superior to
the ex situ measuring method. Another research study was conducted by Huyskens
et al. (2008), using an online measuring method. In this study, the removable and
irremovable fouling intensities of MBR were evaluated in a reproducible way. This
method seems to be more practical approach to evaluate fouling in MBRs. These
research studies state that it is possible to develop online method or in situ method
to determine removable/irremovable fouling or determine critical flux. It is also of
great interest to develop an apparatus or a unified measuring method to verify
membrane propensity.
As mentioned previously, irremovable fouling plays an important role in the
long-term MBR operation. Therefore, chemical cleaning is necessary to maintain
MBR operation. But, chemical cleaning for the sake of eliminating irremovable
membrane fouling should be limited to a minimum because repeated chemical
cleaning may shorten membrane lifespan, degrade the membrane and the disposal of
spent chemical agents causes environmental issues (the chemical agents are not
friendly to environment as it leads to pollution of water) (Yamamura et al. 2007a, b, c).
On the other hand, removable fouling can be eliminated by the execution of physical
cleaning (e.g. backwashing/backflushing/relaxation) (Meng et al. 2009). Figure 3.4
depicts the process of formation of removable and irremovable fouling and their
elimination in membrane bioreactors.
Organic fouling
Schafer et al. (2005) outlines that organic fouling is an irreversible process caused
by the adsorption/retention of dissolved organic materials. Whilst, Meng et al.
(2009) define organic fouling as the deposition of (soluble microbial product) SMP
or NOM (natural organic matter) which is composed of proteins, polysaccharides
and humic substances on the surface of membrane bioreactors. SMP or NOM can
be easily retained onto the membrane surface due to the small size and the permeate
flow as the back transport to the bulk phase due to lift forces is very weak compared
with large particles (e.g. colloids and sludge flocs). For NOM, humic substances
have been considered as major foulants which can cause severe irreversible foulants
in pressure-driven membrane processes through membrane adsorption and pore
blocking (Escobar 2005). This results in a flux decline. Also polysaccharides (with
large particle size) are of high importance for membrane fouling when
pressure-driven membrane (UF) is used for water recycling (Laabs et al. 2006).
48 3 Fouling in Membrane Bioreactors

Fig. 3.4 Schematic illustration of the formation and removal of removable and irremovable
fouling in membrane bioreactors. Adapted from Meng et al. (2009), Pollice et al. (2005)

It is difficult to recognise the mechanism attributed with organic fouling due to

the chemical properties of the molecule, the interactions of chemicals properties
with the membrane materials and strong effects of organic types. Nevertheless,
colloidal fouling and organic fouling usually intertwine for some reasons. First, the
colloids adsorb organic matter in the natural environment and a negatively charged
surface to stabilise them. Second, some organics with the sizes ranging from 1 nm
to 1 lm can be referred to colloids, such as natural organic matter (NOM). Up until
now, the only two vital mechanisms that can explain organic fouling are gel layer
formation and initial adsorption.
Gel layer is formed as a result of an excess solubility of organic molecules and the
appearance of organic flocculation. Generally, it is attributed with the concentration
3.1 Membrane Fouling 49

polarisation when the rise in concentration reaches the top layer of the membrane
surface. Many investigators identify Natural Organic Matter (NOM) as the major
foulant associated with organic fouling (Al-Amoudi and Farooque 2005; Rana and
Matsuura 2010; Roudman and Digiano 2000). Kim et al. (2007) characterised the
formation of NOM on flat sheet membrane surface using dead-end cell filtration. The
results of Scanning Emission Microscope (SEM) indicate that NOM gets accumu-
lated and a gel layer is formed on the membrane surface though it does not breach the
membrane body. In contrast to other research studies, NOM can reduce the effective
pore size by adsorbing on the pore wall. Rana and Matsuura (2010) state that NOM
could be controlled by electric double layer repulsion and permeation hindrance. It
has been demonstrated that the hydrophobic fraction of NOM was the major factor in
causing the flux decline. This is because of the strong adsorption of hydrophobic
NOM on the membrane surface. The hydrophilic fraction of NOM had a relatively
small effect on the membrane fouling (Nilson and DiGiano 1996). Recently,
(Metzger et al. 2007) have performed a comprehensive research study to characterise
the deposited biopolymers in MBRs. After membrane filtration, the fouling layers
were divided into three layers (upper layer, intermediate layer and lower layer) using
rinsing (washing), backwashing and chemical cleaning. The results showed that the
upper fouling layer was composed of a porous, loosely bound cake layer with the
same composition to sludge flocs (biomass flocs). The intermediate fouling layer
equally consisted of soluble microbial product (SMP) and biomass aggregates,
resulted in a high concentration of polysaccharides. Whilst, the lower layer was
predominated by SMP and represented the irremovable fouling fraction, which had a
relative higher concentration of strongly bound proteins. This study showed the
spatial distribution of SMP on the surface of membrane.
Whilst adsorption occurs when organic matter and membrane interact
physico-chemically. Combe et al. (1999) confirmed that the organic components
directly adsorb to the membrane surface or inside the pores in a form of a thin layer,
using humic acid as the foulant model. Hence, the characteristics of the membrane
surface such as hydrophobicity, surface charges and pore size change. The afore-
mentioned characteristics result in fouling to some extent. It should be noticed that
after the initial adsorption of the organics, the newly formed thin surface might have
completely distinct characteristics compared with the original membrane surface,
which mainly depends on the solutes. Under this consideration, gel layer formation
seems to be more responsible for the organic fouling.
In order to figure out the detailed information on the deposited biopolymers (i.e.
Protein, humic substances, polysaccharides), the identification of these substances
is indispensible part. Fourier transform infrared spectroscopy (FTIR), excitation–
emission matrix fluorescence spectroscopy (three dimension tool) EEM and high
performance size exclusion chromatography (HOP-SEC) are three analytical tools
used to investigate organic fouling. The major components of NOM foulants were
identified as protein using FTIR (Lee et al. 2004) whilst EEM were usually used to
characterise protein-like or humic-like substances in membrane foulants.
50 3 Fouling in Membrane Bioreactors

Inorganic fouling or scaling

Fouling in membrane bioreactors is mainly dominated by organic fouling and
biofouling, whilst inorganic fouling is the weakest threat. All of them occur
simultaneously during the membrane filtration of activated sludge (Meng et al.
2009). Despite numerous research studies focused on membrane fouling, not much
light has been shed on inorganic fouling in MBRs. Speth et al. (1998) define
inorganic fouling as the agglomeration of materials on the surface of a membrane,
or in membrane pores. Van De Lisdonk et al. (2000), Kochkodan and Hilal (2015)
contend that inorganic fouling is the result of high concentration of one or more
inorganic salts in raw water beyond the inorganic salts limited solubility and their
ultimate precipitation on the membranes. Conspicuously, this can be seen vividly in
the region near the surface of nanofiltration membranes NF and also near the RO
membrane surface where the concentration of dissolved salts is 4–10 times higher
than the bulk feed water. This is due to concentration polarisation (CP), resulting in
the precipitation of constituent ions (e.g. BaSO4 and CaCO3) on membrane surface
(Van De Lisdonk et al. 2000; Wu 2012). It is documented that inorganic substances
are a contributor factor to less than 15 % of membrane foulants in pilot nanofil-
tration plant for the treatment of surface water. A severe fouling is expected when
the presence of calcium and alginate is due to the complexation between them.
Scaling refers to the formation of inverse solubility salts, such as CaSO4.xH2O,
CaCO3, SiO2, Mg (OH) 2 and Ca3 (PO4) 2 deposits. These salts are responsible for
inorganic fouling on the membrane surface and their solubility products are illus-
trated below in Table 3.2 (Lee et al. 1999; Van De Lisdonk et al. 2000; Lin et al.
2005; Shirazi et al. 2006). According to (Hasson et al. 2001), the compounds with
the greatest scaling in NF and RO are CaCO3 and CaCO4.2H2O, whilst other
potential scaling compounds are BaSO4, SrSO4, Ca3(PO4)2 and Fe(OH)3. The salt
precipitates when the solubility product of the constituent ions exceeds the solu-
bility limit. Table 3.2 illustrates the solubility product of the common inorganic
salts that cause scaling on the surface of the membrane.
Other investigators, for example Kang et al. (2002) and Ognier et al. (2002a, b, c)
suggest that inorganic fouling may take place more readily on inorganic membranes.
Due to the cohesive properties, a cake of inorganic material can generally become
irremovable. Recently, Wang et al. (2008) asserted that the cake layer is formed by
organic substances and inorganic elements such as Mg, Al, Fe, Ca, Si, etc. When the
organic foulants are coupled with the inorganic foulants, precipitation promotes the
formation of a cake layer.
Recently, inorganic fouling has been investigated in MBR processes. Ognier
et al. (2002a, b, c) state that severe CaCO3 fouling is expected in a pilot MBR with
a ceramic ultrafiltration membrane. They prepared synthetic wastewater with hard
tap water (Ca+2 = 120 mg/l; Mg+2 = 8 mg/I). They concluded that higher alkalinity
of the activated sludge (pH = 8–9) leads to pre-precipitation of CaCO3. Lyko et al.
(2007) found that metal substances (i.e. Fe+3) were regarded as major contributors
to membrane fouling than biopolymers (i.e. protein, polysaccharides). You et al.
(2006) point out that the fouling caused by inorganic scaling is not readily removed
3.1 Membrane Fouling 51

Table 3.2 Solubility Fouling salt Solubility product

products of the common
inorganic salts that cause CaCO3 2.8  10−9
scaling on membrane surfaces CaHPO4 1  10−7
(Pollice et al. 2005; Xie et al. CaSO4 4.93  10−5
2004) Ca3(PO4)2 2.07  10−29
MgCO3.3H2O 2.38  10−6
Mg3(PO4)2 1.04  10−24
AlPO4 9.83  10−21
Al(OH)3 1.3  10−33
Ca(OH)2 5.5  10−6
CaHPO4 1.0  10−9
Fe(OH)3 2.79  10−39
FePO4.2H2O 9.92  10−29

by chemical cleaning. These research studies demonstrate that inorganic fouling has
become paramount in MBRs. The understanding of inorganic fouling however is
still vague. Studies conducted on metal ions with limited concentrations submerged
in the feed of wastewater may promote inorganic fouling, and this may be an
important area of research in the foreseeable future. Even though, the chemical
composition of wastewater is directly correlated with precipitants formed.
As noted by (Meng et al. 2009), inorganic fouling can be formed by two paths as
shown schematically in Fig. 4.6. The first way is referred as chemical precipita-
tion and the second one is biological precipitation. In membrane bioreactors, a
variety of cations and anions and others are present such as Ca2+, Mg2+, Al3+, Fe3+,
CO32+, SO42−, PO43− and OH−. Concentration polarisation will lead to higher
concentration of deposited salts on the surface of membrane, particularly for
applications of RO and NF.
Chemical precipitation on the one hand, takes place when the concentration of
chemical species exceeds the saturation concentrations owing to concentration
polarisation. Furthermore, as biocake or biofilm is naturally elastic, In addition, the
fouling layer on the membrane surface can protect the surface layer from shear
stress as biocake is naturally elastic, resulting in higher concentration polarisation
(CP) and precipitation of inorganic salts (Sheikholaslami 1999; Sheikholeslami
1999). Carbonates are one type of the predominant salts in inorganic fouling. The
carbonates of metals such as Ca, Mg and Fe can potentially increase membrane
scaling (You et al. 2005).
Biological precipitation, by contrast, is another factor to inorganic fouling. The
biopolymers (i.e. Protein) contain negative ions such as COO−, CO32−, SO42−,
PO43− and OH−. The metal ions can be readily caught by these negative ions.
Acidic functional groups (R–COOH) and calcium (Ca+2), in some cases, can
produce complexes and build a dense gel layer (a network of rigid organic matter)
that may lead to flux decline (Costa et al. 2006). When the metal ions pass through
the membranes, they could be captured by the attached biocake layer on membrane
52 3 Fouling in Membrane Bioreactors

Fig. 3.5 Schematic

illustration of the formation of
inorganic fouling in
membrane bioreactors, as well
as a representation of
biological precipitation.
Adapted from Meng et al.
(2009), Pollice et al. (2005)

through charge neutralisation and complexation and therefore speed up membrane

fouling. Connection between the deposited cells and biopolymers further enhanced
the compactness of the fouling layer and then form a dense cake layer on mem-
branes (Hong et al. 1997). The synergistic interaction between different types of
fouling (biofouling, organic fouling and inorganic fouling) could result in more
foulants deposited on the surface of membrane. Figure 3.5 illustrates chemical and
biological precipitation.
Bear in mind, inorganic fouling is a complex phenomenon in membrane biore-
actors. Therefore, different methods have been performed to avert inorganic fouling.
One of these methods is pretreatment of feed water or use of chemical cleaning.
Chemical cleaning is very straightforward method and simpler than physical one in
removal of inorganic precipitation as inorganic fouling can result in severe irre-
movable fouling. Meng et al. (2009) propose using Ethylenediaminetetraacetic acid
(EDTA) (is an amino polycarboxylic acid, a colourless and water-soluble solid) as
chemical agents that might eliminate inorganic materials on the membrane surface
effectively. Indeed, EDTA can produce a strong complex when reacts with Ca+2.
Thus, biopolymers associated with Ca+2 ions are exchanged by EDTA through a
ligand exchange reaction (Al-Amoudi and Lovitt 2007). Kim and Jang (2006) state
that the existence of metal ions (e.g. calcium) in membrane bioreactors can be
3.1 Membrane Fouling 53

beneficial for the membrane permeation in some membrane processes due to its
positive effect on colloid or sludge flocculation.
The mechanism of inorganic fouling involves the crystallisation of the salts ion
precipitated from the bulk feed solution and particulate fouling. Lee et al. (1999)
point out that there are indeed two ways of crystallisation in the membrane filtration
using CaSO4 as the fouling salt: the first way is surface crystallisation (homoge-
nous) and the second one is bulk crystallisation (heterogeneous). Surface crys-
tallisation (homogenous), on the one hand, produces solid crystals directly on
membrane surface. It is caused by formation of nuclei on the membrane active sites
or impurities on the membrane surface as nucleation sites and lateral growth of
crystals. By contrast, bulk crystallisation occurs due to the homogenous or sec-
ondary crystallisation in the bulk phase and then deposited to the membrane surface
(Okazaki and Kimura 1984; Pervov 1991). These two mechanisms of crystallisation
may simultaneously emerge through membrane filtration, and flux decline takes
place (Lee and Lee 2000). Figure 3.6 shows the scale formation mechanisms in NF.
Biofouling
Biofouling is generally one of the most common and serious issues for membrane
used in many applications such as bioseparation, water and wastewater treatments,
membrane bioreactors, reverse osmosis, desalination (Xu et al. 2010; Miura et al.
2007; Kramer et al. 1995; Flemming 1997; Flemming et al. 1997; Baker and Dudly

Fig. 3.6 Schematic representation of inorganic fouling mechanisms. Adapted from Shirazi et al.
(2010)
54 3 Fouling in Membrane Bioreactors

1998; Guo et al. 2012; Liao et al. 2004; Ramesh et al. 2006; Liu et al. 2012; Yao
et al. 2010, 2011). It appears after organic, inorganic and colloidal fouling.
Many researchers, for example Baker and Dudly (1998), Huang et al. (2012b),
Khan et al. (2011), Vrouwenvelder et al. (2011), Baker (2004), Flemming and
Schaule (1988) state that membrane biofouling causes a number of serious issues
which include
1. A reduction in membrane permeation due to establishment of a gel-like diffusion
barrier (e.g. the biofilm) on the membrane surface.
2. An increase in solute concentration polarisation accompanied by lower solute
rejection (in RO and NF membranes).
3. An increase in the module differential pressure (DP) and feed pressure being
required to maintain the same production rate due to biofilm resistance.
4. Biodegradation and/or biodeterioration of the membrane polymer or other
module construction materials (e.g. polyurethane-based glue lines).
5. Establishment of concentrated populations of primary or secondary human
pathogens on membrane surfaces.
6. Increased energy requirements due to the higher pressure being required to
control the biofilm resistance and the flux decline.
7. Shortens membrane lifespan.
As noted by Pang et al. (2005), Wang et al. (2005), biofouling refers to
deposition/retention, growth, and metabolism of bacteria cells (marine bacteria,
diatoms and green algae) or flocs on the membranes, which is a significant concern
in membrane filtration processes. Biofouling is also a major hitch for pressure—
driven membranes such as ultrafiltration and microfiltration (used for treating
wastewater) because most foulants (colloids and sludge flocs) in MBRs are much
larger than the membrane pore size. Kochkodan (2012) defined membrane bio-
fouling as a dynamic process of microbial colonisation and growth, which results in
the formation of microbial films onto membrane surface, differentiation of micro-
bial films into mature biofilm and eventually biofilm detachment and dispersal as
shown schematically in Fig. 3.7.
Biofouling often makes the membrane surface become non-regenerable and
therefore more replacement or cleaning of the membrane is required, which con-
tributes significantly to the application cost (Baker and Dudly 1998). As a matter of
fact, biofouling term used to describe many fouling phenomena where biologically
active organisms such as fungi, viruses and microorganisms and excreted extra-
cellular biopolymers are involved (Flemming 1997; Flemming et al. 1997; Liao et al.
2004; Ramesh et al. 2006). Biofouling is considered as a common encountered
problem of the synthetic polymeric membrane surface because it diminishes the
treatment process efficiency and cost effectiveness (Flemming and Schaule 1988).
Membrane biofouling is inherently very complicated than other membrane
fouling phenomena because microorganisms can grow, multiply and relocate over
time on the surface of membrane. Biofouling has been regarded as a contributing
factor to more than 45 % of all membrane fouling phenomena (Komlenic 2010).
3.1 Membrane Fouling 55

Fig. 3.7 Models of the development of a mature P. aeruginosa biofilm from planktonic cells.
Adapted from Kim et al. (2007), Wu (2012)

Membrane biofouling is usually initiated by microbes or bacteria that attach and

grow on the surface of the membranes in use (Miura et al. 2007; Vrouwenvelder and
Kooij 2001; Baker and Dudly 1998; Flemming 1997; Flemming et al. 1997). Since
most conventional membranes are prone to bacterial attachment and growth (Baker
and Dudly 1998; Flemming et al. 1997). Baker and Dudly (1998), Chen et al. (2004)
point out that membrane biofouling is mainly caused by Corynebacterium,
Pseudomonas, Bacillus, Arthrobacter, Flavobacterium and Aeromonas bacterial
species and to a minimum extent by fungi such as Trichoderma, Penicillium and
other eukaryotic microorganisms. Some microorganisms inherently seem ‘sticky’
and rapidly tend to adhere to any surface practically, while others respond more
slowly and only adhere to certain surfaces after some time. Flemming and Schaule
(1988) found that Pseudomonas vesicularis, Acinetobacter calcoaceticus and
Staphylococcus warneri have been identified as fast adhering species out of a tap
water microflora: then, the first irreversible attachment of cells take places after few
minutes of contact between membrane and raw water. If non-starving cells are used,
the adhesion process is strongly dependent on the number of cells in suspension with
a linearity between the logarithms of numbers of suspended and adhering cells above
106 cells/ml up to complete covering of the surface (3  107/cm2). Starving cells do
56 3 Fouling in Membrane Bioreactors

not cover the surface completely but colonise it in an island pattern with free
membrane areas in between Flemming and Schaule (1988). As a matter of fact, the
differences in microbial adhesion to membrane surfaces over long time may result
from biological factors such as the nutritional condition and growth plate of the
microbe, but the initial attachment is largely governed by physico-chemical factors
such as hydrodynamic conditions (Kang et al. 2004; Schneider et al. 2005) and
membrane surface properties (Ridgway et al. 1985).
Many investigators propose that soluble microbial product (SMP) and extra-
cellular polymeric substance (EPS) released by bacteria also play important roles in
the formation of biological foulants and cake layer on membrane surfaces by
altering their physico-chemical characteristics such as hydrophilicity and surface
charge (Flemming et al. 1997; Liao et al. 2004; Ramesh et al. 2006; Neu and
Marshall 1990). EPS primarily consists of polysaccharides, proteins, glycoproteins,
lipoproteins and other macromolecules of microbial origin (Beer and Stoodley
2013). It contains both hydrophobic and hydrophilic sites on its chemical structure,
which enable the polymer to settle on both hydrophilic and hydrophobic properties.
As noted by Neu and Marshall (1990), the interaction force between the EPS and
the membrane surface may be physical (adsorption), chemical (covalent bonding)
or electrostatic. EPS account for 50–90 % of the total organic carbon (TOC) of
biofilms and can be considered as the primary matrix material of the biofilm.
Membrane biofouling is usually regarded as irreversible process and is very hard
to handle due to the self-replicating nature of microbes or foulants (Flemming et al.
1997; Kappachery et al. 2010). Therefore, many techniques have been performed
over the last two decades to control membrane biofouling. The common strategy to
deter membrane biofouling is often to add biocides or antibacterial agents, such as
heavy metals, including zinc, copper, chlorine, silver into the feed stream of the
membrane process (Huang et al. 2012b; Zhang et al. 2012; Zhu et al. 2010). The
use of chlorine would kill 99.99 % of bacteria in the feed stream, this approach may
not be effective to eliminate membrane biofouling because they are still enough
bacteria remaining which can migrate to the membrane surface, relocate and
multiply rapidly, especially at high feed temperature and in wastewater treatment or
desalination where higher contents of nutrients are available in the feed for bacterial
growth (Zhu et al. 2010). Besides chlorine, silver is another type of biocide or
antibacterial agent, which is extensively used in different applications, despite the
fact that the study of silver for the purpose of membrane anti-biofouling has been
very limited (Chae et al. 2009; Zhu et al. 2010). Silver nanoparticles have attracted
considerable attention due to their catalytic, optical and conducting properties
(Koga et al. 2009). It is concluded that the use of silver as an effective antibacterial
agent has well known for a long time (Koga et al. 2009; Matsumura et al. 2003).
Lee et al. (2007) argue that the grafting of silver nanoparticles onto the surface of
polyamide nanofiltration membrane was shown to prevent biofouling problem
effectively and also enhance the performance of nanofiltration membrane. Huang
et al. (2014) demonstrate that the incorporation of Ag-SiO2 to PES membrane
would improve the hydrophilicity of the membrane, which will also enhance the
anti-biofouling properties. Apart from silver, zinc has also been used as
3.1 Membrane Fouling 57

anti-biofouling membrane (Zhang et al. 2014). Incorporating zinc into polymer

membranes would improve antibacterial or anti-biofouling performance. Zhang
et al. (2014) concluded that introducing poly (zinc acrylate) (PZA) into PES
membrane would be a simple route to improve the anti-biofouling properties of
membranes. The biofouled membranes can be visualised using different analytical
techniques such as Atomic force microscopy (AFM), Scanning electron microscopy
(SEM), Confocal Laser scanning microscopy (CLSM) and direct observation
through the membrane (DOTM).
Reversible and irreversible fouling
Irreversible fouling is a kind of fouling that exhibits a marked dependence on the
surface membrane properties, whilst reversible fouling is only weakly dependent on
the membrane surface chemistry.
Irreversible fouling is caused by strong adherence to the membrane such as pore
blocking, gel layer formation or biofilm formation. Huyskens et al. (2008), Meng
et al. (2009) point out that irreversible fouling cannot be removed by any methods
including chemical method (using sodium hypochlorite (NaOCl) as chemical agent
for cleaning). But, many researchers (Huang et al. 2012a, b; Judd 2007; Judd and
Jefferson 2003) state that the irreversible fouling can solely be eliminated by
chemical reagent but repeated chemical cleaning may reduce the membrane per-
formance, leading to membrane degradation. Reversible fouling, on the contrary,
occurs due to external deposition of material (cake filtration) and is mostly removed
by hydraulic cleaning such as backwashing or cross-flusing and relaxation.
Concentration polarisation and cake layer formation are often considered as
important reversible fouling mechanisms. A superior control of both reversible and
irreversible fouling would decrease operational costs associated with membrane
cleaning, thereby making MBRs more competitive in comparison to conventional
wastewater treatment plants (Judd 2006). Huyskens et al. (2008) used a new
method to evaluate irreversible and reversible fouling. This method is called the
MBR-VFM (VITO Fouling Measurement). This method is a further modification of
the VFM, which was developed about 5 years ago as an alternative method to
determine the fouling tendency of aqueous feeds in pressure-driven filtration pro-
cesses. Table 3.3 presents typical ranges of various fouling rates at full-scale plant.
As can be seen from the table, each fouling type has a different fouling rate and time
frame over which it appears.

Table 3.3 Typical ranges for different fouling rates occurring at full-scale operation (Guglielmi
et al. 2007a, b; Kraume et al. 2009; Pollice et al. 2005)
Category Fouling rate in mbar/min Time frame
1. Reversible fouling (Cake filtration) 0.1–1 10 min
2. Residual fouling 0.01–0.1 1–2 weeks
3. Irreversible fouling 0.001–0.01 6–12 months
4. Irrecoverable fouling 0.0001–0.001 Years
58 3 Fouling in Membrane Bioreactors

Colloidal and particle fouling

Colloidal fouling refers to membrane fouling with colloidal and suspended particles
in the size range of a few nanometres to a few micrometres. Particulates below this
range are considered to be dissolved in water. A wide number of colloidal and
particulates foulants with different size range have been studied by many investi-
gators (Potts et al. 1981; Yiantsios et al. 2005). Examples of these foulants include
silts and clays, silica salts, humic acid, hydroxides of heavy metals, precipitated
crystals and iron, and aluminium compounds (Buffle and Leppard 1995; Buffle
et al. 1998). Some of these foulants include
• Microorganisms.
• Biological debris (plant and animal).
• Polysaccharides (gums, slime, plankton, fibrils).
• Lipoproteins.
• Clay (hydrous aluminium and iron silicates).
• Silt.
• Oils.
• Kerogen (aged polysaccharides, marine snow).
• Humic acids, lignins, tannins.
• Iron and manganese oxides.
• Calcium carbonate.
• Sulphur and sulphides.
The increased concentration of the rejected ions at the front of the membrane
surface facilities the accumulation of dissolved organic substances, for instance,
natural organic matter (NOM) onto colloidal-sized particles (Hong and Elimelech
1997). Colloidal fouling mainly depends on the colloidal particle relative to the
membrane pore size.
As stated by Boerlage et al. (2003), silt density index (SDI) and modified fouling
index (MFI) are the most widely applied methods in the NF and RO that are used
for evaluation of membrane fouling potential generated by dispersed particulate
matters (colloids, suspended solids) in the feed. Severe fouling is expected to be
high when SDI and MFI are high. SDI and MFI methods use only one number
value to evaluate the feed water. However, these fouling indices are based on feed
passing through a 0.45-µm microfiltration membrane to measure the fouling
potential, they cannot explain the decrease of flux rate effectively because of their
limited ability to retain colloids smaller than 0.45 µm which is responsible for
membrane fouling. As stated by Brauns et al. (2002), SDI and MFI indices use only
one value to predict the fouling propensity of the feed, failing to reflect different
fouling mechanisms of RO/NF membranes. Therefore, development of alternative
robust and predictable fouling indices has been the subject of numerous research
studies. This can be done by modifying fouling index experiments to utilise test
membranes with pore size smaller than 0.45 µm. The colloids film can be formed in
two stages; internal and external fouling (Czekaj et al. 2000; Visvanathan and Ben
aïm 1989) as was discussed earlier in this chapter.
3.1 Membrane Fouling 59

3.1.3 Techniques for the Control of Membrane Fouling

in Membrane Bioreactors

As mentioned previously, membrane fouling is a very complex phenomenon in all

membrane processes, especially membrane bioreactors. The complexity of mem-
brane fouling means that a variety of approaches will be necessary to decrease its
impact (Hilal et al. 2005). These approaches are grouped under six main topics
(1) pretreatment of feed, (2) optimization of operating conditions, (3) cleaning
procedure, (4) membrane materials/surface modification of membrane, (5) gas
sparging and (6) pulsatile. These distinct approaches are discussed in detail in the
following sections.

[Link] Pretreatment of Feed

The effects of membrane fouling can be reduced by feed pretreatment. Feed pre-
treatment is a crucial step in MBR process. This approach is widely used to
eliminate the particulates or macromolecules that cause pore clogging or prevent
them from depositing onto the surface of the membrane. Feed pretreatment is an
effective approach as it contributes to reducing the consequences of membrane
fouling (biofouling) and it involves both physical and chemical approaches. The
physical approaches normally include prefiltration or centrifugation process to
eliminate the suspended particles that have the tendency to plug the membrane
module or attach to the membrane surface. Heat treatment followed by settling is
the most common type of physical process. It is used specifically in dairy plant to
remove fats and immunoglobulin’s from cheese whey prefiltration prior to ultra-
filtration (Aptel and Clifton 1986).
In contrast, chemical approaches are another approach, which include different
processes such as coagulation, precipitation or flocculation and the use of propri-
etary chemicals as disinfectants. pH adjustment of the feed causes foulants to
further away from their isoelectric points which eventually reduce their propensity
to form a gel layer (Peuchot and Aim 1992). Removing any colloids (particulate
matter) and therefore preventing particles from depositing on the surface of
membranes requires the usage of both chemical and physical processes. As stated
by Boissonade et al. (1991), using coagulation agents and flocculation could reduce
membrane fouling by the accumulation of the colloidal fraction, therefore, reducing
the internal blocking of the membrane. The function of the coagulants is to elim-
inate the internal blocking of the membrane by settling the colloidal matters and
supporting them to form large aggregates in order to produce higher rates of per-
meation flux. The addition of coagulant can not only improve permeation flux but
also enhance the quality of membrane effluent. Four distinct mechanisms of
chemical coagulants can impair colloidal particles, which include (i) charge neu-
tralisation, (ii) double layer compression, (iii) enmeshment in a precipitate and
(iv) interparticle bridging (Hilal et al. 2005).
60 3 Fouling in Membrane Bioreactors

A research study was conducted on using coagulants to improve the formation of

large aggregates from the initial molecules that would be easily swept of the
membrane surface. Two types of coagulant have been used for water and
wastewater treatment application such as ferric chloride and alum (also called
aluminium sulphate). These coagulants are thoroughly added to significantly reduce
membrane bioreactor fouling. As noted by Holbrook et al. (2004), when alum
dissolved in water, it forms hydroxide precipitates which adsorb materials such as
suspended particles, colloids and soluble organics. In MBR-based trials, the addi-
tion of alum resulted in significant decrease of the SMPc [fraction of carbohydrate
contained in the sludge solution (mg/gSS)] concentration, along with an amelio-
ration in the hydraulic performance of the membrane. Large microbial flocs are
supposed to have a lower impact on membrane fouling because of back transport
and shear induced fouling control mechanisms. Therefore, the improvement of
permeability or permeate flux in MBRs system is due to the formation of largest
flocs. As stated by Lee et al. (2001b) small biological colloids (from 0.1 to 2 µm)
have been observed to coagulate or condensed and formed larger particles when
alum is added to MBR-activated sludge.
Although highly costly, dosing with ferric chloride (FeCl3) was found to have
higher efficiency than that of alum. It was used to remove large-sized organic
compounds. In MBRs, zeolites have also implemented and promoted the creation of
rigid flocs that have specifically lower fouling resistance. Ferric iron has also been
added to MBRs to enhance the production of iron oxidising bacteria, which is
responsible for the degradation of H2S gas. Specific ferric precipitate, for example
ferric phosphate and K-jarosite (K-Fe3(SO4)2(OH)6) have been seen to foul the
membrane (Park et al. 2005). A recent research study conducted by Itonaga et al.
(2004) showed that both suspension velocity and irreversible fouling can be con-
trolled with the addition of iron as a coagulant. Ferric hydroxide flocs have been used
as membrane precoating agent in membrane bioreactor process. The results showed
that the permeability was higher than that of uncoated MBR system. Also the effluent
quality was improved significantly in this study (Zhang et al. 2004). In that study
ferric chloride was used in MBR systems, which successfully removed the
non-biodegradable organics that aggregated in the MBR systems. This operation
also resulted in significant increase in membrane permeation or permeability flux

[Link] Optimization of Operating Conditions

Improvement of operating conditions at the membrane surface during membrane

operation (for example, CFV (cross-flow velocity) and shear stress) is one of the
approaches used to mitigate membrane fouling as it leads to an increase in mass
transfer coefficient and turbulence, thus weakening concentration polarisation.
Aeration
Many efforts have been conducted on optimisation of air flow rate to reduce the cost
factor of energy involved in providing aeration to membranes (Le-Clech et al. 2006b).
3.1 Membrane Fouling 61

Two distinct parameters to limit membrane fouling are the location of aerators and the
specific design of airflow patterns. Further enhancement in aeration design imple-
mented by membrane bioreactor manufacturers are usually reported in many different
ways (e.g. patent, format) and include cyclic aeration systems (Rabie et al. 2003), and
improved aerator systems (Miyashita et al. 2000). Recently, Mayer et al. (2006)
outlined an exhaustive comparison of various aeration devices used in tubular
membranes. They concluded that complex aeration systems with multiple orifices
injecting air homogeneously in the feed flow worked best. The effect of aeration
differs from hollow fibre membrane modules to flat plate membrane modules.
Bichamber (riser and downcomer) presence in a Kubota MBR has a significant
impact in generating high cross-flow velocity (CFV m/s) (Sofia et al. 2004).
Higher CFV and lower uplift resistance were induced by uniformly distributed fine air
bubbles (produced from a porous media with 0.5 mm holes) in comparison to per-
formances achieved with larger bubbles (from 2 mm hole diffuser) at the same aer-
ation rates. The ratio of air/permeate (m3/m3) is a useful parameter to characterise
aeration intensity which is needed to obtain a specified amount of treated water.
Values given by MBR manufacturers can differ between 24 and 50, depending on
membrane modules (flat sheet versus hollow fibre) and the design of MBR tank
(membrane and aerobic zone combined into one tank or not) (Tao et al. 2005).
Preliminary work implemented in Singapore on large-scale MBRs showed the
original ratios to be quite conservative, since it was possible to decrease them (down
to 56 % of their original value) without significantly increasing fouling (Tao et al.
2005). Numerous research studies have been conducted to increase the critical flux in
submerged MBR by alternating the aeration rates (Howell et al. 2004). During high
throughput period, aeration was increased and dropped to lower values for the low
throughput period, to reduce membrane fouling. This technique was used also to
reduce energy consumption. As stated by Choi et al. (2005), when pseudosteady state
is achieved, the tangential shear was found to have no effect on permeation flux
decline in cross-flow MBR device. Increasing CFV has no capability to reduce
fouling when the layer begins to deposit and dominate the permeation flux behaviour.
Flux decline was caused predominantly by reversible fouling when CFV was not
present, when CFV was present slightly higher irreversible fouling was observed
(Choi et al. 2005). Intermittent operation of aeration has also been reported for (de)
nitrification MBR systems (Yeom et al. 1999; Nagaoka and Nemoto 2005). In this
uncommon scheme, a single tank MBR was used for anoxic and aerobic biological
degradation; filtration process is executed during the aerobic phase to take advantage
of the antifouling properties of the air scouring. As soon as air sparging ceased, severe
fouling was observed when researchers tested intermittent aeration, therefore they
concluded that this kind of test is not useful (Jiang et al. 2005; Psoch and Schiewer
2005). Other investigators have indicated that using intermittent bubbling is an effi-
cient way to control fouling (Judd et al. 2006; Fane 2005). Pulsing air at a frequency of
1 s on/1 s off prompted further enhancement in operating flux ranging from 20 to
100 % and was noted to be a more effective method than using lower frequencies
(5–10 s on/5–10 s off) which is commonly used industrially (Judd et al. 2006).
62 3 Fouling in Membrane Bioreactors

However, such system may need the operation of robust activators and valves at these
high frequencies and may not be economically practical.
Other operating conditions
Le-Clech et al. (2006b) defined solid retention time (SRT) as one of the main
operating parameters defining the properties of the biomass suspension and its
fouling tendency. It also influences membrane bioreactor performance, especially in
the control of fouling. With numerous research studies explaining the relationship
between SRT and concentrations of both extracellular polymeric substances
(EPS) and soluble microbial product (SMP), it is evident that overall performance
of the MBRs is almost related to SRT value. To enhance filtration performance a
long SRT is used, this also minimises SMP and EPS formation by producing
starved conditions (Judd 2006). However, using a very long SRT, severe membrane
fouling is to be expected as a consequence of the accumulation of MLSS or sludge
(filamentous) production.
Moreover, the performance of MBR is reduced due to low biomass when the
SRT is extremely too short (down to 2 days) (Meng and Yang 2007). Meng and
Yang (2007) stated that higher ratio of Food/Microorganism can also increase the
concentration of EPS because of high food utilisation by biomass.
Further optimizations of operating conditions through reactor design have been
investigated and included the addition of a spiral flocculator (Guo et al. 2004),
vibrating membranes (Genkin et al. 2005), helical baffles (Ghaffour et al. 2004),
suction mode (Kim et al. 2004) and high performance compact reactor (Yeon et al.
2005), novel types of air lift (Chang and Judd 2002), porous and flexible suspended
membrane carriers (Yang et al. 2006a) and the sequencing batch MBR (Zhang et al.
2006a), for example. Lastly, the design of membrane modules remains as another
vital factor in the optimization of the MBR operation, and more accurately, the use
of air sparging method. Higher permeability was obtained, when a specific module
was designed with air bubbles confined in close proximity to the hollow fibre
(Ghosh 2006).
Sustainable flux
The energy requirement for operation is a potential weakness for the future
development of the MBR systems. In comparison to the conventional activated
sludge systems, it is acknowledged that the energy usage of MBRs is still higher
because of the need to alleviate membrane fouling by different techniques
(Le-Clech et al. 2006b). At the end of the day, MBRs can be economically feasible
only if it produces a reasonable flux rate without significant fouling. When per-
meation rate and membrane fouling reduce simultaneously, most MBR systems
operate at low fluxes to alleviate excessive membrane fouling. Generally, sustain-
able flux can be defined as subcritical flux by default. Though, in MBR it can be
defined as the flux where the rate of transmembrane pressure (TMP) rises gradually
at an allowable rate, removing the need for chemical cleaning (Ng et al. 2005).
Before chemical cleaning is required, both the rate of TMP increase and the period
of filtration are left to the operator’s discretion, and hence a more detailed definition
3.1 Membrane Fouling 63

of sustainable flux cannot be possible. While vital flux was commonly determined
during short-term experiments, sustainable flux can only be assessed through longer
filtration periods. In sustainable flux systems, the value of flux is vital, but the
methods used to maintain and achieve the given flux value are also of great
importance.

[Link] Cleaning Procedures

Cleaning process is paramount step towards regenerating the membranes, making

them very active for usage or application. Cleaning procedure has to be done when
the flux is slightly reduced and transmembrane pressure is increasing drastically.
Cleaning procedure is usually performed in three different forms; physical, chem-
ical and combination of physical and chemical cleaning. Physical and chemical
cleaning can remove foulants (microbial flocs) from membrane surface through
backwashing, relaxation, hydraulic scouring and chemical reactions.
Physical cleaning
In MBR systems, physical cleaning techniques are used to recover membrane
permeability significantly. It mainly includes two processes: the first process is
relaxation process (occurs where the filtration process is ceased) and the second one
membrane backwashing (where the effluent is delivered back through the mem-
brane into the feed channel to remove the deposited particles on the surface of
membrane) (Le-Clech et al. 2006b). Relaxation and backwashing techniques have
been used in membrane bioreactor systems as standard operating techniques to
alleviate membrane fouling; although potent backwashing is not a suitable option
for flat plate submerged membranes.
Backwashing (Backflushing or water rinsing) was used to remove reversible
fouling effectively, remove contaminants aggregated on the membrane surface and
also allowed efficient flux recovery. Frequency, duration and their ratio are the key
parameters in the design of backwashing. Jiang et al. (2005) state that using less
frequent and longer backwashing duration (600 s filtration/45 s backwashing) has
been found to be more effective than using more frequent and less backwashing
duration (200 s filtration/15 s backwashing) (Jiang et al. 2005). In another research
study, using backwash duration (between 8 and 16 min) was found to be very
effective in removing membrane fouling than using either the aeration intensity
(0.3–0.9 m3/m2 h) or backwash duration (25–45 s) (Schoeberl et al. 2005) for
hallow fibre immersed membrane bioreactor systems. Whilst more fouling is
anticipated to be eliminated in more frequent, longer, and stronger backflushing
duration, possible modification or alteration is required, exploring to minimise
energy consumption. This has been achieved by designing a generic control system
which automatically optimised the backflush duration according to the monitored
value of transmembrane pressure (Smith et al. 2005). However, a large number of
research studies have not taken into consideration the loss of productivity that
results from the use of permeation flux during the backwashing.
64 3 Fouling in Membrane Bioreactors

Obviously, the antifouling operation affects operating costs, as more energy is

needed to achieve a suitable pressure for flow reversal. Furthermore, between 5 and
30 % of the permeation flux produced is thoroughly used in this process. In com-
parison to hollow fibre MBR, flat sheet membrane bioreactor module has achieved a
slightly higher overall permeate flux when operating the membrane constantly at low
flux (Judd 2002). In this example, flat sheet membranes (which cannot be back-
washed) were operated constantly with flux ranging between 20 and 27 LMH. The
hollow fibre membrane bioreactor module on the other hand was operated at higher
flux, ranging from 23 to 33 LMH but with 25 % of the permeate product being
recycled for backwashing (45 secs of backwashing after every 600 secs of operation).
As noted by (Sun et al. 2004), air can be used to affect backflushing.
Approximately 400 % increase in the flux has been achieved from continuous
operation mode using an air backflush. 15 min of air backwash was needed for
every 15 min of filtration to obtain this result (Visvanathan et al. 1997). Whilst, air
backwashing is more effective method used to recover membrane permeability.
However, air backflushing may present some potential issues of membrane which
become rewetting and breakable (emrittlement).
Membrane relaxation (so-called non-continuous process of the membrane or
batch process) is intermittent cessation of permeation for flux recovery if the
membrane is submerged, and scoured with air when the permeation is ceased. It
improves the productivity of membrane significantly. Under this operation, in
nature, back transport of foulants (microbial flocs) is enhanced as non-irreversibly
attached foulants, which can diffuse away from the surface of membrane via
concentration gradient improved by the shear generated by air scouring (Hong et al.
2002; Chua et al. 2002). Comprehensive studies of the behaviour of transmembrane
pressure during this operation has been showed that although the rate of fouling is
generally higher than for continuous filtration, membrane relaxation allows filtra-
tion to be kept for longer period of time before the need for intense chemical
cleaning (Ng et al. 2005). Although some research studies have mentioned that this
operation may not be feasible economically for large-scale MBRs (Hong et al.
2002), productivity analyses and further cost are possibly required to compare this
method against backwashing process.
Recent research studies evaluating another technique to control membrane
fouling have been tended to merge relaxation with backwashing for optimum
results (Zhang et al. 2005; Vallero et al. 2005). Combination of relax/permeate and
backflush/permeate can reduce chemical cleaning and shorten membrane lifespan
(Zsirai et al. 2012).
To sum up, physical cleaning only eliminates the coarse solid or cake layer from
the membrane surface, whilst chemical cleaning eliminates the flocs. Physical
cleaning can also eliminate the strong matters that attach on the surface of mem-
brane. The energy consumption for physical cleaning up to 30 % of the (permeate)
must be taken into careful consideration.
3.1 Membrane Fouling 65

Chemical cleaning
As expected, the effectiveness of membrane backwashing and relaxation tend to
decrease with operation time as more irreversible fouling aggregates on the
membrane surface. Thus, in comparison to the physical cleaning strategies, various
chemical cleaning strategies have been recommended or proposed (Le-Clech et al.
2006b). They include
• Enhanced backwash chemically (this can be done each day).
• Maintenance cleaning with higher concentration of chemical agent (this should
be done weekly).
• Intensive (or recovery) chemical cleaning (this must be done once or twice a
year). This should be done if the membrane permeation is no longer sufficient.
This is designed to remove irreversible fouling.
Maintenance cleaning is used to recover membrane permeability, and to reduce
the frequency of intensive cleaning. Chemical cleaning controls membrane fouling
especially, scaling, organic fouling and biofouling which is not removed by
physical cleaning. In general, exhaustive cleaning is conducted when further fil-
tration is no longer sustainable because of higher transmembrane pressure (TMP).
Each of the four main MBR suppliers (Kubota, Memcor, Mitsubishi and Zenon)
proposes their own chemical cleaning recipes, which differ mainly in terms of
concentrations and methods as presented in Table 3.4.
Normally, sodium hypochlorite (0.1–0.5 wt%) is the prevalent chemical agent
used to remove organic fouling and biofouling effectively, whilst, citric acid is used
to remove inorganic scalants. Sodium hypochlorite (NaOCl) and hydrogen peroxide
(H2O2) are the most common oxidant agents, which function through oxidation and
disinfection. (NaOCl) and (H2O2) are used to hydrolyse the organic molecules, and
therefore slacken the biofilm and particles that sticked to the membranes. The
influences of cleaning chemical agents like NaOCl on microbial community have

Table 3.4 Intensive chemical cleaning protocols for four MBR suppliers (Le-Clech et al. 2005a)
MBR Type Chemicals Concentration Protocols
Suppliers (%)
Mitsubishi CIL NaOCl 0.3 Backflow through membrane
Citric acid 0.2 (2 h) + soaking (2 h)
Zenon CIP NaOCl 0.2 Backpulse and recirculate
Citric acid 0.2–0.3
Memcor CIP NaOCl 0.01 Recirculate through lumens, mixed
Citric acid 0.02 liquors and in-tank air manifolds
Kubota CIL NaOCl 0.5 Backflow and soaking (2 h)
Oxalic 0.1
acid
CIL cleaning in line where chemical solutions are generally backflow (under gravity) inside the
membrane. CIP cleaning in place where membrane tank is isolated and drained; the module is
rinsed before being soaked in the cleaning solution and rinsed to remove excess of chlorine
66 3 Fouling in Membrane Bioreactors

been conducted for modelled MBR systems (Lim et al. 2004). They postulated that
the performance of organic degradation of the microbial community in the occur-
rence of NaOCl was hampered. They also suggested that adding additional amounts
of NaOCl caused an inhibition of organic degradation and cell lysis.
It is also usually for MBR manufactures to adjust specific protocols for chemical
cleaning (i.e. cleaning frequencies and chemical concentrations) and for individual
facilities (Tao et al. 2005; Kox 2004; Le-Clech et al. 2005a). It also has been
mentioned that the level of pollutants (measured as TOC (total organic carbon)) in
the permeate (effluent) rises just after the chemical cleaning episodes (Tao et al.
2005). This is important for MBRs utilised in reclamation process trains (i.e.
upstream of RO). Until now, no systematic research studies have been conducted
on cleaning procedures (Liao et al. 2004). This is probably due to the site-specific
nature of the membrane bioreactors fouling.
Maintenance cleaning takes up to 30–120 min for a cycle to be completed.
Usually, it is implemented every 3–7 days (approximately 1 week), using NaOCl as
chemical agent. The concentration of NaOCl should be moderate (200–500 mg/l)
or 0.01 wt% NaOCl for aerobic membrane bioreactor systems. Recovery cleaning
uses rather higher reagent concentrations of 0.2–0.5 wt% NaOCl coupled with 0.2–
0.3 wt% citric acid or 0.5–1 wt% oxalic acid (Judd 2011).

[Link] Optimization of Membrane Characteristics

It is another approach used to avoid fouling in MBRs system and increased

membrane permeability. Chemical modification of the membrane surface has been
found to improve antifouling performance efficiently and effectively. When
hydrophobic membranes are used in the MBR, more severe fouling is expected.
Therefore, numerous research studies have been conducted on hydrophilisation
(make the membrane more hydrophilic) of membrane. Yu et al. (2005a, b) modified
polypropylene (PP) hollow fibre membranes using NH3 and CO2 plasma treat-
ments. In both research studies, X-ray photoelectron spectroscopy and scanning
electron microscopy were conducted to characterise the morphology and chemical
structure of the modified PP membrane surface. Introducing polar groups (from
oxygen and nitrogen) into the membrane surface, membrane hydrophilicity
increased significantly and the modified membranes showed excellent separation
performances and flux recovery ratio in comparison to the neat membranes
(Le-Clech et al. 2006b). A detail overview will be provided in chapter four on
surface modification.

[Link] Gas Sparging/Air Sparging

Gas or air sparging is another technique used to generate high surface shear at
membrane surfaces, reducing membrane fouling and significantly improving the
performance of some membrane processes (i.e. UF or MF) due the advantageous
3.1 Membrane Fouling 67

bubbling method to control the concentration polarisation and cake layer deposition
(Cui et al. 2003). In MBRs processes, air sparging method is usually employed
because the MBRs required aeration system to provide oxygen as a substrate for
biomass suspension and microorganism. Oxygen is very necessary in MBRs to
keep the existing biomass alive and to degrade the biodegradable pollutants. By
directly injecting air in the concentrate section during the filtration process, air
sparging creates an intermittent two-phase flow (gas/liquid) along a membrane
surface, leading to reduce fouling to a minimum, enhanced flux and increase surface
shear. Ducom et al. (2002) stated that air sparging is very effective method used
with both tubular membranes and hollow fibre membranes for Escherichia coli
suspensions. Air sparging effectively enhanced the membrane permeation in
microfiltration and ultrafiltration for a wide range of applications, particularly for
particles or solutes in water. However, air sparging technique is not as efficient as
the use of turbulence promoters (e.g. spiral wire, metal grill, static rods) due to the
handling problem of gas injected into the membrane (Wakeman and Williams
2002b).
The method of injecting air into the feed stream to mitigate colloidal or par-
ticulate membrane fouling in organic hollow fibres has been widely reported in the
literature. The efficiency of a two-phase flow (gas/liquid) was assessed to prevent
cake layer formation; while the effects of injecting air on permeation flux at dif-
ferent velocities were scrutinised by Cabassud et al. (1997). The results showed that
the permeation flux (in case of non-injecting air in the feed stream) decreased with
time during filtration operation. However, during the first few minutes, the per-
meation flux showed a significant decrease due to the depositing particle within the
membrane, therefore, the added flow resistance. In contrast, the permeation flux (in
case of injection air in the feed stream) decreased with time, but the rate of flux
decreasing was very low. In case of using higher air velocity, the permeate flux
experienced a higher level. Furthermore, increasing air velocity results in particle
deposit formation with less mass transfer resistance. Also, the flow of an inter-
mittent gas seems to be effectively less than a steady one in similar experimental
operations. It was well documented that there is the evidence of change of fouling
layer or cake structure with the application of gas sparging to the microfiltration of
particles. This affects its specific resistance by reducing it (Cabassud et al. 1997).
An improved flux over time was a result of alterations in the cake structure or
fouling layer with the gas-sparged ultrafiltration of clay suspension.
The effects of injecting air into the feed side of flat sheet membrane modules on
protein transmission and permeation flux were scrutinised using four foulant
models such a human immunoglobulin G (IgG), bovine serum albumin (BSA),
human serum albumin (HSA) and lysozyme (Lys) as test media (Li et al. 1998).
Polysulfone and polyethersulfone were the two membranes used in this study. The
results showed that gas sparging enhanced membrane flux up to 50 % but protein
reduction/retention was reduced significantly. It was found that at TMP of
approximately 50 kPa, with using a mixture of BSA and Lys, the gas injection
increased membrane flux by only 10 % but had a more powerful effect on protein
separation. In another research study, the flux was increased between 60 and 270 %
68 3 Fouling in Membrane Bioreactors

due to gas sparging obtained on ultrafiltration of (BSA and dextran) solutions and
also in the microfiltration of yeast suspensions using tubular membranes (Cui and
Wright 1994; Cui 1993; Lee et al. 1993; Imasaka et al. 1993; Cui and Wright 1996).
A method of incorporating gas into the feed stream as a process of separating the
dense cake layer on the membranes was scrutinised using two-phase (gas–liquid)
cross-flow ultrafiltration in the downward flow condition using a tubular membrane
module (Cui and Wright 1996). The module was vertically installed, with both the
gas bubbles and feed solution flowing downward in the membrane. The membrane
permeation achieved in this method was in comparison to that in conventional
single-phase ultrafiltration and gas-sparged upward cross-flow operations. The
operating parameters which were scrutinised with dextran solutions (protein model)
included gas flows, liquid flows, transmembrane pressure (TMP) and feed con-
centrations. The results showed that the permeation flux was increased up to 320 %.
It was noted that the addition of gas in both upward and downward flows resulted in
significant enhancement in permeation flux. This confirmed the technique to be
very useful in deterring concentration polarisation and hampering flux in compar-
ison to any other technique known at that time. The improvement in permeation
flux was more obvious when the concentration polarisation was very severe,
indicating the validity of the disruption. Using a low flow rate of gas sparging
results in improved ultrafiltration while the introduction of the bubbles enhanced an
early transition from laminar flow to turbulent flow. The bubbles could represent as
static baffles or slow moving baffles to decrease the rate of flow gas, depending on
the process conditions.
Air sparging is a strategy that is employed to enhance the efficiency of back-
washing in a dead-end fibre module. It was also investigated and effectively con-
firmed for the removal of the cake layer formed during the filtration of bentonite
suspensions (Serra et al. 1999; Ducom et al. 2002). The rinse phase efficiency was
significantly enhanced after the introduction of air, acting as a piston to flush out the
major part of the free volume in the module.
The combination of air sparging and back shock enhances the productivity as
less permeation flux is consumed during backwash process. On the other hand, the
decline of permeation flux caused by membrane fouling usually cannot fully be
refilled through gas sparging because the internal pore fouling is not reversed by
surface shear. Therefore, bubbling or gas sparging can efficiently be used for
membrane processes, especially microfiltration and ultrafiltration processes. It can
also be used within membrane modules or in submerged membrane bioreactors
systems as they have been proved to improve the rates of permeation flux and
reduce membrane fouling to a minimum.
Air sparging performance was examined on submerged MBR systems used for
wastewater treatment with emphasis on two techniques. The first technique included
the use of air injection into membrane tube channels to allow circulation of mixed
liquor in the bioreactor, and the second one used periodic air jets into the membrane
tube. The results achieved from both the techniques showed that the cake layer was
sufficiently detached or separated from the membrane due to use air injection.
3.1 Membrane Fouling 69

Another application of using air sparging for improvement of membrane flux or

permeation flux in nanofiltration membranes was studied using droplet suspensions
in water (Ducom et al. 2002). The process was examined on a flat sheet membrane
for two feeds: stabilised and non-stabilised oil–water emulsions. The focus of the
study was based on using nanofiltration membranes in the industrial section
including treatment of cutting oil fluids, which are encountered in metal manu-
facturing, metal working, and processing. The function of this study was to remove
the dissolved organic components from the aqueous phase and also to separate the
oily dispersed phase from the membrane. The experiments were conducted to
achieve two objectives: the first one was to achieve an oily phase as concentrated in
oil as possible so to be able to reuse the oil; whilst the second one was to obtain an
aqueous phase in accordance with the regulation standards for industrial wastew-
ater. The preliminary results of the experiments showed that the injection of air at
very high velocities did not change the permeability or permeate flux to pure water.
Air sparging with non-stabilised oil–water emulsions also showed lower filtra-
tion capability due to the formation of an oil layer at the surface of membrane as the
membrane hydrophobicity increases in the absence of surfactants. It was noted that
in both cases, a significant increase in permeation flux was achieved with air
sparging. This was a result of the capability of air bubbles for distorting the oil layer
over the surface of membrane.
Air sparging has also been proved to be more effective and very efficient with
both tubular membranes and hollow fibre membranes for E. coli suspensions,
dextran or albumin solutions (Bellara et al. 1996), clay suspensions, clay particles
(Mercier et al. 1997; Laborie et al. 1998) and natural surface waters (Cabassud et al.
2001).

[Link] Pulsatile Flow

The use of pulsatile flow has been equipped towards producing unsteady flows and
oscillations. Oscillations and unsteady flows are obtained by introducing pulsations
into the feed (filtrate) and permeate channels (Wakeman and Williams 2002b). The
filtration performance of yeast cell harvesting was significantly improved using
oscillatory flow mixing in both flat sheet and tubular membranes. The advantage of
implementing the method was a sevenfold increase in the membrane permeation.
However, studies are still in progress to determine the effects of frequency and
amplitude (Howell et al. 1993; Wu et al. 1993). Many researchers noticed that the
enhancement in membrane permeation was roughly 300 % increase when they used
periodically spaced, doughnut-shaped baffles in ultrafiltration tubes and pulse flows.
Pulsing the flow results increased the permeability (flux) by 50 % (Finnigan and
Howell 1989; Gupta et al. 1993), and 20 % when tangential inlet ports are used to
induce helical flow (Holdich and Zhang 1992).
A variation of the pulsating flow technique was also studied using as an inter-
mittent jet of fluid at the inlet to a tubular filter. The results showed that the
70 3 Fouling in Membrane Bioreactors

permeation fluxes (2.5 times higher) were higher than those achieved without
intermittent jets (Arroyo and Fonade 1993). It was documented that a further
variation of the pulsating flow technique was also possible using a flexible tube at
the inlet to a ceramic with the tube subjected to alternating pressure. The results
illustrated that the fluxes were increased to 60 % in this study (Bertram et al. 1993).
Researchers have stated that using a periodically spaced baffle with pulsatile
flow is effective method in significantly enhanced microfiltration. Whilst, other
researchers have verified the effectiveness of pulsatile flow techniques for
enhancing permeation flux via using a rotating perforated disc placed in front of the
entry section of a bundle of tubular membranes (Wenten 1995; Mackay et al. 1991;
Wang et al. 1994; Spiazzi et al. 1993; Gupta et al. 1992; Belfort 1989). This would
result in temporarily increase in velocity in the different tubes. It was also showed
that the rate of pulsatile flow increased the rate of wall shear as velocity increased at
high frequencies (Winzeler and Belfort 1993).
Another technique that was evaluated was the air flush technique, which
involves using an intermittent two-phase (gas or liquid) flush via the tube to shift
and remove the deposition of cake layer. It was concluded that air flush technique
[using two-phase (gas or liquid)] is more efficient technique than using a
single-phase liquid flush (Verbeck et al. 2000).

[Link] Bubbling

As mentioned before, aeration in MBRs consumes more energy, leading to higher

operating costs for all the MBRs in common use. It also reduces membrane fouling
to a minimum. Therefore, numerous methods have been outlined to enhance the
hydrodynamic properties in different membrane modules. Bubble inducing surface
shear is a major technique to control the higher costs of aeration and membrane
replacement which is related directly to membrane fouling (Cui et al. 2003; Drews
et al. 2010; Samir et al. 1992; Martinelli et al. 2010; Ndinisa et al. 2006;
Phattaranawik et al. 2007; Taha and Cui 2002; Yamanoi and Kageyama 2010).
A number of various two-phase flow models from bubble flow to slug flow can
be induced by various bubbling regimes. It is evident that slug bubbles have
desirable hydrodynamics properties, improve membrane permeation (effluent) and
improve selectivity in different membrane processes and for different membrane
modules (Cabassud et al. 2001; Cheng and Li 2007; Ducom et al. 2002; Essemiani
et al. 2001; Li et al. 1997, 1998; Mercier et al. 1997; Taha and Cui 2002; Willems
et al. 2009). Although the membrane plants have different economies of scales, the
energy required of membrane bioreactor systems in treatment plants of municipal
wastewater is higher (about 2–4 times) in comparison with conventional activated
sludge process (CASP) (Gil et al. 2010; Verrecht et al. 2008). Zhang et al. (2009)
stated that frequency and bubble size have a powerful impact on the hydrodynamic
properties in slug bubbling flat sheet membrane bioreactor modules. Traditionally,
the need is for some high areation intensity in order to induce scouring of the
membrane while also providing oxygen sufficiently to the biomass. In comparison
3.1 Membrane Fouling 71

to free bubbling, periodic slug bubbles in flat sheet membrane bioreactor systems
are economically and effectively improve the mass transfer coefficient, inducing
higher wall shear stress while consuming only a very modest amount of air. One
can envisage meeting the biological requirements via fine bubble aeration coupled
with the use of periodic slug bubbling to control membrane fouling in membrane
bioreactor systems. This combined aeration technique will reduce the requirement
of aeration and energy in MBRs. Zhang et al. (2011c) concluded that slug bubbles
showed excellent antifouling properties in flat sheet membrane bioreactor systems
under both short-term and long-term flux operations. In short-term operation, high
flux was expected 40 L m−2 h−1 for 36 h operation. In short-term filtration oper-
ation, high flux was expected (40 L m-2 h-1) for 36 hr operation. In contrast, in
long-term filtration operation, moderate flux was achieved (initial flux was 24 L m-2
h-1) for 14 days operation. At low density (2.5 L/min), the slug bubbling reduces
the occurrence of irreversible membrane fouling effectively in the initial step and
also reduces reversible fouling drastically during long-term filtration operation.
Conversely, in free bubbles, the fouling, which is accumulated at the open stage
was greater (not completely cleaned) when aerated with free bubble at the same low
density. This will lead to an increase in the formation of cake layer when the MBR
is preceded.
With increasing consideration being given to energy consumption, slug bubbling
in flat sheet membrane bioreactor systems seemed to be energy saving should be an
attractive option to free bubble.

3.2 Conclusions

In this chapter, membrane fouling is a repugnant problem in all membrane pro-

cesses especially, in membrane bioreactors, where the efficacy of the process is
restrained by the aggregation of materials on the membrane surface or within the
membrane pores. Membrane fouling was thoroughly addressed. Depending on the
specific membrane process, membrane fouling can be classified into organic foul-
ing, inorganic fouling, biofouling, particulate or colloidal fouling, reversible and
irreversible fouling and removable or irremovable fouling. Organic, inorganic and
biofouling occur simultaneously during filtration process and are merged with each
other. The interaction between different types of foulants leads to decline perme-
ation flux of the membrane. A number of methods have been used to mitigate
membrane fouling to a great extent. Using absorbents or coagulants can reduce the
internal clogging of the membrane or reduce the amounts of solute in the solution,
and improve the flocculation ability of flocs, which cannot improve membrane
permeation but also notably enhance the quality of membrane. Air sparging is an
effective method used to remove cake layer from the membrane surface and control
concentration polarisation. Hydrodynamics conditions is one of the efficient
methods in controlling membrane fouling, any additional improvement would be
helpful in mitigating membrane fouling. For example, merging aeration system with
72 3 Fouling in Membrane Bioreactors

membrane module design with CFD simulators might be very effective in

enhancing of hydrodynamic conditions. Also operation below the critical flux is
very efficient way to avert fouling within a specific filtration system. Physical and
chemical cleaning can recover membrane permeation greatly, therefore enhancing
antifouling property of membrane.

References

Ahmad AL (1997) Electrophoretic membrane cleaning in dead-end ultrafiltration processes. In:

Regional symposium on chemical engineering, UTM, Johor Bharu, pp 281–288
Ahmed A (1997) Electrophoteric membrane cleaning in dead end ultrafiltration process. Paper
presented at the regional symposium of chemical engineers, UTM
Al-Amoudi AS, Farooque AM (2005) Performance restoration and autopsy of NF membranes
used in seawater pretreatment. Desalination 178(1–3 SPEC. ISS.):261–271. doi:10.1016/j.
desal.2004.11.048
Al-Amoudi A, Lovitt RW (2007) Fouling strategies and the cleaning system of NF membranes and
factors affecting cleaning efficiency. J Membr Sci 303(1–2):4–28
Ang WS, et al (2011) Fouling and cleaning of RO membranes fouled by mixtures of organic
foulants simulating wastewater effluent. J Membrane Sci 376(1–2):196–206
Aptel P, Clifton M (1986) Ultrafiltation. In: Bungay MP, Lonsdale HK, de Pinho MN
(eds) Synthetic membranes: science engineering and application. D Reidel Publishing Co,
pp 283–288
Arroyo G, Fonade C (1993) Use of intermittent jets to enhance flux in crossflow filtration.
J Membr Sci 80(1):117–129. doi:10.1016/0376-7388(93)85137-L
Asatekin A, Kang S, Elimelech M, Mayes AM (2007) Anti-fouling ultrafiltration membranes
containing polyacrylonitrile-graft-poly(ethylene oxide) comb copolymer additives. J Membr
Sci 298(1–2):136–146
Bai R, Leow HF (2002a) Microfiltration of activated sludge wastewater-The effect of system
operation parameters. Sep Purif Technol 29(2):189–198
Bai R, Leow HF (2002b) Modeling and experimental study of microfiltration using a composite
module. J Membr Sci 204(1–2):359–377
Baker RW (2004) Membrane technology and applications, 2nd edn. Wiley, England
Baker R (2012) Membrane technology and application, 3rd edn. Wiley, UK
Baker J, Dudly L (1998) Biofouling in membrane systems—a review. Desalination 118:81–89
Belfort G (1989) Fluid mechanics in membrane filtration: recent developments. J Membr Sci 40
(2):123–147. doi:10.1016/0376-7388(89)89001-5
Bellara SR, Cui ZF, Pepper DS (1996) Gas sparging to enhance permeate flux in ultrafiltration
using hollow fibre membranes. J Membr Sci 121(2):175–184. doi:10.1016/S0376-7388(96)
00173-1
Bertram CD, Hoogland MR, Li H, Odell RA, Fane AG (1993) Flux enhancement in crossflow
microfiltration using a collapsible-tube pulsation generator. J Membr Sci 84(3):279–292.
doi:10.1016/0376-7388(93)80023-Q
Boerlage SFE, Kennedy M, Aniye MP, Schippers JC (2003) Applications of the MFI-UF to
measure and predict particulate fouling in RO systems. J Membr Sci 220(1–2):97–116
Boissonade G, ORichaud, Milisic V (1991) Couplage d’un traitement biologique et d’un procede de
separation par membrane. Proc Recents Progres en Genie des Procedes Compiegne 5:117–122
Bouhabila EH, Aïm RB, Buisson H (1998) Microfiltration of activated sludge using submerged
membrane with air bubbling (application to wastewater treatment). Desalination 118(1–3):
315–322
References 73

Brauns E, Van Hoof E, Molenberghs B, Dotremont C, Doyen W, Leysen R (2002) A new method
of measuring and presenting the membrane fouling potential. Desalination 150(1):31–43
Brindle K, Stephenson T (1996) The application of membrane biological reactors for the treatment
of wastewaters. Biotechnol Bioeng 49(6):601–610
Buffle J, Leppard GG (1995) Characterization of aquatic colloids and macromolecules. 1. Structure
and behavior of colloidal material. Environ Sci Technol 29(9):2169–2175
Buffle J, Wilkinson KJ, Stoll S, Filella M, Zhang J (1998) A generalized description of aquatic
colloidal interactions: the three-culloidal component approach. Environ Sci Technol 32
(19):2887–2899. doi:10.1021/es980217h
Cabassud C, Laborie S, Lainé JM (1997) How slug flow can improve ultrafiltration flux in organic
hollow fibres. J Membr Sci 128(1):93–101. doi:10.1016/S0376-7388(96)00316-X
Cabassud C, Laborie S, Durand-Bourlier L, Lainé JM (2001) Air sparging in ultrafiltration hollow
fibers: relationship between flux enhancement, cake characteristics and hydrodynamic
parameters. J Membr Sci 181(1):57–69. doi:10.1016/S0376-7388(00)00538-X
Chae SR, Ahn YT, Kang ST, Shin HS (2006) Mitigated membrane fouling in a vertical submerged
membrane bioreactor (VSMBR). J Membr Sci 280(1–2):572–581. doi:10.1016/[Link].2006.
02.015
Chae SR, Wang S, Hendren ZD, Wiesner MR, Watanabe Y, Gunsch CK (2009) Effects of
fullerene nanoparticles on Escherichia coli K12 respiratory activity in aqueous suspension and
potential use for membrane biofouling control. J Membr Sci 329(1–2):68–74
Chang IS, Judd SJ (2002) Air sparging of a submerged MBR for municipal wastewater treatment.
Process Biochem 37(8):915–920. doi:10.1016/S0032-9592(01)00291-6
Chang IS, Kim SN (2005) Wastewater treatment using membrane filtration—effect of biosolids
concentration on cake resistance. Process Biochem 40(3–4):1307–1314. doi:10.1016/[Link].
2004.06.019
Chang IS, Lee CH (1998) Membrane filtration characteristics in membrane-coupled activated
sludge system—the effect of physiological states of activated sludge on membrane fouling.
Desalination 120(3):221–233
Chang IS, Clech PL, Jefferson B, Judd S (2002) Membrane fouling in membrane bioreactors for
wastewater treatment. J Environ Eng 128(11):1018–1029
Cheng TW, Li LN (2007) Gas-sparging cross-flow ultrafiltration in flat-plate membrane module:
Effects of channel height and membrane inclination. Sep Purif Technol 55(1):50–55. doi:10.
1016/[Link].2006.10.026
Chen CL, Liu WT, Chong ML, Wong MT, Ong SL, Seah H, Ng WJ (2004) Community structure
of microbial biofilms associated with membrane-based water purification processes as revealed
using a polyphasic approach. Appl Microbiol Biotechnol 63(4):466–473. doi:10.1007/s00253-
003-1286-7
Cho BD, Fane AG (2002) Fouling transients in nominally sub-critical flux operation of a
membrane bioreactor. J Membr Sci 209(2):391–403
Cho J, Song KG, Hyup Lee S, Ahn KH (2005a) Sequencing anoxic/anaerobic membrane
bioreactor (SAM) pilot plant for advanced wastewater treatment. Desalination 178(1–3 SPEC.
ISS.):219–225. doi:10.1016/[Link].2004.12.018
Cho JW, Song KG, Ahn KH (2005b) The activated sludge and microbial substances influences on
membrane fouling in submerged membrane bioreactor: unstirred batch cell test. Desalination
183(1–3):425–429
Choi H, Zhang K, Dionysiou DD, Oerther DB, Sorial GA (2005) Effect of permeate flux and
tangential flow on membrane fouling for wastewater treatment. Sep Purif Technol 45(1):68–78.
doi:10.1016/[Link].2005.02.010
Chon K, Cho J, Shon HK (2013) Fouling characteristics of a membrane bioreactor and
nanofiltration hybrid system for municipal wastewater reclamation. Bioresource Technol
130:239–247
Chua HC, Arnot TC, Howell JA (2002) Controlling fouling in membrane bioreactors operated
with a variable throughput. Desalination 149(1–3):225–229. doi:10.1016/S0011-9164(02)
00764-6
74 3 Fouling in Membrane Bioreactors

Cicek N, Franco J, Suidan M, Urbain V, Manem J (1999) Characterization and comparison of a

membrane boireactor and a conventional activated-sludge system in the treatment of waste
water containing high molecular weight compounds. Water Environ Res 71(1):64–70
Combe C, Molis E, Lucas P, Riley R, Clark MM (1999) The effect of CA membrane properties on
adsorptive fouling by humic acid. J Membr Sci 154(1):73–87
Costa AR, de Pinho MN, Elimelech M (2006) Mechanisms of colloidal natural organic matter
fouling in ultrafiltration. J Membr Sci 281(1–2):716–725
Cui ZF (1993) Experimental investigation on enhancement of crossflow ultrafiltration with air
sparging
Cui ZF, Wright KIT (1994) Gas-liquid two-phase cross-flow ultrafiltration of BSA and dextran
solutions. J Membr Sci 90(1–2):183–189. doi:10.1016/0376-7388(94)80045-6
Cui ZF, Wright KIT (1996) Flux enhancements with gas sparging in downwards crossflow
ultrafiltration: Performance and mechanism. J Membr Sci 117(1–2):109–116. doi:10.1016/
0376-7388(96)00040-3
Cui ZF, Chang S, Fane AG (2003) The use of gas bubbling to enhance membrane processes.
J Membr Sci 221(1–2):1–35. doi:10.1016/S0376-7388(03)00246-1
Cui X, Choo KH (2013) Granular iron oxide adsorbents to control natural organic matter and
membrane fouling in ultrafiltration water treatment. Water Res 47(13):4227–4237
Czekaj P, López F, Güell C (2000) Membrane fouling during microfiltration of fermented
beverages. J Membr Sci 166(2):199–212
De Beer D, Stoodley P (2013) Microbial Biofilms, in The Prokaryotes: Applied bacteriology and
biotechnology Rosenberg E, et al (eds) Springer Berlin Heidelberg: Berlin, Heidelberg. p. 343–
372
De La Torre T, Lesjean B, Drews A, Kraume M (2008) Monitoring of transparent exopolymer
particles (TEP) in a membrane bioreactor (MBR) and correlation with other fouling indicators.
Water Sci Technol 58:1903–1909
Diagne F, et al (2012) Polyelectrolyte and silver nanoparticle modification of microfiltration
membranes to mitigate organic and bacterial fouling. Environ Sci Technol 46(7):4025–4033
Drews A, Lee CH, Kraume M (2006a) Membrane fouling—a review on the role of EPS.
Desalination 200(1–3):186–188
Drews A, Vocks M, Iversen V, Lesjean B, Kraume M (2006b) Influence of unsteady membrane
bioreactor operation on EPS formation and filtration resistance. Desalination 192(1–3):1–9
Drews A, Mante J, Iversen V, Vocks M, Lesjean B, Kraume M (2007) Impact of ambient
conditions on SMP elimination and rejection in MBRs. Water Res 41(17):3850–3858
Drews A, Prieske H, Meyer EL, Senger G, Kraume M (2010) Advantageous and detrimental
effects of air sparging in membrane filtration: bubble movement, exerted shear and particle
classification. Desalination 250(3):1083–1086. doi:10.1016/[Link].2009.09.113
Ducom G, Matamoros H, Cabassud C (2002) Air sparging for flux enhancement in nanofiltration
membranes: application to O/W stabilised and non-stabilised emulsions. J Membr Sci 204(1–
2):221–236. doi:10.1016/S0376-7388(02)00044-3
Escobar I (2005) Hydraulic and chemical cleaning of cellulose acetate ultrafiltration membranes.
In: AIChE annual meeting, conference proceedings, p 2031
Essemiani K, Ducom G, Cabassud C, Liné A (2001) Spherical cap bubbles in a flat sheet
nanofiltration module: experiments and numerical simulation. Chem Eng Sci 56(21–22):6321–
6327. doi:10.1016/S0009-2509(01)00282-2
Evenblij H, van der Graaf JHJM (2004) Occurrence of EPS in activated sludge from a membrane
bioreactor treating municipal wastewater. Water Sci Technol 50:293–300
Fan X, Urbain V, Qian Y, Manem J (2000) Ultrafiltration of activated sludge with ceramic
membranes in a cross-flow membrane bioreactor process. Water Sci Technol 41(10/11):243–250
Fan F, Zhou H, Husain H (2006) Identification of wastewater sludge characteristics to predict
critical flux for membrane bioreactor processes. Water Res 40(2):205–212
Fane AG (2005) Towards sustainability in membrane processes for water and wastewater
processing. In: Proceedings of the international congress on membranes and membrane
processes (ICOM), Seoul, Korea
References 75

Field RW, Wu D, Howell JA, Gupta BB (1995) Critical flux concept for microfiltration fouling.
J Membr Sci 100(3):259–272
Finnigan SM, Howell JA (1989) Effect of pulsatile flow on ultrafiltration fluxes in a baffled tubular
membrane system. Chem Eng Res Des 67(3):278–282
Flemming HC (1997) Reverse osmosis membrane biofouling. Exp Thermal Fluid Sci 14(4):382–391
Flemming HC, Schaule G (1988) Biofouling on membranes—a microbiological approach.
Desalination 70(1–3):95–119. doi:10.1016/0011-9164(88)85047-1
Flemming HC, Schaule G, Griebe T, Schmitt J, Tamachkiarowa A (1997) Biofouling—the
Achilles heel of membrane processes. Desalination 113(2–3):215–225
Geng Z, Hall ER (2007) A comparative study of fouling-related properties of sludge from
conventional and membrane enhanced biological phosphorus removal processes. Water Res 41
(19):4329–4338
Genkin G, Waite TD, Fane T, Chang S (2005) The effet of axial vibratins on the filtration
performance of submerged hollow fibre membranes. In: Proceedings of the international
congress on membranes and membrane processes (ICOM), Seoul, Korea
Ghaffour N, Jassim R, Khir T (2004) Flux enhancement by using helical baffles in ultrafiltration of
suspended solids. Desalination 167(1–3):201–207. doi:10.1016/[Link].2004.06.129
Ghosh R (2006) Enhancement of membrane permeability by gas-sparging in submerged hollow
fibre ultrafiltration of macromolecular solutions: role of module design. J Membr Sci 274(1–
2):73–82. doi:10.1016/[Link].2005.08.002
Gil JA, Túa L, Rueda A, Montaño B, Rodríguez M, Prats D (2010) Monitoring and analysis of the
energy cost of an MBR. Desalination 250(3):997–1001. doi:10.1016/[Link].2009.09.089
Guglielmi G, Chiarani D, Judd SJ, Andreottola G (2007a) Flux criticality and sustainability in a
hollow fibre submerged membrane bioreactor for municipal wastewater treatment. J Membr Sci
289(1–2):241–248
Guglielmi G, Saroj DP, Chiarani D, Andreottola G (2007b) Sub-critical fouling in a membrane
bioreactor for municipal wastewater treatment: experimental investigation and mathematical
modelling. Water Res 41(17):3903–3914
Guo WS, Vigneswaran S, Ngo HH (2004) A rational approach in controlling membrane fouling
problems: pretreatments to a submerged hollow fiber membrane system. In: Proceedings of the
water environment-membrane technology conference, Seoul, Korea
Guo WS, Vigneswaran S, Ngo HH, Xing W (2007) Experimental investigation on acclimatized
wastewater for membrane bioreactors. Desalination 207(1–3):383–391. doi:10.1016/[Link].
2006.07.013
Guo W, Ngo HH, Li J (2012) A mini-review on membrane fouling. Bioresour Technol 122:27–34
Gupta BB, Blanpain P, Jaffrin MY (1992) Permeate flux enhancement by pressure and flow
pulsations in microfiltration with mineral membranes. J Membr Sci 70(2–3):257–266. doi:10.
1016/0376-7388(92)80111-V
Gupta BB, Zaboubi B, Jaffrin MY (1993) Scaling up pulsatile filtration flow methods to a pilot
apparatus equipped with mineral membranes. J Membr Sci 80(1):13–20. doi:10.1016/0376-
7388(93)85128-J
Hasson D, Drak A, Semiat R (2001) Inception of CaSO4 scaling on RO membranes at various
water recovery levels. Desalination 139(1–3):73–81
Hilal N, Ogunbiyi OO, Miles NJ, Nigmatullin R (2005) Methods employed for control of fouling
in MF and UF membranes: a comprehensive review. Sep Sci Technol 40(10):1957–2005
Holbrook RD, Higgins MJ, Murthy SN, Fonseca AD, Fleischer EJ, Daigger GT, Grizzard TJ,
Love NG, Novak JT (2004) Effect of alum addition on the performance of submerged
membranes for wastewater treatment. Water Environ Res 76(7):2699–2702
Holdich RG, Zhang GM (1992) Crossflow microfiltration incorporating rotational fluid flow.
Chem Eng Res Des 70(A5):527–536
Hong S, Elimelech M (1997) Chemical and physical aspects of natural organic matter
(NOM) fouling of nanofiltration membranes. J Membrane Sci 132(2):159-181
Hong SP, Bae TH, Tak TM, Hong S, Randall A (2002) Fouling control in activated sludge
submerged hollow fiber membrane bioreactors. Desalination 143(3):219–228
76 3 Fouling in Membrane Bioreactors

Houari A, Seyer D, Couquard F, Kecili K, Démocrate C, Heim V, Di Martino P (2010)

Characterization of the biofouling and cleaning efficiency of nanofiltration membranes.
Biofouling 26(1):15–21
Howell JA, Field RW, Wu D (1993) Yeast cell microfiltration: flux enhancement in baffled and
pulsatile flow systems. J Membr Sci 80(1):59–71. doi:10.1016/0376-7388(93)85132-G
Howell JA, Chua HC, Arnot TC (2004) In situ manipulation of critical flux in a submerged
membrane bioreactor using variable aeration rates, and effects of membrane history. J Membr
Sci 242(1–2):13–19. doi:10.1016/[Link].2004.05.013
Huang X, Liu R, Qian Y (2000) Behaviour of soluble microbial products in a membrane
bioreactor. Process Biochem 36(5):401–406
Huang X, Xiao K, Shen Y (2010) Recent advances in membrane bioreactor technology for
wastewater treatment in China. Front Environ Sci Eng China 4(3):245–271
Huang J, Arthanareeswaran G, Zhang K (2012a) Effect of silver loaded sodium zirconium
phosphate (nanoAgZ) nanoparticles incorporation on PES membrane performance.
Desalination 285:100–107
Huang J, Zhang K, Wang K, Xie Z, Ladewig B, Wang H (2012b) Fabrication of
polyethersulfone-mesoporous silica nanocomposite ultrafiltration membranes with antifouling
properties. J Membr Sci 423–424:362–370
Huang J, Wang H, Zhang K (2014) Modification of PES membrane with Ag-SiO2: reduction of
biofouling and improvement of filtration performance. Desalination 336(1):8–17
Huyskens C, Brauns E, Van Hoof E, De Wever H (2008) A new method for the evaluation of the
reversible and irreversible fouling propensity of MBR mixed liquor. J Membr Sci 323(1):
185–192
Hwang BK, Lee WN, Park PK, Lee CH, Chang IS (2007) Effect of membrane fouling reducer on
cake structure and membrane permeability in membrane bioreactor. J Membr Sci 288(1–
2):149–156. doi:10.1016/[Link].2006.11.032
Imasaka T, So H, Matsushita K, Furukawa T, Kanekuni N (1993) Application of gas-liquid
two-phase cross-flow filtration to pilot-scale methane fermentation. Drying Technol 11(4):
769–785
Itonaga T, Kimura K, Watanabe Y (2004) Influence of suspension viscosity and colloidal particles
on permeability of membrane used in membrane bioreactor (MBR). Water Sci Technol
50:301–309
Jang N, Ren X, Cho J, Kim IS (2006) Steady-state modeling of bio-fouling potentials with respect
to the biological kinetics in the submerged membrane bioreactor (SMBR). J Membr Sci 284(1–
2):352–360
Jeong TY, Cha GC, Yoo IK, Kim DJ (2007) Characteristics of bio-fouling in a submerged MBR.
Desalination 207(1–3):107–113. doi:10.1016/[Link].2006.07.006
Ji J, Qiu J, Fs Wong, Li Y (2008) Enhancement of filterability in MBR achieved by improvement
of supernatant and floc characteristics via filter aids addition. Water Res 42(14):3611–3622.
doi:10.1016/[Link].2008.05.022
Ji J, Qiu J, Wai N, Wong FS, Li Y (2010) Influence of organic and inorganic flocculants on
physical-chemical properties of biomass and membrane-fouling rate. Water Res 44(5):1627–
1635. doi:10.1016/[Link].2009.11.013
Jiang T, Kennedy MD, Guinzbourg BF, Vanrolleghem PA, Schippers JC (2005) Optimising the
operation of a MBR pilot plant by quantitative analysis of the membrane fouling mechanism.
Water Sci Technol 51:19–25
Judd S (2002) Submerged membrane bioreactors: flat plate or hollow fibre? Filtr Sep 39(5):30–31.
doi:10.1016/S0015-1882(02)80169-0
Judd S (2006) Principles and applications of membrane bioreactors in water and waste water
treatment, 1st edn. Elsevier, UK
Judd S (2007) The status of membrane bioreactor technology. Trends Biotechnol 26(2):109–116
Judd S (2011) Chapter 3—Design, operation and maintenance. In: The MBR Book, 2nd edn.
Butterworth-Heinemann, Oxford, pp 209–288. doi:[Link]
096682-3.10003-4
References 77

Judd S, Jefferson B (2003) Membranes for industrial wastewater recovery and re-use. Elesevier
Judd S, Alvarez-vazquez H, Jefferson B (2006) The impact of intermittent aeration on the
operation of air-lift tubular membrane bioreactors under sub-critical conditions. Sep Sci
Technol 41(7):1293–1302. doi:10.1080/01496390600634541
Kang IJ, Yoon SH, Lee CH (2002) Comparison of the filtration characteristics of organic and
inorganic membranes in a membrane-coupled anaerobic bioreactor. Water Res 36(7):1803–1813
Kang IJ, Lee CH, Kim KJ (2003) Characteristics of microfiltration membranes in a membrane
coupled sequencing batch reactor system. Water Res 37(5):1192–1197
Kang ST, Subramani A, Hoek EMV, Deshusses MA, Matsumoto MR (2004) Direct observation of
biofouling in cross-flow microfiltration: mechanisms of deposition and release. J Membr Sci
244(1–2):151–165. doi:10.1016/[Link].2004.07.011
Kappachery S, Paul D, Yoon J, Kweon JH (2010) Vanillin, a potential agent to prevent biofouling
of reverse osmosis membrane. Biofouling 26(6):667–672
Khan MMT, Stewart PS, Moll DJ, Mickols WE, Nelson SE, Camper AK (2011) Characterization
and effect of biofouling on polyamide reverse osmosis and nanofiltration membrane surfaces.
Biofouling 27(2):173–183
Kim IS, Jang N (2006) The effect of calcium on the membrane biofouling in the membrane
bioreactor (MBR). Water Res 40(14):2756–2764
Kim J, Jang M, Chio H, Kim S (2004) Characteristics of membrane and module affecting
membrane fouling. In: Proceedings of the water environment-membrane technology confer-
ence, Seoul, Korea
Kim J, Shi W, Yuan Y, Benjamin MM (2007) A serial filtration investigation of membrane fouling
by natural organic matter. J Membr Sci 294(1–2):115–126
Kimura K, Hane Y, Watanabe Y, Amy C, Ohkuma N (2004) Irreversible membrane fouling during
filtration of surface water. Water Res 38:3431–3441
Kimura K, Yamato N, Yamamura H, Watanabe Y (2005) Membrane fouling in pilot-scale
membrane bioreactors (MBRs) treating municipal wastewater. Environ Sci Technol 39
(16):6293–6299
Kochkodan V, Johnson DJ, Hilal N (2014) Polymeric membranes: Surface modification for
minimizing (bio) colloidal fouling. Adv Colloid Interfac 206:116––140
Kochkodan V, Hilal N (2015) A comprehensive review on surface modified polymer membranes
for biofouling mitigation. Desalination 356:187–207. doi:10.1016/[Link].2014.09.015
Koga H, Kitaoka T, Wariishi H (2009) In situ synthesis of silver nanoparticles on zinc oxide
whiskers incorporated in a paper matrix for antibacterial applications. J Mater Chem 19
(15):2135–2140
Komlenic R (2010) Rethinking the causes of membrane biofouling. Filtr Sep 47(5):26–28. doi:10.
1016/S0015-1882(10)70211-1
Koseoglu H, Yigit NO, Iversen V, Drews A, Kitis M, Lesjean B, Kraume M (2008) Effects of
several different flux enhancing chemicals on filterability and fouling reduction of membrane
bioreactor (MBR) mixed liquors. J Membr Sci 320(1–2):57–64. doi:10.1016/[Link].2008.
03.053
Kox LSDM (2004) Membrane bioreactor in Varsseveld, the Dutch approach. In: Proceedings of
the water environment-membrane technology conference, Seoul, Korea
Kramer JF, Tracey DA (1995) The solution to reverse osmosis biofouling. In Proceedings of IDA
world congress on desalination and water use, Abu Dhabi, Saudi Arabia, November 19[25]95;
4:33–44
Kraume M, Wedi D, Schaller J, Iversen V, Drews A (2009) Fouling in MBR—what use are lab
investigations for full scale operation. Desalination 236:94–103
Laabs CN, Amy GL, Jekel M (2006) Understanding the size and character of fouling-causing
substances from effluent organic matter (EfOM) in low-pressure membrane filtration. Environ
Sci Technol 40(14):4495–4499. doi:10.1021/es060070r
Laborie S, Cabassud C, Durand-Bourlier L, Lainé JM (1998) Fouling control by air sparging
inside hollow fibre membranes—effects on energy consumption. Desalination 118(1–3):189–
196. doi:10.1016/S0011-9164(98)00124-6
78 3 Fouling in Membrane Bioreactors

Le Clech P, Jefferson B, Chang IS, Judd SJ (2003) Critical flux determination by the flux-step
method in a submerged membrane bioreactor. J Membr Sci 227(1–2):81–93
Lebegue J, Heran M, Grasmick A (2008) Membrane bioreactor: distribution of critical flux
throughout an immersed HF bundle. Desalination 231(1–3):245–252
Le-Clech P, Fane A, Leslie G, Childress A (2005a) The operator’s perspective. Filtr Sep 42:20–23
Le-Clech P, Jefferson B, Judd SJ (2005b) A comparison of submerged and sidestream tubular
membrane bioreactor configurations. Desalination 173(2):113–122
Le-Clech P, Cao Z, Wan PY, Wiley DE, Fane AG (2006a) The application of constant temperature
anemometry to membrane processes. J Membr Sci 284(1–2):416–423
Le-Clech P, Chen V, Fane TAG (2006b) Fouling in membrane bioreactors used in wastewater
treatment. J Membr Sci 284(1–2):17–53
Le-Clech P, Marselina Y, Stuetz R, Chen V (2006c) Fouling visualisation of soluble microbial
product models in MBRs. Desalination 199(1–3):477–479
Lee S, Lee CH (2000) Effect of operating conditions on CaSO4 scale formation mechanism in
nanofiltration for water softening. Water Res 34(15):3854–3866
Lee CK, Chang WG, Ju YH (1993) Air slugs entrapped cross-flow filtration of bacterial
suspensions. Biotechnol Bioeng 41(5):525–530. doi:10.1002/bit.260410504
Lee S, Kim J, Lee CH (1999) Analysis of CaSO4 scale formation mechanism in various
nanofiltration modules. J Membr Sci 163(1):63–74
Lee J, Ahn WY, Lee CH (2001a) Comparison of the filtration characteristics between attached and
suspended growth microorganisms in submerged membrane bioreactor. Water Res 35
(10):2435–2445
Lee JC, Kim JS, Kang IJ, Cho MH, Park PK, Lee CH (2001b) Potential and limitations of alum or
zeolite addition to improve the performance of a submerged membrane bioreactor. Water Sci
Technol 43:59–66
Lee W, Kang S, Shin H (2003) Sludge characteristics and their contribution to microfiltration in
submerged membrane bioreactors. J Membr Sci 216(1–2):217–227
Lee DH, Kim H-I, Kim SS (2004) Surface modification of polymeric membranes by UV grafting.
In: Advanced materials for membrane separations. ACS Symposium Series, American
Chemical Society 876:281-299
Lee SY, Kim HJ, Patel R, Im SJ, Kim JH, Min BR (2007) Silver nanoparticles immobilized on
thin film composite polyamide membrane: characterization, nanofiltration, antifouling
properties. Polym Adv Technol 18(7):562–568
Leiknes TO (2012) Membrane bioreactors. In: Peinemann K-V, Nunes SP (eds) Membranes for
water treatment. Wiley, New York, pp 193–226
Lesjean B, Rosenberger S, Laabs C, Jekel M, Gnirss R, Amy G (2005) Correlation between
membrane fouling and soluble/colloidal organic substances in membrane bioreactors for
municipal wastewater treatment. Water Sci Technol 51:1–8
Li XY, Yang SF (2007) Influence of loosely bound extracellular polymeric substances (EPS) on
the flocculation, sedimentation and dewaterability of activated sludge. Water Res 41(5):1022–
1030
Li QY, Cui ZF, Pepper DS (1997) Effect of bubble size and frequency on the permeate flux of gas
sparged ultrafiltration with tubular membranes. Chem Eng J 67(1):71–75. doi:10.1016/S1385-
8947(97)00016-8
Li QY, Ghosh R, Bellara SR, Cui ZF, Pepper DS (1998) Enhancement of ultrafiltration by gas
sparging with flat sheet membrane modules. Sep Purif Technol 14(1–3):79–83. doi:10.1016/
S1383-5866(98)00062-8
Li M, Zhao Y, Zhou S, Xing W, Wong FS (2007) Resistance analysis for ceramic membrane
microfiltration of raw soy sauce. J Membr Sci 299(1–2):122–129. doi:10.1016/[Link].2007.
04.033
Liang S, Liu C, Song L (2007) Soluble microbial products in membrane bioreactor operation:
behaviors, characteristics, and fouling potential. Water Res 41(1):95–101
Liao BQ, Bagley DM, Kraemer HE, Leppard GG, Liss SN (2004) A review of biofouling and its
control in membrane separation bioreactors. Water Environ Res 76(5):425–436
References 79

Lim BR, Ahn KH, Song KG, Woo CJ (2004) Microbial community in biofilm on membrane
surface of submerged MBR: effect of in-line cleaning chemical agent. In: Proceedings of the
water environment-membrane technology conference, Seoul, Korea
Lin CJ, Shirazi S, Rao P (2005) Mechanistic model for CaSO4 fouling on nanofiltration
membrane. J Environ Eng 131(10):1387–1392
Lin X, et al (2015) Composite ultrafiltration membranes from polymer and its quaternary
phosphonium-functionalized derivative with enhanced water flux. J Membrane Sci 482: p. 67–
75.
Liu R, Huang X, Xi J, Qian Y (2005) Microbial behaviour in a membrane bioreactor with
complete sludge retention. Process Biochem 40(10):3165–3170
Liu Y, Liu H, Cui L, Zhang K (2012) The ratio of food-to-microorganism (F/M) on membrane
fouling of anaerobic membrane bioreactors treating low-strength wastewater. Desalination
297:97–103
Lyko S, Al-Halbouni D, Wintgens T, Janot A, Hollender J, Dott W, Melin T (2007) Polymeric
compounds in activated sludge supernatant—characterisation and retention mechanisms at a
full-scale municipal membrane bioreactor. Water Res 41(17):3894–3902
Ma H, Hakim LF, Bowman CN, Davis RH (2001a) Factors affecting membrane fouling reduction
by surface modification and backpulsing. J Membr Sci 189(2):255–270
Ma H, Nielsen DR, Bowman CN, Davis RH (2001b) Membrane surface modification and
backpulsing for wastewater treatment. Sep Sci Technol 36(7):1557–1573
Ma W, Zhang J, Wang X, Wang S (2007) Effect of PMMA on crystallization behavior and
hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in
semi-dilute solutions. Appl Surf Sci 253(20):8377–8388
Mackay ME, Mackley MR, Wang Y (1991) Oscillatory flow within tubes containing wall or
central baffles. Chem Eng Res Des 69(6):506–513
Mansouri J, Harrisson S, Chen V (2010) Strategies for controlling biofouling in membrane
filtration systems: challenges and opportunities. J Mater Chem 20(22):4567–4586
Martinelli L, Guigui C, Line A (2010) Characterisation of hydrodynamics induced by air injection
related to membrane fouling behaviour. Desalination 250(2):587–591. doi:10.1016/[Link].
2009.09.029
Matsumura Y, Yoshikata K, Kunisaki SI, Tsuchido T (2003) Mode of bactericidal action of silver
zeolite and its comparison with that of silver nitrate. Appl Environ Microbiol 69(7):4278–4281
Mayer M, Braun R, Fuchs W (2006) Comparison of various aeration devices for air sparging in
crossflow membrane filtration. J Membr Sci 277(1–2):258–269. doi:10.1016/[Link].2005.
10.035
Meng F, Yang F (2007) Fouling mechanisms of deflocculated sludge, normal sludge, and bulking
sludge in membrane bioreactor. J Membr Sci 305(1–2):48–56. doi:10.1016/[Link].2007.07.
038
Meng F, Shi B, Yang F, Zhang H (2007) Effect of hydraulic retention time on membrane fouling
and biomass characteristics in submerged membrane bioreactors. Bioprocess Biosyst Eng
30:359–367
Meng F, et al. (2007) Characterization of cake layer in submerged membrane bioreactor. Environ
Sci Technol 41(11): p. 4065–4070
Meng F, Chae SR, Drews A, Kraume M, Shin HS, Yang F (2009) Recent advances in membrane
bioreactors (MBRs): Membrane fouling and membrane material. Water Res 43(6):1489–1512
Mercier M, Fonade C, Lafforgue-Delorme C (1997) How slug flow can enhance the ultrafiltration
flux in mineral tubular membranes. J Membr Sci 128(1):103–113. doi:10.1016/S0376-7388
(96)00317-1
Metzger U, Le-Clech P, Stuetz RM, Frimmel FH, Chen V (2007) Characterisation of polymeric
fouling in membrane bioreactors and the effect of different filtration modes. J Membr Sci 301
(1–2):180–189
Miura Y, Watanabe Y, Okabe S (2007) Membrane biofouling in pilot-scale membrane bioreactors
(MBRs) treating municipal wastewater: Impact of biofilm formation. Environ Sci Technol 41
(2):632–638. doi:10.1021/es0615371
80 3 Fouling in Membrane Bioreactors

Miyashita S, Honjyo K, Kato O, Watari K, Takashima T, Itakura M, Okazaki H, Kinoshita I,

Inoue N (2000) Gas diffuser for aeration vessel of membrane assembly. United States Patent
Patent
Mo Y, et al (2012) Improved antifouling properties of polyamide nanofiltration membranes by
reducing the density of surface carboxyl groups. Environ Sci Technol. 46(24):13253–13261
Nagaoka H, Nemoto H (2005) Influence of extracellular polymeric substance on nitrogen removal
in an intermittently-aerated membrane bioreactor. Water Sci Technol 51:151–158
Nagaoka H, Ueda S, Miya A (1996) Influence of bacterial extracellular polymers on the membrane
separation activated sludge process. Water Sci Technol 34:165–172
Ndinisa NV, Fane AG, Wiley DE, Fletcher DF (2006) Fouling control in a submerged flat sheet
membrane system: part II—two-phase flow characterization and CFD simulations. Sep Sci
Technol 41(7):1411–1445. doi:10.1080/01496390600633915
Neu TR, Marshall KC (1990) Bacterial polymers: physicochemical aspects of their interactions at
interfaces. J Biomater Appl 5(2):107–133
Ng CA, Sun D, Zhang J, Chua HC, Bing W, Tay S, Fane A (2005) Strategies to improve the
sustainable operation of membrane bioreactors. In: Proceedings of the international desalina-
tion association conference, Singapore
Ng HY, Tan TW, Ong SL (2006) Membrane fouling of submerged membrane bioreactors: impact
of mean cell residence time and the contributing factors. Environ Sci Technol 40(8):2706–2713
Nilson JA, DiGiano FA (1996) Influence of NOM composition on nanofiltration. J Am Water
Works Assoc 88(5):53–66
Ognier S, Wisniewski C, Grasmick A (2002a) Characterisation and modelling of fouling in
membrane bioreactors. Desalination 146(1–3):141–147
Ognier S, Wisniewski C, Grasmick A (2002b) Influence of macromolecule adsorption during
filtration of a membrane bioreactor mixed liquor suspension. J Membr Sci 209(1):27–37
Ognier S, Wisniewski C, Grasmick A (2002c) Membrane fouling during constant flux filtration in
membrane bioreactors. Membr Technol 147:6–10
Ognier S, Wisniewski C, Grasmick A (2004) Membrane bioreactor fouling in sub-critical filtration
conditions: a local critical flux concept. J Membr Sci 229(1–2):171–177
Oh SJ, Kim N, Lee YT (2009) Preparation and characterization of PVDF/TiO2 organic-inorganic
composite membranes for fouling resistance improvement. J Membr Sci 345(1–2):13–20
Okazaki M, Kimura S (1984) scale formation on reverse-osmosis membranes. J Chem Eng Jpn 17
(2):145–151
Pan JR, Su YC, Huang C, Lee HC (2010) Effect of sludge characteristics on membrane fouling in
membrane bioreactors. J Membr Sci 349(1–2):287–294
Pang CM, Hong P, Guo H, Liu WT (2005) Biofilm formation characteristics of bacterial isolates
retrieved from a reverse osmosis membrane. Environ Sci Technol 39(19):7541–7550
Park D, Lee DS, Park JM (2005) Continuous biological ferrous iron oxidation in a submerged
membrane bioreactor. Water Sci Technol 51:59–68
Pervov AG (1991) Scale formation prognosis and cleaning procedure schedules in reverse osmosis
systems operation. Desalination 83(1-3):77–118
Peuchot MM, Aim RB (1992) Improvement of cross-flow microfiltration performances with
flocculation. J Membr Sci 68:241–248
Phattaranawik J, Fane AG, Pasquier ACS, Wu B (2007) Membrane bioreactor with bubble-size
transformer: design and fouling control. AIChE J 53(1):243–248. doi:10.1002/aic.11040
Phuntsho S, et al (2012) Influence of temperature and temperature difference in the performance of
forward osmosis desalination process. J Membrane Sci 415–416:734–744
Pollice A, Brookes A, Jefferson B, Judd S (2005) Sub-critical flux fouling in membrane bioreactors
—a review of recent literature. Desalination 174(3):221–230
Porcelli N, Judd S (2010) Chemical cleaning of potable water membranes: a review. Sep Purif
Technol 71(2):137–143
Potts DE, Ahlert RC, Wang SS (1981) A critical review of fouling of reverse osmosis membranes.
Desalination 36(3):235–264
References 81

Psoch C, Schiewer S (2005) Long-term study of an intermittent air sparged MBR for synthetic
wastewater treatment. J Membr Sci 260(1–2):56–65. doi:10.1016/[Link].2005.03.021
Psoch C, Schiewer S (2006) Anti-fouling application of air sparging and backflushing for MBR.
J Membr Sci 283(1–2):273–280. doi:10.1016/[Link].2006.06.042
Rabie HR, Cote P, Singh M, Janson A (2003) Cyclic aeration system for submerged membrane
modules. United States Patent Patent
Ramesh A, Lee DJ, Wang ML, Hsu JP, Juang RS, Hwang KJ, Liu JC, Tseng SJ (2006) Biofouling
in membrane bioreactor. Sep Sci Technol 41(7):1345–1370
Ramesh A, Lee DJ, Lai JV (2007) Membrane biofouling by extracellular polymeric substances or
soluble mcirobial products from membrane bioreactor sludge. Appl Microbiol Biotechnol
74:699–707
Rana D, Matsuura T (2010) Surface modifications for antifouling membranes. Chem Rev 110
(4):2448–2471
Ridgway HF, Rigby MG, Argo DG (1985) Bacterial adhesion and fouling of reverse osmosis
membranes. J Am Water Works Assoc 77(7):97–106
Rosenberger S, Kraume M (2002) Filterability of activated sludge in membrane bioreactors.
Desalination 146(1–3):373–379
Rosenberger S, Krüger U, Witzig R, Manz W, Szewzyk U, Kraume M (2002a) Performance of a
bioreactor with submerged membranes for aerobic treatment of municipal waste water. Water
Res 36(2):413–420
Rosenberger S, Kubin K, Kraume M (2002b) Rheology of activated sludge in membrane
activation reactors. Chemie-Ingenieur-Technik 74(4):487–494 + 373
Roudman AR, Digiano FA (2000) Surface energy of experimental and commercial nanofiltration
membranes: Effects of wetting and natural organic matter fouling. J Membr Sci 175(1):61–73
Samir K, Kusakabe K, Raghunathan K, Fan LS (1992) Mechanism of heat transfer in bubbly
liquid and liquid-solid systems: single bubble injection. AIChE J 38(5):733–741
Schafer A, Fane A, Waite T (2005) Nanofiltation: principles and applications, 1st edn. Elsevier
Advanced Technology, Oxford, UK
Schneider RP, Ferreira LM, Binder P, Bejarano EM, Góes KP, Slongo E, Machado CR,
Rosa GMZ (2005) Dynamics of organic carbon and of bacterial populations in a conventional
pretreatment train of a reverse osmosis unit experiencing severe biofouling. J Membr Sci 266
(1–2):18–29. doi:10.1016/[Link].2005.05.006
Schoeberl P, Brik M, Bertoni M, Braun R, Fuchs W (2005) Optimization of operational parameters
for a submerged membrane bioreactor treating dyehouse wastewater. Sep Purif Technol 44
(1):61–68. doi:10.1016/[Link].2004.12.004
Serra C, Durand-Bourlier L, Clifton MJ, Moulin P, Rouch JC, Aptel P (1999) Use of air sparging
to improve backwash efficiency in hollow-fiber modules. J Membr Sci 161(1–2):95–113.
doi:10.1016/S0376-7388(99)00106-4
Sheikholaslami R (1999) Composite fouling—inorganic and biological: a review. Environ Prog 18
(2):113–122
Sheikholeslami R (1999) Fouling mitigation in membrane processes. Desalination 123(1):45–53
Shin HS, Kang ST (2003) Characteristics and fates of soluble microbial products in ceramic
membrane bioreactor at various sludge retention times. Water Res 37(1):121–127
Shirazi S, Lin CJ, Doshi S, Agarwal S, Rao P (2006) Comparison of fouling mechanism by CaSO4
and CaHPO4 on nanofiltration membranes. Sep Sci Technol 41(13):2861–2882. doi:10.1080/
01496390600854529
Shirazi S, Lin CJ, Chen D (2010) Inorganic fouling of pressure-driven membrane processes—a
critical review. Desalination 250(1):236–248
Simon A, Price WE, Nghiem LD (2013) Influence of formulated chemical cleaning reagents on the
surface properties and separation efficiency of nanofiltrationmembranes. J Membrane Sci
432:73–82
Smith PJ, Vigneswaran S, Ngo HH, Ben-Aim R, Nguyen H (2005) Design of a generic control
system for optimising back flush durations in a submerged membrane hybrid reactor. J Membr
Sci 255(1–2):99–106. doi:10.1016/[Link].2005.01.026
82 3 Fouling in Membrane Bioreactors

Sofia A, Ng WJ, Ong SL (2004) Engineering design approaches for minimum fouling in
submerged MBR. Desalination 160(1):67–74. doi:10.1016/S0011-9164(04)90018-5
Sperandio M, Masse A, Espinosa-Bouchot MC, Cabassud C (2005) Characterization of sludge
structure and activity in submerged membrane bioreactor. Water Sci Technol 52(10–11):401–
408
Speth T, Summers R, Gusses A (1998) Nanofiltration foulants from a treated surface water.
Environ Sci Technol 32:3612–3617
Spiazzi E, Lenoir J, Grangeon A (1993) A new generator of unsteady-state flow regime in tubular
membranes as an anti-fouling technique: a hydrodynamic approach. J Membr Sci 80(1):49–57.
doi:10.1016/0376-7388(93)85131-F
Sun Y, Huang X, Chen F, Wen XA (2004) dual functional filtration/aeration membrane bioreactor
for domestic wastewater treatment. In: Proceedings of the water environment-membrane
technology conference, Seoul, Korea
Sun Y, Wang Y, Huang X (2007) Relationship between sludge settleability and membrane fouling
in a membrane bioreactor. Front Environ Sci Eng China 1(2):221–225
Taha T, Cui ZF (2002) CFD modelling of gas-sparged ultrafiltration in tubular membranes.
J Membr Sci 210(1):13–27. doi:10.1016/S0376-7388(02)00360-5
Tansel B, Sager J, Garland J, Xu S, Levine L, Bisbee P (2006) Deposition of extracellular
polymeric substances (EPS) and microtopographical changes on membrane surfaces during
intermittent filtration conditions. J Membr Sci 285(1–2):225–231. doi:10.1016/[Link].2006.
08.031
Tao G, Kekre K, Wei Z, Lee TC, Viswanath B, Seah H (2005) Membrane bioreactors for water
reclamation. Water Sci Technol 51:431–440
Tardieu E, Grasmick A, Geaugey V, Manem J (1998) Hydrodynamic control of bioparticle
deposition in a MBR applied to wastewater treatment. J Membr Sci 147(1):1–12. doi:10.1016/
S0376-7388(98)00091-X
Teychene B, Guigui C, Cabassud C (2011) Engineering of an MBR supernatant fouling layer by
fine particles addition: a possible way to control cake compressibility. Water Res 45(5):2060–
2072. doi:10.1016/[Link].2010.12.018
Tiraferri A, et al (2012) Superhydrophilic thin-film composite forward osmosis membranes for
organic fouling control: Fouling behavior and antifouling mechanisms. Environ Sci Technol 46
(20):11135–11144
Tradieu E, Grasmick A, Geaugey V, Manem J (1998) Hydrodynamic control of bioparticle
deposition in a MBR applied to waste water treatment. Membr Sci 147:1–12
Trussell RS, Merlo RP, Hermanowicz SW, Jenkins D (2006) The effect of organic loading on
process performance and membrane fouling in a submerged membrane bioreactor treating
municipal wastewater. Water Res 40(14):2675–2683. doi:10.1016/[Link].2006.04.020
Trussell RS, Merlo RP, Hermanowicz SW, Jenkins D (2007) Influence of mixed liquor properties
and aeration intensity on membrane fouling in a submerged membrane bioreactor at high
mixed liquor suspended solids concentrations. Water Res 41(5):947–958. doi:10.1016/[Link].
2006.11.012
Ueda T, Hata K, Kikuoka Y (1996) Treatment of domestic sewage from rural settlements by a
membrane bioreactor. Water Sci Technol 34:189–196
Vallero MVG, Lettinga G, Lens PNL (2005) High rate sulfate reduction in a submerged anaerobic
membrane bioreactor (SAMBaR) at high salinity. J Membr Sci 253(1–2):217–232. doi:10.
1016/[Link].2004.12.032
Van De Lisdonk CAC, Van Paassen JAM, Schippers JC (2000) Monitoring scaling in
nanofiltration and reverse osmosis membrane systems. Desalination 132(1–3):101–108
Verbeck J, Worm G, Futselaar H, Dijk JCV (2000) Combined air water flush in dead-end
ultrafiltration. In: Proceedings of the IWA conference on drinking and industrial water
production, Paris, pp 655–663
Verrecht B, Judd S, Guglielmi G, Brepols C, Mulder JW (2008) An aeration energy model for an
immersed membrane bioreactor. Water Res 42(19):4761–4770. doi:10.1016/[Link].2008.09.
013
References 83

Visvanathan C, Ben aïm R (1989) Studies on colloidal membrane fouling mechanisms in

crossflow microfiltration. J Membr Sci 45(1–2):3–15
Visvanathan C, Yang BS, Muttamara S, Maythanukhraw R (1997) Application of air backflushing
technique in membrane bioreactor. Water Sci Technol 36(12):259–266. doi:10.1016/S0273-
1223(97)00727-0
Vrouwenvelder JS, van der Kooij D (2003) Diagnosis of fouling problems of NF and RO
membrane installations by a quick scan. Desalination 153(1–3):121–124
Vrouwenvelder JS, van Loosdrecht MCM, Kruithof JC (2011) Early warning of biofouling in
spiral wound nanofiltration and reverse osmosis membranes. Desalination 265(1–3):206–212
Wakeman R, Williams C (2002a) Additional techniques to improve microfiltration. Sep Purif
Technol 26:3–18
Wakeman RJ, Williams CJ (2002b) Additional techniques to improve microfiltration. Sep Purif
Technol 26(1):3–18. doi:10.1016/S1383-5866(01)00112-5
Wang Y, Howell JA, Field RW, Wu D (1994) Simulation of cross-flow filtration for baffled tubular
channels and pulsatile flow. J Membr Sci 95(3):243–258. doi:10.1016/0376-7388(94)00130-8
Wang S, Guillen G, Hoek EMV (2005) Direct observation of microbial adhesion to membranes.
Environ Sci Technol 39(17):6461–6469
Wang Z, Wu Z, Yin X, Tian L (2008) Membrane fouling in a submerged membrane bioreactor
(MBR) under sub-critical flux operation: membrane foulant and gel layer characterization.
J Membr Sci 325(1):238–244
Wang, XM, Li XY, Shih K (2011) In situ embedment and growth of anhydrous and hydrated
aluminum oxide particles on polyvinylidene fluoride (PVDF) membranes. J Membrane Sci 368
(1–2):134–143
Wang D, Zou W, Li L, Wei Q, Sun S, Zhao C (2011a) Preparation and characterization of
functional carboxylic polyethersulfone membrane. J Membr Sci 374(1–2):93–101. doi:10.
1016/[Link].2011.03.021
Wang XM, Li XY, Shih K (2011b) In situ embedment and growth of anhydrous and hydrated
aluminum oxide particles on polyvinylidene fluoride (PVDF) membranes. J Membr Sci 368(1–
2):134–143. doi:10.1016/[Link].2010.11.038
Watanabe Y, Kimura K, Itonaga T (2006) Influence of dissolved organic carbon and suspension
viscosity on membrane fouling in submerged membrane bioreactor. Sep Sci Technol 41
(7):1371–1382. doi:10.1080/01496390600633832
Wenten IG (1995) Mechanisms and control of fouling in crossflow microfiltration. Filtr Sep 32
(3):252–253. doi:10.1016/S0015-1882(97)84049-9
Wicaksana F, Fane AG, Chen V (2006) Fibre movement induced by bubbling using submerged
hollow fibre membranes. J Membr Sci 271(1–2):186–195. doi:10.1016/[Link].2005.07.024
Wiesner M, Veerapaneni S, Brejchova D (1992) Improvement in microfiltration using coagulation
pretreatment. In: Nice F, Klute R, Hahn H (eds) Proceedings of the fifth Gothenburg
symposium on chemical water and waste water treatment, NewYork. Springer, pp 20–40
Willems P, Kemperman AJB, Lammertink RGH, Wessling M, van Sint Annaland M, Deen NG,
Kuipers JAM, van der Meer WGJ (2009) Bubbles in spacers: direct observation of bubble
behavior in spacer filled membrane channels. J Membr Sci 333(1–2):38–44. doi:10.1016/j.
memsci.2009.01.040
Winzeler HB, Belfort G (1993) Enhanced performance for pressure-driven membrane processes:
the argument for fluid instabilities. J Membr Sci 80(1):35–47. doi:10.1016/0376-7388(93)
85130-O
Wisniewski C, Grasmick A (1998) Floc size distribution in a membrane bioreactor and
consequences for membrane fouling. Colloids Surf, A 138(2–3):403–411
Wu H (2012) Improving the anti-fouling and fouling release of PVDF UF membrane by
chemically modified SiO2 nanoparticles, New South Wales, Sydney, Australia
Wu J, Huang X (2010a) Use of azonation to mitigate fouling in a long-term membrane bioreactor.
Bioresour Technol 101:6019–6027
Wu J, Huang X (2010b) Use of ozonation to mitigate fouling in a long-term membrane bioreactor.
Bioresour Technol 101(15):6019–6027
84 3 Fouling in Membrane Bioreactors

Wu D, Howell JA, Field RW (1993) Pulsatile flow filtration of yeast cell debris: influence of
preincubation on performance. Biotechnol Bioeng 41(10):998–1002
Wu Z, Wang Q, Wang Z, Ma Y, Zhou Q, Yang D (2010) Membrane fouling properties under
different filtration modes in a submerged membrane bioreactor. Process Biochem 45(10):1699–
1706
Xiao K, Wang X, Huang X, Waite TD, Wen X (2011) Combined effect of membrane and foulant
hydrophobicity and surface charge on adsorptive fouling during microfiltration. J Membr Sci
373(1–2):140–151. doi:10.1016/[Link].2011.02.041
Xie RJ, Gomez MJ, Xing YJ, Klose PS (2004) Fouling assessment in a municipal water
reclamation reverse osmosis system as related to concentration factor. J Environ Eng Sci 3
(1):61–72
Xu P, Bellona C, Drewes JE (2010) Fouling of nanofiltration and reverse osmosis membranes
during municipal wastewater reclamation: Membrane autopsy results from pilot-scale
investigations. J Membrane Sci 353(1–2):111–121
Yamamoto K, Hiasa M, Mohmood T, Matsuo T (1989) Direct solid-liquid separation using hollow
fiber membrane in an activated-sludge aeration tank. Water Sci Technol 21:43–54
Yamamura H, Chae S, Kimura K, Watanabe Y (2007a) Transition in fouling mechanism in
microfiltration of a surface water. Water Res 41(17):3812–3822
Yamamura H, Kimura K, Watanabe Y (2007b) Mechanism involved in the evolution of physically
irreversible fouling in microfiltration and ultrafiltration membranes used for drinking water
treatment. Environ Sci Technol 41(19):6789–6794
Yamamura H, Okimoto K, Kimura K, Watanabe Y (2007c) Influence of calcium on the evolution
of irreversible fouling in microfiltration/ultrafiltration membranes. J Water Supply Res
Technol AQUA 56(6–7):425–434
Yamanoi I, Kageyama K (2010) Evaluation of bubble flow properties between flat sheet
membranes in membrane bioreactor. J Membr Sci 360(1–2):102–108. doi:10.1016/[Link].
2010.05.006
Yang Q, Chen J, Zhang F (2006a) Membrane fouling control in a submerged membrane bioreactor
with porous, flexible suspended carriers. Desalination 189 (1-3 SPEC. ISS.):292-302. doi:10.
1016/[Link].2005.07.011
Yang W, Cicek N, Ilg J (2006b) State-of-the-art of membrane bioreactors: Worldwide research and
commercial applications in North America. J Membr Sci 270(1–2):201–211
Yao M, Zhang K, Cui L (2010) Characterization of protein-polysaccharide ratios on membrane
fouling. Desalination 259(1–3):11–16
Yao M, Ladewig B, Zhang K (2011) Identification of the change of soluble microbial products on
membrane fouling in membrane bioreactor (MBR). Desalination 278(1–3):126–131
Yeom IT, Nah YM, Ahn KH (1999) Treatment of household wastewater using an intermittently
aerated membrane bioreactor. Desalination 124(1–3):193–204. doi:10.1016/S0011-9164(99)
00104-6
Yeon KM, Park JS, Lee CH, Kim SM (2005) Membrane coupled high-performance compact
reactor: a new MBR system for advanced wastewater treatment. Water Res 39(10):1954–1961.
doi:10.1016/[Link].2005.03.006
Yiantsios SG, Sioutopoulos D, Karabelas AJ (2005) Colloidal fouling of RO membranes: an
overview of key issues and efforts to develop improved prediction techniques. Desalination
183(1–3):257–272
You HS, et al (2005) A novel application of an anaerobic membrane process in wastewater
treatment, in Water Sci Technol pp 45–50
You HS, Huang CP, Pan JR, Chang SC (2006) Behavior of membrane scaling during crossflow
filtration in the anaerobic MBR system. Sep Sci Technol 41(7):1265–1278
Yu HY, Hu MX, Xu ZK, Wang JL, Wang SY (2005a) Surface modification of polypropylene
microporous membranes to improve their antifouling property in MBR: NH3 plasma treatment.
Sep Purif Technol 45(1):8–15. doi:10.1016/[Link].2005.01.012
References 85

Yu HY, Xie YJ, Hu MX, Wang JL, Wang SY, Xu ZK (2005b) Surface modification of
polypropylene microporous membrane to improve its antifouling property in MBR: CO2
plasma treatment. J Membr Sci 254(1–2):219–227. doi:10.1016/[Link].2005.01.010
Zeng Y (2007) Membrane bioreactor technology. National Defense Industry press, Beijing, China
Zhang Y, Bu D, Liu C, Luo X, Gu P (2004) Study on retarding membrane fouling by ferric salts
dosing in membrane bioreactors. In: Proceedings of the water environment-membrane
technology conference, Seoul, Korea
Zhang S, Qu Y, Liu Y, Yang F, Zhang X, Furukawa K, Yamada Y (2005) Experimental study of
domestic sewage treatment with a metal membrane bioreactor. Desalination 177(1–3):83–93.
doi:10.1016/[Link].2004.10.034
Zhang HM, Xiao JN, Cheng YJ, Liu LF, Zhang XW, Yang FL (2006a) Comparison between a
sequencing batch membrane bioreactor and a conventional membrane bioreactor. Process
Biochem 41(1):87–95. doi:10.1016/[Link].2005.03.072
Zhang JS, Chuan CH, Zhou JT, Fane AG (2006b) Effect of sludge retention time on membrane
bio-fouling intensity in a submerged membrane bioreactor. Sep Sci Technol 41(7):1313–1329
Zhang K, Cui Z, Field RW (2009) Effect of bubble size and frequency on mass transfer in flat sheet
MBR. J Membr Sci 332(1–2):30–37. doi:10.1016/[Link].2009.01.033
Zhang H, Gao J, Jiang T, Gao D, Zhang S, Li H, Yang F (2011a) A novel approach to evaluate the
permeability of cake layer during cross-flow filtration in the flocculants added membrane
bioreactor. Bioresour Technol 102:11121–11131
Zhang K, Wei P, Yao M, Field R, Cui Z (2011b) Effect of the bubbling regimes on the
performance and energy cost of flat sheet MBRs. Desalination 283:221–226
Zhang K, Wei P, Yao M, Field RW, Cui Z (2011c) Effect of the bubbling regimes on the
performance and energy cost of flat sheet MBRs. Desalination 283:221–226. doi:10.1016/j.
desal.2011.04.023
Zhang M, Zhang K, De Gusseme B, Verstraete W (2012) Biogenic silver nanoparticles (bio-Ag 0)
decrease biofouling of bio-Ag 0/PES nanocomposite membranes. Water Res 46(7):2077–2087
Zhang J, Zhang M, Zhang K (2014) Fabrication of poly(ether sulfone)/poly(zinc acrylate)
ultrafiltration membrane with anti-biofouling properties. J Membr Sci 460:18–24
Zhao C, Xue J, Ran F, Sun S (2013a) Modification of polyethersulfone membranes—a review of
methods. Prog Mater Sci 58(1):76–150
Zhao YH, Qian YL, Zhu, BK, et al (2008c), 'Modification of porouspoly(vinylidene fluoride)
membrane using amphiphilic polymers with different structures inphase inversion process',
Journal of Membrane Science, 310(1-2), 567–76
Zhou R, Ren PF, Yang HC, Xu ZK (2014) Fabrication of antifouling membrane surface by poly
(sulfobetaine methacrylate)/polydopamine co-deposition. J Membr Sci 466:18–25
Zhu X, Bai R, Wee KH, Liu C, Tang SL (2010) Membrane surfaces immobilized with ionic or
reduced silver and their anti-biofouling performances. J Membr Sci 363(1–2):278–286
Zsirai T, Buzatu P, Aerts P, Judd S (2012) Efficacy of relaxation, backflushing, chemical cleaning
and clogging removal for an immersed hollow fibre membrane bioreactor. Water Res 46
(14):4499–4507. doi:10.1016/[Link].2012.05.004
Zularisam AW, Ismail AF, Salim R (2006) Behaviours of natural organic matter in membrane
filtration for surface water treatment—a review. Desalination 194(1–3):211–231
Chapter 4
Surface Modification of Polyethersulfone
Membranes

Polyethersulfone (PES) membranes have been broadly used in scientific research

and industrial processes due to their outstanding properties, such as high
mechanical strength, high thermal stability, good chemical resistance and mem-
brane forming ability. They have also been used in a cross range of applications,
particularly wastewater treatment. This membrane is intrinsically hydrophobic in
nature. Therefore, this property make PES membranes more prone to fouling, so
surface modification techniques are an excellent pathway to improve hydropho-
bicity and enhance antifouling performance. In this chapter, we present different
techniques to alleviate membrane fouling. This chapter sheds light specifically on
surface modification of membranes. In this chapter, various types of modification
techniques are outlined, including bulk modification, blending, grafting procedures
and coating methods.

4.1 Introduction

Since the early 1960s and the emergence of widespread industrial membrane
separations, there has been extensive research into alleviating membrane fouling,
especially in membrane bioreactors (Kochkodan and Hilal 2015). An extremely
wide range of approaches have been explored, including pre-treatment of feed
(flocculation), optimisation of operating conditions, gas sparging, pulsatile,
aggressive and frequent cleaning of the membrane, radiation and membrane
modification (Baker 2012; Belfort et al. 1994; Chae et al. 2006; Hai et al. 2008;
Hilal et al. 2005; Le-Clech et al. 2006a; b, c; McCloskey et al. 2012; Ridgway et al.
1984; Rosenberger et al. 2002; Sheikholaslami 1999; Sheikholeslami 1999; Wu
et al. 2008; Wu and Huang 2008).
Among these methods, surface modification of membrane is considered to be an
effective technology or an effective way to reduce the interactions between mem-
brane surface and foulants, thereby reduce membrane fouling, enhancing membrane
© Springer Nature Singapore Pte Ltd. 2017 87
B. Ladewig and M.N.Z. Al-Shaeli, Fundamentals of Membrane Bioreactors,
Springer Transactions in Civil and Environmental Engineering,
DOI 10.1007/978-981-10-2014-8_4
88 4 Surface Modification of Polyethersulfone Membranes

longevity and performance, and also reducing the adsorption of protein on a

membrane surface (Liu and Kim 2011; McCloskey et al. 2012; Shannon et al.
2008). As noted by (Moghimifar et al. 2014), surface modification of membrane is
one of the techniques used to modify the membrane surface by increasing the
hydrophilicity of the membrane and minimising membrane fouling to a minimum.
In general, it is evident that the increase in membrane surface hydrophilicity
enhances antifouling capability because most of the natural biopolymers (i.e. pro-
teins) exhibit hydrophobic properties (Li et al. 2014). Theoretically, hydrophilic
surfaces have the capability to display a buffer layer composed of water molecules
and prevent foulants from depositing on membrane surface or at membrane pores
which results in a stable and higher water flux (Peeva et al. 2012).
The surface modification of membrane may be performed by two distinct groups
of polymer surface modifications: the first group is referred as chemical modifi-
cation and the second group is physical modification (Mittal 2009). Physical
modification of a polymer surface involves exposure of polymer to plasma, flame,
radiation and ion beams method and is time-dependent (Chu et al. 2005). Chemical
modification of a polymer surface necessitates or requires chemical reaction
between polymer surface and functional groups and the modified polymer surface is
reasonably stable over time.
Surface modification of membranes includes generation of two layers (made of
two different polymeric materials) on the membranes. The first layer (thin layer)
controls the flux, selectivity and adsorption of solute whilst the second layer (thick
substrate) provides mechanical strength and chemical stability.
In term of protein separation or concentration using membrane processes, sur-
face modification of polymeric membranes mostly takes the form of introducing
hydrophilic functional groups or incorporating hydrophilic layers onto the surface
of membrane. Examples of surface modifications aimed at improving surface
resistance to adsorption of protein and membrane permeation property include the
introducing of hydrophilic polymers or inorganic fillers through blending
(Rajagopalan et al. 2004; Van Der Bruggen 2009a; Wang et al. 2006a, b; Zhao et al.
2011, 2013b), coating (Razmjou et al. 2011a; Brink et al. 1993; Hilal et al. 2005;
Wei et al. 2005; La et al. 2011; Yu et al. 2011) and surface grafting (Kim et al.
2002; Ulbricht and Riedel 1998; Yune et al. 2011; Kang et al. 2007; Liu et al. 2008;
Rahimpour 2011b; Rana and Matsuura 2010; Ulbricht and Belfort 1996; Ulbricht
et al. 1996; Revanur et al. 2007a), self-assembly monomers (Luo et al. 2005). These
techniques have successfully enhanced membrane surface properties, such as
improving membrane permeation, improving mechanical strength, hydrophilicity
and fouling resistance (Zhu et al. 2014). However, they also have some short-
comings or limitations hindering their further popularity in membrane industry, for
instance, coating method can be simply applied at industrial scale but the coating
layer is instable (easily removable in use. In contrast, grafting is easily adhering but
not easy to apply at industrial use. They usually need substantial post treatment
process, leading to high cost of membrane fabrication costs (Zhu et al. 2014).
To conclude, surface modification of membrane is an effective strategy to
modify the membrane surface and enhance its surface characteristics such as
4.1 Introduction 89

increase membrane hydrophilicity, increase water flux and minimise adhering

inorganic, organic and biological materials on the membrane surface. Bear in mind,
inorganic, organic and biological materials are the main cause of occurrence fouling
in membrane bioreactors.

4.2 Surface Modification

As aforementioned, PES membrane is intrinsically hydrophobic in nature. Numerous

research studies for example (Khulbe et al. 2010a, b; Van Der Bruggen 2009a) stated
that membrane fouling is related directly to hydrophobic membranes. Therefore, this
membrane needs to be modified in order to alleviate membrane fouling to a certain
extent. Three approaches have been used to modify PES membrane: (1) bulk mod-
ification of the prepared PES membrane, and then to prepare modified membrane;
(2) surface modification of prepared PES membrane; and (3) blending (it is regarded
as a surface modification). Membrane modification method can be used to find a
compromise between hydrophobicity and hydrophilicity, by localising hydrophilic
functional groups specifically in the membrane pores. They have a great impact on
membrane permeation, morphology of membrane, and provide the membrane with
stimuli-responsivity and better blood compatibility (Zhao et al. 2013a). The first
membrane modification process which was reported in the literature is annealing of
porous membranes through heat treatment (Khayet et al. 2003; Pinnau and Freeman
2000). The porous membrane was used in different applications such as reverse
osmosis, gas separation and ultrafiltration membranes.
Table 4.1 shows a number of membrane modification methods such as annealing
with heat treatment, solvent treatment, surface coating, chemical treatment, and
their application in an industrial area.
Van Der Bruggen (2009a) studied the chemical and physicochemical modification
methods, which were used to enhance membrane hydrophilicity of PSF/PES
nanofiltration (NF) membranes. In case of increasing hydrophilicity of membranes,
modification of membranes can be implemented in different techniques. Physical or
chemical modification methods after the membrane is prepared or formed can endow
the membranes with hydrophilic surfaces. Such modification processes include
(1) graft polymerization process (hydrophilic monomers are chemically attached to
the surface of membrane) (2) plasma treatment process (incorporate the functional
graft chains on the surface of membrane); and (3) physical pre-adsorption of
hydrophilic groups to the surface of membrane.
Obviously, various modification methods have been used to modify PES
membranes including physical processes such as blending and surface-coating
processes (Li et al. 2010; Liu et al. 2009; Ran et al. 2011; Reddy et al. 2003; Wang
et al. 2009b), and chemical processes including photo-induced grafting (Zhao et al.
2003), gamma ray (Filho and Comes 2006; Deng et al. 2009) and electron
beam-induced grafting (Keszler et al. 1991; Schulze et al. 2010), plasma treatment
and plasma-induced grafting (Batsch et al. 2005; Gancarz et al. 1999b; Van Der
Bruggen 2009a), thermal-induced grafting and immobilisation (Fang et al. 2009,
90 4 Surface Modification of Polyethersulfone Membranes

Table 4.1 Common membrane modifications

Modification method Function Application
Annealing – Elimination of membrane defects RO, GS, UF
– Heat treatment – Control of pore size
– Solvent treatment
Solvent exchange – Elimination of membrane defects GS, UF
Surface coating – Elimination of membrane defects GS, RO, NF,UF
– Melioration of fouling resistance
Chemical treatment Improvement of flux and selectivity GS
– Fluorination Improvement of chemical resistance UF
– Cross-linking Improvement of flux and selectivity RO, GS, PV
– Pyrolysis
GS gas separation, RO reverse osmosis, UF ultrafiltration, NF nanofiltration, PV pervaporation
(Pinnau and Freeman 2000)

2010; Kroll et al. 2007; Liu et al. 2009; Shi et al. 2010a, b), surface-initiated atom
transfer radical polymerization (Li et al. 2009c, d, e, f), and so on (Cao et al. 2010;
Liu et al. 2008; Rana and Matsuura 2010; Tari et al. 2010; Sun et al. 2003). These
methods have successfully modified the surface of polymeric membranes, such as
PES, PVDF, and PP and so on. The function of these methods is to make the
membrane super hydrophilic and reduce membrane fouling to a great extent.
With the development in membrane modification process, reversible
addition-fragmentation chain transfer polymerization (RAFT) and click chemistry
methods are new techniques used recently to modify PES membranes. They are
discovered by CSIRO.

4.3 Bulk Modification

Bulk modification methods are usually very simple methods because they are used
to a polymer solution, and not on a membrane surface (Peyravi et al. 2012).
However, the entire or whole membrane is modified in this way, therefore leading
to a lower net effect and, possibly, an enhanced effect of swelling in the structure of
the resulting membrane (Zhu et al. 2007a, b). Sulfonation and carboxylation are the
most commonly reported methods in many journal articles. But sulphonation is one
of the membrane modification methods, which used widely in industrial section
(Wang et al. 2009a; Rahimpour et al. 2010a; Cao et al. 2010). Sulfonation of PES
membrane is an electrophilic reaction, in which the negatively charged sulfonic acid
groups are introduced onto PES membranes, resulting in replacing the hydrogen
atom with sulfonic acid groups as shown in Fig. 4.1 (Van Der Bruggen 2009a). As
can be seen from the figure, the sulfonic group is localised in ortho positions on the
aromatic rings of PES polymer because this electron donating oxygen atom which
activates ortho position (Blanco et al. 2001; Iojoiu et al. 2005). Sulphonation
method is affected by the electron donating properties of a polymer and elec-
trophilicity of the sulphonating agent. However, PES matrix is thoroughly hard to
4.3 Bulk Modification 91

sulphonate due to the electron withdrawing effect of the sulfonic linkages, which
deactivates the adjacent aromatic rings for electrophilic substitution. PES mem-
branes generated by sulphonation reaction are super hydrophilic, have excellent
antifouling property, proton conductivity and better selectivity. The sulphonation of
PES has been described in many journal articles with different sulphonating agents
and solvents used: SO3/CH2Cl2 [5, 7], ClSO3H/CH2Cl2 [8], SO3-triethylphosphate
(TEP)/CH2Cl2 [9], oleum/concentrated sulfuric acid [10].
In contrast, carboxylation is a practical method, which involves addition of
carboxylic groups to polymeric PES membrane matrix, in which carboxyl group
substitutes the hydrogen atom at an aromatic hydrocarbon. In carboxylation
method, PES can be oxidised or acetylated at specific conditions as explained in
Fig. 4.2. PES membranes generated by carboxylation, have a great influence on the
hydrophilicity of the polymer, which was verified by measurements of water
adsorption and measurements of contact angle (Zhao et al. 2013b, a). Introducing
carboxylic groups to PES matrix, as shown in Fig. 4.2, could increase the
hydrophilicity of membranes.
Apart from sulphonation and carboxylation methods, nitration is another method
used to introduce amine groups to the polymeric PES membrane to modify its
surface. Van Der Bruggen (2009a) states that the limitation of bulk modifications
can be solved through blending method, which is the same to the use of copolymers
but using a physical route. This also allows the use of “simple” polymers. Recently,
different functional groups were introduced to PES membranes. PES was firstly
sulfonated by chlorosulfonic acid (ClSO3) at 0 °C for 2 h to form sulfonated PES.
The degree of sulphonation was about 15 %. Then sulfonated PES was chlorinated
by phosphorous pentachloride to form SPES/SO2Cl as presented schematically in
Fig. 4.3 (Bai et al. 2010). Sulphonated PES is more reactive toward amine group,
hydroxyl group, carboxyl group and methyl group as shown in Fig. 4.3.
Shi et al. (2010) grafted methacylic acid (MAA) onto polymeric PES membrane
network in heterogeneous reaction, using benzoyl peroxide (BPO) as a chemical
initiator. The polymerisation process was implemented in an aqueous medium.
Because of the conformational change of PMAA chains with environmental pH,
membrane cast from PMAA-g-PES exhibited reversible pH dependent permeability
as the pH value of feed solution was varied (Zhao et al. 2013a).

SO3 H
O

S O

n
O

Fig. 4.1 Polyethersulfone, with the sulfonic acid group on the benzene ring
92 4 Surface Modification of Polyethersulfone Membranes

O O
AlCl3, CH3COCl, 2h
S O S O
O stirring, refluxing, 90 C O
n n
COCH3
O O
NaOH, KMnO 4, 6h
S O S O
O stirring, 80 C
n O n
COCH3 COOH

Fig. 4.2 Fabrication of polyethersulfone membranes by carboxylation method (adapted from

Wang et al. 2011)

SO3H/SO2Cl
O O
ClSO2H
S O S O
O CH2Cl2 O
n n
PES PES-SO3H/SO2Cl

H2N-CH2CH2NH2
PES-SO2Cl PES-SO2-NHCH2CH2-NH2
OH-CH2CH2OH
PES-SO2Cl PES-SO2-OCH2CH2-OH
NH2CH2COOH
PES-SO2Cl PES-SO2-NHCH2-COOH
H2N-CH2CH3
PES-SO2Cl PES-SO2-NHCH2-CH3

Fig. 4.3 Synthesis of PES with different functional groups (Adapted from Zhao et al. 2013a; Bai
et al. 2010)

4.4 Physical Modification of PES

Physical modification of PES usually involves one of two distinctive approaches,

either the blending technique or the surface coating technique.

4.4.1 Blending

Blending is the simplest method and most effective modification process to modify
polymeric membranes (both flat-sheet and hollow fiber membranes PES mem-
branes), since the results might not very effective at certain time (Zhao et al. 2013a).
Moreover, it is regarded as the most practical way, which can be used to an
4.4 Physical Modification of PES 93

industrial scale production. PES membranes are very easy to modify in this method.
This method is often employed to obtain the desired functional properties along
with the membrane preparation. Thus, both inside pores of membranes and the
membrane surfaces can be modified simultaneous through the interactions between
the basic polymer and additives. This can enable the prepared membrane to have
the comprehensive properties of the blend materials (Venault et al. 2014; Bottino
et al. 2000; Ying et al. 2002; Madaeni et al. 2011).
By directly blending hydrophilic polymers additives, for example polyvinyl-
pyrrolidone (PVP) (Barzin et al. 2004; Dang et al. 2008) and polyethyleneglycol
(PEG) (Wang et al. 2006a, b, c; Su et al. 2008; Dang et al. 2008) into membrane bulk,
the membrane hydrophilicity increased, the antifouling performance and blood
compatibility are also increased. PVP and PEG are homopolymeric polymers that
used as pore—forming agents. These additives are water-soluble and can be leached
out from hydrophobic PES membranes during membrane preparation and operation
processes, leading to deterioration of membrane performance. Therefore,
cross-linking with additives or covalent grafting has been proposed to tackle the issue
of leaching out these additives (Park et al. 2006; Tripathi et al. 2012). Tripathi et al.
(2014) prepared highly hydrophilic and fouling resistant porous membranes by
covalent cross-linking of sulfonated PES with amino terminated poly ethylene
glycol. PES was sulfonated and cross-linked with poly (ethyleneglycol) bis-
(3-aminopropyl)terminated via sulfonamide linkage using1,1′-carbonyldiimidazole
(CDI). The cross-linked membranes showed superior water permeation flux, rejec-
tion, and antifouling performance in comparison to the neat membranes. The protein
adsorption on membrane surface was about10-foldless than that of the control PES
membrane The results reveal that, hydrophilicity was increased due to the existence
of PEG, leading to the 3-fold increase in water permeation flux and more than 90 %
protein rejection efficiency.
Another approach to avoid the leaching out of these additives is using
Amphiphilic copolymers. Recently, these polymers are synthesised and used as
additives to fabricate PES membranes (Zhu et al. 2008a, b).
Various blending methods have been devoted or performed to modify PES
membranes to enhance their antifouling properties and improve the hydrophilicity.
These methods include blending with hydrophilic nanoparticles, blending with
homopolymeric membranes (e.g. PVP and PEG), blending with amphiphilic
polymers, and blending with zwitterionic polymers, and blending with surface
modifying macromolecules.
Blending with hydrophilic nanoparticles has become a new domain of interest in
membrane separation technology due to its ease and simplicity (Jamshidi Gohari
et al. 2014). The resulting membranes have unique properties, including excellent
separation performance, reasonable operation under harsh conditions (Yang et al.
2006), adaptability to milder environments, good thermal and chemical stability,
and excellent antifouling properties (Molinari et al. 2002; Akar et al. 2013). The
purpose of incorporating nanoparticles into polymeric membranes is to improve
hydrophilicity and to improve pore formation and interconnectivity (Rahimpour
and Madaeni 2010; Rahimpour et al. 2010b, c). Nanoparticles have indeed unique
94 4 Surface Modification of Polyethersulfone Membranes

properties such as chemical properties; thermal and mechanical stable properties,

electrical properties, small size, large surface area and strong additives. Therefore,
they have attracted a great deal of attention recently. Akar et al. (2013) states that
incorporating nanoparticles with membrane results in improved membrane surface
properties (regarding to chemical and thermal resistance), improved separation
performance, mechanical properties and antifouling properties. Therefore, various
nanoparticles have been utilised in fabricating PES membrane, including, titanium
dioxide (TiO2) (Arthanareeswaran et al. 2008; Luo et al. 2005, 2011; Razmjou et al.
2011a, b; Devrim et al. 2009; Sotto et al. 2011), mesoporous silica (MS) (Huang
et al. 2012; Yu et al. 2009b; Yin et al. 2012), modified multi-walled carbon nan-
otubes (Daraei et al. 2013b), silver (Huang et al. 2012), magnesium hydroxide Mg
(OH)2 (Dong et al. 2012), calcium carbonate nanoparticles (CCNP) (Nair et al.
2013) and Carbon nanotube (CNT) (Majeed et al. 2012; Ajmani et al. 2012) and
HNTs (Liu et al. 2009).
Chen et al. (2013) investigated the effects of halloysite nanotubes—chitosan
(CHI)—Ag nanoparticles on the antifouling properties and performance of PES
membranes and the results demonstrated that the adding halloysite nanotubes—CHI
—Ag nanoparticles into PES membranes could lead to an increase in the
hydrophilicity of the modified membrane and then resulted in excellent both
membrane permeation and flux recovery ratio (FRR) in comparison to the neat PES
membrane.
Razmjou et al. (2012) investigated the effect of TiO2 nanoparticles on the
morphology, performance and antifouling properties of PES membrane. They
concluded that incorporating TiO2 nanoparticles into PES membranes, indicating
good membrane hydrophilicity, lower contact angle and higher FRR.
Dong et al. (2012) point out that Mg (OH)2 nanoparticles are very efficient in
preventing flux declines, causing the hybrid membrane to show excellent
antifouling performance, and higher hydrophilicity than the unmodified membrane.
The performance of membranes is enhanced due to the existence of—OH groups on
the surface of membrane.
Nair et al. (2013), also investigated the effect of OH groups on the hydrophilicity
of membranes when the hydroxyl group was formed from CCNP to Ca–OH in an
aqueous medium.
Jamshidi Gohari et al. (2014) investigated the introducing of hydrous manganese
dioxide (HMO) nanoparticles to PES ultrafiltration membrane. They concluded that
these nanoparticles have higher capability for enhancing the properties of UF
membranes, especially their antifouling properties. HMO nanoparticles offer several
advantages, such as microporous structure, large surface area and can be readily
prepared through redox reaction (Taffarel and Rubio 2010; Teng et al. 2009).
Razali et al. (2013) investigated the effect of incorporating polyaniline
nanoparticles as polymeric additives to PES membranes. They stated that these
nanoparticles have the capability to enhance the hydrophilic properties and per-
meability of the substrate membrane. Polyaniline nanoparticles are used to achieve
super hydrophilic surfaces due to their high-surface energy and hydrophilic prop-
erties (Fan et al. 2008).
4.4 Physical Modification of PES 95

Recently, Zinadini et al. (2014) investigated the blending of graphene oxide

nanoparticles (GO) onto PES based-UF membrane. They demonstrated that these
inorganic nanoparticles have had the best antifouling property when 0.5 wt%
concentrations added to the dope solution.
Huang et al. (2012) used MS particles as an advanced antifouling membrane
material. The membrane hydrophilicity and antifouling performance were improved
significantly. Li et al. (2014) employed Polydopamine (PD) coating and
PD-graft-poly(ethylene glycol) (PD-g-PEG). The results showed that the modified
membrane had a fine mechanical stability, and the PD-g-PEG modified membrane
had a better chemical stability. The membrane hydrophilicity was increased
according to the measurements of contact angle. In comparison to the pristine
membranes, the modified membranes adsorbed less BSA under the same condition.
Furthermore, PD-g-PEG modified membrane seems to have less adsorptive fouling
potential than PD-coating membrane. Generally, PD-g-PEG modification should be
more promising in industrial application or scale.
Modified PES UF membranes by SiO2@N-Halamine. The membrane
hydrophilicity was significantly enhanced after introducing SiO2@N-Halamine.
The filtration results indicated that the permeation properties of the hybrid mem-
branes were significantly superior in compared to the control PES membrane. The
water flux of the hybrid membranes increased with the additional amount of
SiO2@N-Halamine increased. When the amount of SiO2@N-Halamine was 5 %,
the membrane permeation of hybrid membrane reached the maximum at 384.4 L
m−2 h−1. Furthermore, the hybrid membranes showed good antifouling and
antibacterial properties, which might extend the usage of PES in the application of
water treatment and could make some potential contributions to membrane
antifouling.
Pang et al. (2014) developed a simple in situ method for the preparation of
hydrous zirconia ZrO2/PES UF. They merged an ion-exchange method with a
classic immersion precipitation method. The solution of hydrous zirconia (ZrO2)
was prepared by addition of anion-exchange resin in N, N-dimethylformamide
(DMF) solvent containing zirconyl chloride. The results indicated that the ZrO2
nanoparticles were dispersed well into PES matrix and the diameter of the prepared
nanoparticles was about 5–10 nm. The hydrophilicity of the hybrid membranes was
improved significantly. The adsorption of protein was reduced as a result of
incorporating ZrO2 nanoparticles in the PES matrix.
Zhao et al. (2015) developed a new method for modifying PES/ZnO UF
membranes. Nano-ZnO was coated with PVP polymer using DMF as solvent. The
obtained ZnO-DMF dispersion was blended as an additive to fabricate PES/ZnO
membranes via wet phase separation. The results showed that the antifouling per-
formance was improved. The thermal stability of the hybrid membranes was also
enhanced in comparison to the pristine PES membranes.
Martín et al. (2015) modified PES UF membranes by incorporating
mesostructured modified silica particles in PES membranes. The antifouling
properties of the treated membranes were improved, particularly against irreversible
96 4 Surface Modification of Polyethersulfone Membranes

fouling. Multi-run fouling experiments of the hybrid membranes verified the sta-
bility of membrane permeation after introducing mesostructured modified silica.
Xiang et al. (2014) prepared ionic-strength-sensitive membrane through in situ
cross-linked polymerization of sulfobetaine methacrylate (SBMA) in PES solution
and a liquid–liquid phase separation process. The membrane with high amounts of
PSBMA showed an obvious ionic-strength-sensitive property and ionic-strength
reversibility, which are expressed by the fluxes of salt solutions. At the same time,
the antifouling property and blood compatibility are increased significantly when
the amount of PSBMA increased in the PES membrane.
Xie et al. (2015) prepared a novel zwitterionic glycosyl modified PES UF
membranes through coupling in situ cross-linking polymerization process with
phase inversion process. The results showed the modified membranes have an
excellent antifouling performance, and the FRR could reach almost 100 %.
Menawhile, the blood compatibility of the membranes was determined by protein
adsorption experiment; platelet adhesion activated partial thromboplastin time
(APTT), and thrombin time (TT). The results indicated that the surface modified
PES membranes had good antifouling performance and blood compatibility
(anticoagulant).
Duan et al. (2015) modified PES ultrafiltration membrane by blending with N-
halamine grafted HNTs (halamine@HNTs), which is anticipated to improve the
antibacterial property and the permeability of the membranes. The results indicated
that the membrane hydrophilicity was enhanced significantly after adding N-
halamine@HNTs. The membrane permeability (Water flux) of the hybrid mem-
branes could reach as high as 248.3 L m−2 h−1 when the amount of N-
halamine@HNTs was 1.0 wt%. Additionally, the antibacterial experiment indicated
that the hybrid membranes showed good antibacterial activity against E. coli
(Table 4.2).
Ultimately, one of the most significant issues with blending nanoparticles into
polymer matrix is the agglomeration phenomenon. An agglomeration phenomenon
causes the non-uniform distribution of particles in the membrane and the instability
of the casting solution. This will lead to a big change in microstructure, topography
and performance and also the potential decreasing of antifouling ability of
nanoparticles. There have been a number of articles reporting that agglomeration
phenomena is due to the nature properties of nanoparticles (e.g. small size and high
surface energy) and the bad compatibility with hydrophobic PVDF bulk (Kang and
Cao 2014). Agglomeration phenomena can be reduced by three approaches:
1. Functionalisation of nanoparticles or surface modification of nanoparticles
(Zhang et al. 2014; Razmjou et al. 2011b; Shi et al. 2013)
2. In situ formation of nanoparticles via sol-gel method (Yu et al. 2009b)
3. Creating the bridge to improve the interaction between nanoparticles by the
addition of a third component. Therefore, the nanoparticles have to be carefully
selected to ensure their dispersion in the membrane matrix to avoid agglomer-
ation issues.
Table 4.2 Illustrates some of the recent research studies that have been conducted PES membranes through blending technique using different nanoparticles
(Jamshidi Gohari et al. 2014)
Polymer Nanoparticles Pure water flux Protein flux Rejection (%) Contact Flux Reference
(L/m2h) (L/m2h) angle (˚) recovery (%)
PES
PES Halloysite nanotubes-chitosan-Ag 357.6 at 1 bar 0.75 N/A 55 97.6 Chen et al. (2013)
NIPS normalised
flux
PES Functionalised multi-walled 25 at 4 bar 5–10 (whey 97 (whey 49.8 95 Daraei et al.
carbon nanotube protein) protein) (2013a)
4.4 Physical Modification of PES

PES Mesoporous silica 180.2 at 2 bar 75.8 96.1 BSA 56.6 76.2 Yin et al. (2012)
PES Ag-loaded sodium zirconium 100.6 at 1 bar 51 96.7 BSA 58.4 78.4 Huang et al. (2012)
phosphate NPs
PES PANi/PMA NPs 320 at 2 bar 225 99 BSA 72.3 72.8 Taffarel and Rubio
(2010)
PES Copper particles 69 (0.5–1.5) bar N/A 86.3 BSA 55.3 76.3 Akar et al. (2013)
PES Biogenic silver NPs 520 at 2 bar N/A N/A 51.4 N/A Teng et al. (2009)
PES TiO2 55 at 1 bar N/A 95 (dextran 50 61.54 Razmjou et al.
500 Da) (2012)
PES PES/PVP semi-interpenetrating 243.2 at 0.5 bar 50–60 93 BSA 53 94 Su et al. (2010)
network NPs
PES TiO2 450 at 1 bar N/A 94 (dextran 62 84 Mishra and Vijaya
500 Da) (2007)
SPES TiO2 113.5 at 2 bar N/A 34.5 24.5 N/A Luo et al. (2011)
(PEG-400)
PES Silica 168.4 at 1.1 bar 110 96.3 BSA 52.6 70.4 Parida et al. (1981)
PES TiO2 102.9 at 2 bar N/A 34.5 19.2 N/A Luo et al. (2005)
(PEG-5000)
97
98 4 Surface Modification of Polyethersulfone Membranes

Surface Coatings
Surface coating is an alternative technique that has been extensively used in dif-
ferent applications and it may apply as liquid, gas or solid. It has been specifically
used to alleviate membrane fouling in membrane bioreactors (Razmjou et al. 2012).
In this technique, a thin selective layer is directly deposited as a coating layer (thin
film layer) on the top surface of membrane (Zhao et al. 2013a). Surface coating
method is simple and economical than other processes; however, the main chal-
lenge of coating method is instability of the coating layer and limited diffusion of
the modification agent. There have been numerous studies reporting that surface
coating can be simply applied successfully in industrial scale but the coating layer is
readily removable in use after long usage of membranes (Li et al. 2014; Rana and
Matsuura 2010). Table 4.3 summarises surface modification of polymeric mem-
branes via surface coating techniques.
A variety of coating techniques have been described in many research articles,
including chemical vapour deposition (CVD) (Ha et al. 1996; Yan et al. 1994),
physical vapour deposition (PVD) (Yun and Ted Oyama 2011), chemical (solution
adsorption and sol-gel method) (Luo et al. 2005; Mansourpanah et al. 2009;
Rahimpour et al. 2008) and plasma spraying (Lin et al. 2012) coatings. These
techniques are mostly employed for the modification of membranes, in particular
ceramic membranes with gas separation applications. Each technique has limita-
tions, which impair its widespread application for fabrication of polymeric mem-
brane. For example CVD, PVD and plasma spraying are very expensive due to the
need to work at high temperature and pressure, the need for a high vacuum, and as
such they require high energy usage and the substrate geometry is limited to a flat
surface (Yun and Ted Oyama 2011). However the chemical paths are much more
applicable to polymer membranes as they can feasibly operate at low temperature
and pressure, and consume much less energy than the previously mentioned routes.
Chemical modification of PES
Chemical modification of PES membranes involves different techniques, which can
be classified as follows.
Photo-induced grafting (Photochemical-initiated graft polymerization)
Photochemical surface functionalization is an attractive approach used to modify
polymeric membranes (e.g. PES). It has been widely investigated by many scholars,
especially the UV grafting method (Hilal et al. 2003, 2004; Kaeselev et al. 2001;
Kilduff et al. 2000; Pieracci et al. 1999, 2000; Qiu et al. 2007; Taniguchi and
Belfort 2004). UV method is more applicable to modify flat-sheet membrane; it is
hard to modify hollow fiber membranes, particularly to modify the internal surface
of hollow fiber membrane.
Photochemical-initiated graft polymerization has several advantages and limi-
tations. The advantages of this method are inexpensive method (low cost), operate
under harsh or milder reaction conditions and low temperature may be used to the
reaction; the possibility of choosing different reactive groups or monomers in the
4.4 Physical Modification of PES 99

Table 4.3 Surface modification of polymeric membranes through surface coating techniques
(Rana and Matsuura 2010)
Base material Treatment or remedy Function of the membrane Reference
Cross-linked Fluorinated long-chain Sodium humate filtration; the Speaker
polystyrene pyridinium bromide modified membranes were (1986)
embedded prepared by deposition of
into PE fluorinated amphiphilic
compound in an oriented
layer of the Langmuir–
Blodgett type
PS PEI UF membranes, flux Nyström
reduction in ovalbumin (1989)
solution; hydrophilicity of the
membrane appeared to be a
more important factor in flux
reduction than the charge
PES Polyurea/PU UF membranes, flux Hvid et al.
reduction in PEG, BSA, (1990)
dextran and surfactant
solutions; flux enhancement
are possible with the
modifications
Reinforced Polypyrrole Electrodialysis Sata (1993)
PVC (ED) membranes, flux
reduction in organic foulants;
modified membranes showed
excellent anti-organic fouling
properties in electrodialysis
Sulphonated Quaternized poly(vinyl UF membranes, flux Millesime
PS and PES imidazole) reduction in BSA solution, et al.
and lysozyme solutions; (1994b)
significant improvement in
protein adsorption was
observed for modified
membranes at low ionic
strength
PES Bentonite, diatomite, iron UF membranes, treatment of Galjaard
oxide, kaolinite, titanium surface water from Twenty et al. (2001)
dioxide, zeolite, etc. canal, lake, and reservoir
(Delft, Netherlands);
pre-coating results initially in
higher rate of fouling, which
stabilises after several
filtration cycles
PES Hydrophilic triblock Pulp and paper effluent Maartens
copolymer, filtration; increasing the et al. (2002)
PEO-b-PPO-b-PEO, hydrophilic characteristics of
surfactant the membrane before filtration
could reduce the amount of
organic foulants adsorbed to
the membrane
(continued)
100 4 Surface Modification of Polyethersulfone Membranes

Table 4.3 (continued)

Base material Treatment or remedy Function of the membrane Reference
CA and Phospholipid Microfiltration Akhtar et al.
PVDF (MF) membranes, flux (1995)
reduction in BSA solution;
phospholipid coating
improved flux more in the
PVDF membrane than in CA
membrane
PVDF Polyether-b-PA block UF, oil-water emulsion from Nunes et al.
copolymer metal industry; composite (1995)
membrane was found to
perform similar to Amicom
YM30 cellulose membrane,
but with lower susceptibility
to fouling in the UF of
oil-water waste
Zirconium Quaternized poly(vinyl UF, flux reduction in BSA Millesime
oxide imidazole solution, and lysozyme et al.
inorganic solutions; modified presumed (1994a)
membrane to be negatively charged
CTA, PES, Phospholipid (MPC) MF, flux reduction in BSA Reuben
and PVDF solution, yeast fermentation et al. (1995)
broth, beer, and orange juice;
the coating increased the
initial flux and decreased the
fouling rate; the fouling was
caused by mostly
polysaccharide rather than
protein
PES PVA UF membranes, flux Ma et al.
reduction in BSA solution; (2007)
improved the antifouling
property of PES membrane.
The flux recovery ratio
increased significantly
PES PEGDA and BSA filtration; the modified Mu and
trimethylolpropane membranes were less Zhao (2009)
trimethylacrylate via a susceptible to fouling and had
thermal-induced surface grater flux recoveries after
cross-linking process cleaning as compared to
pristine membrane
PVDF Dip and surface flow coated BSA adsorption and filtration; Boributh
chitosan the modified membranes were et al. (2009)
observed higher flux recovery
than neat membranes;
membrane modified by
combined dip coating and
surface flow methods
displayed the best antifouling
properties
(continued)
4.4 Physical Modification of PES 101

Table 4.3 (continued)

Base material Treatment or remedy Function of the membrane Reference
PVDF Coated with PVA and BSA filtration and natural Du et al.
cross-linked by water of Grand River (2009)
glutaraldehyde vapour (Kitchener, Canada); the
reduction in BSA flux
solution was remarkably
lowered, and higher flux and
slower rate of fouling were
noticed during natural water
filtration by modified
membrane
PVC MPC copolymer (PMB) Adhesion in platelet-rich Berrocal
plasma (PRP) by fluorescence et al. (2002)
micrograph; the modified
membrane exhibited
significant reduction in
biofouling phenomena
PS Pluronic triblock copolymer, Proteins adsorption, and Higuchi
PEO-b-PPO-b-PEO, adhesion in PRP; it was et al. (2003)
surfactant suggested that the bioinert
property of PEO segments in
the pluronic suppresses the
adsorption of plasma proteins
and platelets to the coated
membranes
PVDF PEO-b-PA 12 block UF spiral-wound membranes, Freeman
copolymer motor oil-water emulsion and Pinnau
filtration; the coated (2004)
membranes exhibited
significantly low-fouling
properties
PVDF PVDF-g-POEM graft Oleic acid-triethanol Akthakul
copolymer amine-water filtration; et al. (2004)
modified membranes exhibit
nanoscale size selectivity with
good wetting properties
PVDF Hydrophilic polymer UF membranes, BSA and Wei et al.
enzyme filtration, and (2006b)
adhesion in human PRP; as
the antifouling properties
were excellent, the membrane
could be cleaned without
using any cleaning agent
PVDF Poly(cyclooctene)-g-PEG UF, soybean oil-water Revanur
graft copolymer emulsion filtration; the et al.
stability and lifetime of the (2007b)
coated membrane against oil
droplet were good, and after a
long run the coated membrane
flux crosses over the control
(continued)
102 4 Surface Modification of Polyethersulfone Membranes

Table 4.3 (continued)

Base material Treatment or remedy Function of the membrane Reference
Microporous Quarterisation cross-linking BSA and lysozyme filtration; Yang et al.
PP hydrophilic and positively the modified membranes (2009a, b)
charged coating by poly resisted effectively protein
(ethylene imine), cross-linked fouling below the isoelectric
with p-xylylene dichloride point; furthermore, MF
and quaternized by characteristic has been
iodomethane after plasma unchanged
pre-treatment
PS and PVDF Coated with poly Oil-water emulsion; Emrick et al.
(cyclooctane-g-PEG) copolymers-coated films (2008)
reduced fouling for water
purification
Polypropylene Coated with poly(sulfobetaine UF: BSA, Hgb and LYs Zhou et al.
methacrylate) and filtration, the coated (2014)
polydopamine co- deposition membranes exhibited
significantly excellent
antifouling property and
water flux
PES Coated with polydopamine UF: BSA filtration; the Li et al.
(PD) and PD-graft-poly mechanical stability of the (2014)
(ethylene glycol) membranes were fine and the
PD-g-PEG modified
membrane had a better
chemical stability, the
modified membrane had less
flux reduction and lower
adsorptive amount of BSA
PES Corona air plasma and coated UF: significant enhancement Moghimifar
with TiO2 nanoparticles of the surface hydrophilicity, et al. (2014)
improvement of the
antifouling properties and
permeation fluxes for all
modified membranes, the
modified membranes had a
lower fouling tendency and
long term flux stability in
comparison to the virgin PES
membranes
PES Coated with Nanoporous UF: improved Prihandana
Parylene biocompatibility of the PES et al. (2012)
membranes
PES Coated with sulfonated poly UF: the modified membranes Singh et al.
(propyleneoxide) PPO has lower water flux, (1997)
enhancement in
hydrophilicity surface, and
lower membrane fouling
(continued)
4.4 Physical Modification of PES 103

Table 4.3 (continued)

Base material Treatment or remedy Function of the membrane Reference
PES Preadsorption of poly UF: the surface modified Reddy et al.
(sodium 4-styrenesulfonate) membranes shower excellent (2003)
antifouling properties
PES Coated with UF: The modified membranes Li et al.
polydopamine-grafted had less flux reduction in (2014)
polyethylene glycol filtration and lower adsorptive
amount of BSA in isothermal
adsorption tests. The PD-g-
PEG modification improves
the stability of the PES
membrane and the
adsorbability for BSA more
significantly

grafting procedure and respective excitation wavelength; possibility of easy intro-

duction into the final stages of a membrane manufacturing process, and high
selectivity to absorb UV light without affecting the bulk polymer (Hilal et al. 2003).
The disadvantages of this method is that it usually adheres at small scale but not so
easily for industrial scale (Li et al. 2014). Photo-induced grafting can be achieved
via two routes: either with or without photoinitiator. The mechanisms of
photo-induced grafting without photoinitiator, on the one hand, involves the direct
generation of free radicals on the backbone of the membrane polymer under UV
irradiation, which react with the monomer free radical to form the grafted
copolymer (Seman et al. 2012). Due to the sensitivity of PES, PS polymer toward
UV irridation, the photoinitiator is not required. Different hydrophilic monomers
have been grafted onto the membrane surface of PS and PES to decrease their
fouling by proteins and increase their hydrophilicity, including N-Vinyl-2-
pyrrolidinone (NVP), 2-hydroxylethyl methacrylate (HEMA), acrylic acid (AA),
acrylamide (AAm), and 2-acrylamidoglycolic acid (AAG) (Kilduff et al. 2000;
Mohd Yusof and Ulbricht 2008; Pieracci et al. 2000; Taniguchi and Belfort 2004;
Yamagishi et al. 1995a, b). As stated by numerous research studies, HEMA was the
most effective hydrophilic monomer to decrease both static adsorption and the
membrane fouling during BSA filtration. Other hydrophilic monomers have been
grafted onto PES ultrafiltration membranes via photo-irradiation process to enhance
the anti-fouling property of membranes. These monomers include AA (Abu Seman
et al. 2010; Gupta et al. 1992, 2009; Kouwonou et al. 2008; Malaisamy et al. 2010;
Taniguchi and Belfort 2004; Taniguchi et al. 2003), 2-acrylamidoglycolic acid
monohydrate (AAG) (Kaeselev et al. 2001; Taniguchi and Belfort 2004; Taniguchi
et al. 2003; Wei et al. 2006b), 2-acrylamido-2-methyl-1-propanesulfonic acid
(AAP) (Kaeselev et al. 2001), 2-(acryloyloxy)ethyl trimethyl ammonium chloride
(AETMA) (Madaeni et al. 2011), AAm (Gupta et al. 2009), 2-acrylamido-2-
methyl-1-propanesulfonic acid (AMPS) (Hilal et al. 2003; Taniguchi and Belfort
104 4 Surface Modification of Polyethersulfone Membranes

2004; Taniguchi et al. 2003), quaternary-2-dimethylaminoethyl methacrylate

(qDMAEMA) (Hilal et al. 2003), HEMA (Taniguchi and Belfort 2004; Taniguchi
et al. 2003; Wei et al. 2006b), methacrylic acid (MA) (Wei et al. 2006b), PEG
monomethacrylate (PEGMA) (Rahimpour 2011a; Saha et al. 2009; Susanto et al.
2007; Susanto and Ulbricht 2008), N,N-dimethyl-N-(2-methacryloyloxyethyl-N-
(3-sulfopropyl) ammonium betaine (Rahimpour 2011a; Susanto and Ulbricht
2007), 3-sulfopropyl methacrylate (SPMA) (Taniguchi and Belfort 2004; Taniguchi
et al. 2003) and N-vinylfonnamide (NVF) (Wei et al. 2006b).
In contrast, surface modification with an added photoinitiator; the initiating
radical sites are formed as a result of photoinitiator itself. These sites should be
generated on the surface of membrane through the reaction of photoinitiator with
the hydrogen atom in the base polymer under UV irradiation, yielding the radical
sites required for grafting (Bhattacharya and Misra 2004). A schematic diagram of
the photoinitiated graft polymerization method is shown in Fig. 4.4.
It should be pointed out that a number of factors affect the grafting degree of the
membrane; including the method of UV grafting, the dip or immersion method
(Kilduff et al. 2000; Pieracci et al. 2000) the use of a photoinitiator (Yamagishi et al.
1995b; Lee et al. 2004; Qiu et al. 2005); the application of a degassing agent, for
example, nitrogen or argon (Chu et al. 2006; Liang et al. 2000; Pieracci et al. 2000;
Taniguchi et al. 2003); the nature of the membrane polymer backbone (Kaeselev
et al. 2002; Kuroda et al. 1990; Yamagishi et al. 1995a, b; Puro et al. 2006); the UV
intensity and the wavelength (Hwang and Park 2003; Lee et al. 2004; Qiu et al.
2005; Ji 1996); the employed additive(s) (Bhattacharya and Misra 2004); and the
type of solvent(s) (Lee et al. 2004).
It is noted that the UV-initiated graft polymerization process is used predomi-
nantly for modification of ultrafiltration membranes (Kaeselev et al. 2002; Pieracci
et al. 1999, 2000, 2002a, b; Qiu et al. 2005; Taniguchi et al. 2003; Yamagishi et al.
1995a, b; Susanto and Ulbricht 2008; Xi et al. 2006) and the hydrophilic monomer
is usually utilised to enhance antifouling performance. Table 4.4 illustrates surface
modification of PES via UV technique to enhance antifouling properties of
membranes.
Gamma ray and electron beam-induced grafting
Gamma ray is rarely used as modification method for polymeric PES membrane
because it consumes higher energy via the breaking of chemical bonds and there-
fore affects the membrane strength (Zhao et al. 2013a).
Electron beam irradiation, in contrast, is another approach to motivate grafting
via generating active sites (for example, hydrophilic monomer) on the membrane
surface. This technique is known to be a powerful method of modification used in
the preparation of synthetic polymeric PES membranes with excellent properties
including increased stability, improved separation efficiency and enhanced flux (Lai
et al. 1986; Fritzsche et al. 1986; Haruvy et al. 1988; Saito et al. 1989). Electron
beam irradiation technique can be used for preparation of anionic and cationic
4.4 Physical Modification of PES 105

Fig. 4.4 A schematic

diagram of the photoinitiated
graft polymerization,
a without a photoinitiator and
b using a photoinitiator
(adapted from Bhattacharya
and Misra 2004)

exchange membranes. Keszler et al. (1991) have been modified PES membranes in
a solution of AA and acryl amide monomers by using electron-induced grafting
method. They concluded that the flux and solute retention were increased in
comparison with the unmodified PES. Moreover, the PES membranes also had
pH-responsivity due to the existence of hydroxyl groups (OH) in the PES network
(backbone). Similar research studies conducted by Schulze et al. (2010), they have
been modified PES membrane in a onestep process using electron beam method.
The PES membranes were dipped in an aqueous solutions of functional molecules
(e.g. sulfonic acid, carboxylic acid, phosphoric acid, amines, alcohols and zwitte-
rionic compounds) followed by using electron beam treatment. The results showed
that the protein adsorption of myoglobin and albumin was decreased significantly.
There is no need to use any catalysts, photoinitiator, organic solvents, any toxic
reagents and even additional synthetic or purification steps in this research study of
Schulze et al. (2010). To sum up, electron beam irritation has the capability to
interpenetrate to membrane polymer, and therefore, activate the internal surface of
membrane for the desirable modification reaction.
106 4 Surface Modification of Polyethersulfone Membranes

Table 4.4 Summary of surface modification of polyethersulfone via UV technique

Membranes Treatment Function of membranes References
PES Grafted with N- UF: the membrane Pieracci
(10 KDa) vinyl-2-pyrrolidinone (NVP) hydrophilicity was increased by et al. (1999)
25 %, whilst the BSA rejection
was decreased by 49 %
PES Grafted with N- UF: the treated PES membranes Pieracci
(50 KDa) vinyl-2-pyrrolidinone (NVP) showed considerable decline of et al. (2000)
both membrane permeation and
BSA retention
PES Acrylic acid irradiated with UV MF: the permeability of Kouwonou
light MF PES membrane was et al. (2008)
decreased because the
modification process filled the
pores with copolymer, FRR
was 100 % for the treated PES
membranes
PES Grafted with AA through NF: the membrane permeation Abu Seman
UV-initiated graft was higher for the modified et al. (2010)
polymerization technique PES membrane in comparison
with the neat PES membrane,
the retention of humic acid was
higher, the irreversible fouling
was reduced by humic acid
molecules, the pore size of
membrane was decreased
PES Grafted with hydrophilic The treated PES membranes Gupta et al.
functional moieties (viz. AA, have a good separation (2009)
AM) with UV-initiated capability in comparison to the
photo-modification method neat PES, the flux recovery
ratio (FRR) for the pristine
PES membrane was minimum
in comparison to other two
grafted membranes, the
antifouling performance of
membrane was increased after
grafting AA, increased in pH
led to decrease separation
performance
PES Grafted with AMPS and MF: the number of bacterial Hilal et al.
qDMAEMA) using cells was less for (2003)
photoinduced grafting qDMAEMA-grafted samples in
technique comparison to unmodified PES,
higher anti-biofouling
performance
(continued)
4.4 Physical Modification of PES 107

Table 4.4 (continued)

Membranes Treatment Function of membranes References
PES Heterogeneous Photograft UF: the modified membranes Susanto
copolymerization of PEGMA have higher resistance to and
fouling and higher retention, Ulbricht
the membrane permeation was (2007)
reduced due to pore blocking
by grafted poly PEGMA
PES Grafted with poly (ethylene The antifouling performance Yune et al.
glycol) methyl ether was improved significantly, the (2011)
methacrylate (PEG) with pore size of membrane as
vinylamides including N- decreased
vinylformamide (NVF),
Nvinylacetamide (NVA) or N-
methyl-N-vinylacetamide
(MVA) via a photo-induced
graft polymerization
(PGP) method coupled with a
high throughput platform
(HTP) technology
PES Immersion precipitation by UF: the initial permeate flux Rahimpour
TiO2 nanoparticles and UV was lower than the initial et al. (2008)
irradiation permeate flux of the neat PES
membrane

4.4.2 Plasma Treatment and Plasma-Induced Grafting

Polymerisation

Over the last two decades, plasma treatment of the polymeric membranes has been
extensively investigated by many researchers to enhance membrane hydrophilicity
and to minimise membrane fouling to a minimum (Bryjak et al. 1999; Chen and
Belfort 1999; Gancarz et al. 1999a, b, 2002, 2003; Ulbricht and Belfort 1996;
Wavhal and Fisher 2002a; Zhan et al. 2004; Kim et al. 2002; Dattatray et al. 2005;
Kull et al. 2005; Zhao et al. 2005; Dong et al. 2007; He et al. 2009; Poźniak et al.
2006; Tyszler et al. 2006; Yan et al. 2008; Yu et al. 2005, 2006, 2007, 2008a, b). It
is an effective way to generate functional groups (radical sites that are stable in
vacuum) on the polymeric membrane surface, leading to alterations in membrane
performance. However, the bulk of the polymer remains unaffected. Because the
lower surface energy of plasma treatment, the plasma is often restricted to the
surface of membrane surface and therefore the bulk properties of membrane still
remain unaffected. The thickness of the modified layer can be controlled up to the
angstrom levels.
Kochkodan (2012) states that plasma treatment of the synthetic polymer mem-
branes can be implemented in three various methods: (i) plasma treatment with
non-polymerisable gas molecules; (ii) plasma treatment with polymerizable
vapours; and (iii) plasma treatment with plasma-induced grafting. The plasma
108 4 Surface Modification of Polyethersulfone Membranes

treatment with non-polymerizable gases and plasma-induced grafting are the most
common methods used to modify the synthetic polymer membrane surfaces.
The advantages of plasma treatment are fast, effective technique and meet most
of the ecological regulations for clean technology. It can be employed as radicals
source, which work as anchor points for graft polymerisation.
A number of plasma techniques have been used to obtain permanent functional
groups on the surface of the membrane. These techniques are: (1) Surface cleaning
and etching (2) Surface modification with gas plasma (cross-linking and the cre-
ation of new functional groups) (3) Plasma-initiated polymerization/grafting
(4) Plasma polymerization.
PES polymeric membranes can be modified through plasma, which is produced
after ionisation of water vapour or a gas (e.g. Nitrogen, carbon dioxide, oxygen,
hydrogen, argon) via an electrical discharge at elevated frequencies by using radio
frequency waves and microwaves (Gancarz et al. 1999a, b; Van Der Bruggen
2009a; Castro Vidaurre et al. 2001; Zhao et al. 2013a).
Numerous gases can be employed for the modification of polymeric PES
membrane (Saxena et al. 2009; Wavhal and Fisher 2002b, 2003), including Ar
(Kull et al. 2005; Saxena et al. 2009; Wavhal and Fisher 2003), CO2 (Pal et al.
2008; Wavhal and Fisher 2002b), N2 (Kull et al. 2005), NH3 (Iwa et al. 2004; Kull
et al. 2005), O2 (Pal et al. 2008; Saxena et al. 2009; Cho et al. 2004), and H2O
(Steen et al. 2002). The mechanism of their action is: the membrane surface is
bombarded with ionised plasma components to produce radical sites C–C, C–H,
and C–S bonds can then be attacked by radicals, with exclusion of the aromatic C–
H and C–C bonds (Zhao et al. 2013a). This is the same to the photodegradation
approach or process. The produced radicals can then react with gas molecules,
creating different functionalities, depending on the conditions of plasma as shown
in Fig. 4.5 for O2 (Tyszler et al. 2006). The higher hydrophilicity of the treated
membranes with oxygen plasma for a period of 20 s results in reducing liable
membrane fouling to a minimum for ultrafiltration of gelatine solutions (Kim et al.
2002).
After contacting with the air, the remaining groups (radical sites) bind with
nitrogen or oxygen. These functional groups are carbonyl, carboxylic and hydroxyl.
Surface modification of the polymeric membrane with CO2 plasma results in
introducing oxygen into the surface of membrane in the form of acid, carbonyl and
ester groups, leading to an increase in membrane hydrophilicity. Generally, mod-
ification of membrane surfaces with CO2 plasma results in hydrophilic surfaces and
surface oxidation. He et al. (2009) conclude that treating membranes with CO2
plasma for 30 s shows better regeneration behaviour in ultrafiltration membrane of
specific filtrates (e.g. BSA protein solutions).
Membrane surface treatment with Nitrogen plasma leads to introduce different
functional groups (e.g. imine, amine, amide, and nitrile) on the surface of mem-
brane, making the membrane super hydrophilic and less liable/susceptible to
fouling (Kull et al. 2005). Due to the weak effect of nitrogen plasma, the degra-
dation of polymer may be reduced to certain extent.
4.4 Physical Modification of PES 109

Fig. 4.5 Schematic representation of O2 plasma treatment of a membrane (adapted from Tyszler
et al. 2006)

Modification of polymeric membrane with H2O plasma results in introduction of

oxygen (contains functional groups) onto the membrane surface. XPS and FTIR can
be used to characterise the functional groups. Membrane treatment with Ar plasma
can allow PES membranes to graft or attach other polymers. Plasma treatment has
advantages and disadvantages. The advantages are very shallow modification depth
in comparison to other modification processes. The disadvantages are
(1) time-dependent of the induced changes and therefore, it needs a vacuum system,
which leads to an increase in operation cost, (2) chemical reactions of the plasma
treatment are quite very complicated, so it is hard to understand the surface
chemistry of the treated membrane in detail. Therefore, plasma treatment is not
possible to apply on the large scale.
Thermally induced grafting and immobilisation
Thermal-induced grafting and immobilisation is simplistic routes to surface-modify
PES membrane. Chemical initiators or cleavage agents are always used in this
route. Moreover, many types of biomolecules, such as protein, enzyme and amino
acid, could be covalently immobilised onto polymeric PES membranes through
chemical reaction. It is hard to modify PES membranes by thermal-induced graft
polymerization because the good stability of thermal-induced grafting.
Mu and Zhao (2009) modified of PES porous membranes using thermal-induced
surface cross-linking process. Difunctional poly (ethylene glycol) diacrylate
(PEGDA) was used as the main cross-linking modifier. Trifunctional trimethylol-
propane trimethylacrylate (TMP TMA) was added into the reaction liquid (PEGDA
solution) to enhance the rate of cross-linking on the surface of polymeric PES
porous membranes. The membrane permeation and antifouling performance could
be significantly improved when a moderate mass gain of approximately
150 mg/cm2 was attained. The hydrophilicity of membrane was increased signifi-
cantly due to the cross-linking process.
Another research study conducted by Mansourpanah et al. (2010), nanofiltration
membranes were prepared by dissolving the blend of PES/Polyimide in DMF
solvent, and Afterward the prepared NF membranes were modified using
(PEGtriazine) as a new modifier material and methanol solution containing 10 wt%
110 4 Surface Modification of Polyethersulfone Membranes

ethylenediamine (EDA) as a cross-linker to open the rings of imide group. The

membrane permeation and salt rejection was decreased and increased, respectively
due to the addition of EDA and PEG-triazine. In case of incorporating trimethy-
lacrylate into the membrane recipe, the modified membrane showed lower flux
during the filtration process. Mansourpanah et al. (2010) stated that Diethanolamine
could be also used as a hydrophilic modifier to alter membrane properties.
Shi et al. (2011) prepared poly (MA)-graft-polyethersulfone (PMAA-g-PES)
membrane through non-solvent-induced phase separation process. The enzyme model
trypsin (contains amino functional groups) was conjugated covalently to surface
of membrane via 1-ethyl-(3-3-dimethylaminopropyl)-carbodiimide hydrochloride
(EDC)/N-hydroxysuccinimide (NHS)-activation of carboxylic acid groups enriched
on the membrane surface. The results showed that the treated membranes have
desirable antifouling performance and superior self-cleaning properties. The modified
membranes showed long-term life span for protein filtration due to the higher stability
of trypsin-resided membrane surface. The existence of trypsin on the surface of
membrane did not cause any obvious decline in membrane permeation. However,
after filtration of protein solution, the membranes could recover their initial flux using
washing process
Surface-initiated atom transfer radical polymerization (SI-ATRP)
In recent years, surface-initiated atom transfer radical polymerization (SI-ATRP)
has been shown to one of the prevalent living/controlled polymerization method
utilised for grafting polymers synthesis onto different or various surfaces in a
controlled manner, including grafting density, chain length and chemical compo-
sitions, and therefore produce the high capacity of binding sites of functional
molecules (Edmondson et al. 2004b; Liu et al. 2008; Xu et al. 2005; Zhao et al.
2013a). SI-ATRP method has gained popularity in membrane technology due to its
unique properties, including regulated molecular weight, narrow molecular weight
distribution; operate under hash or milder conditions, and tuneable decorations.
Until now, three kinds of grafting methods using ATRP to modify membranes
have been demonstrated in the literature. These methods are grafting–to, grafting–
through and grafting–from, which concern the synthesis and application of graft
copolymers. The function of these methods is to modify membrane surfaces.
Although all these methods are used, only a few journal articles have been pub-
lished, regarding to use ATRP to modify PES membranes (Li et al. 2009a, b).
Grafting–to is rarely used as modification method of polymeric membranes. It is
simpler than the grafting–from and it has not gained popularity due to the difficulty
of reaching the high grafting density. Furthermore, the grafting density being
restricted by space constraints around the active sites and the situation becomes
worst. This leads to increases layer thickness and consequently the process becomes
self-limiting (Edmondson et al. 2004a). In this technique, preformed polymer
chains (carrying reactive anchor groups on the side chains or at the end) are
attached covalently to the surface of membrane (Zhao and Brittain 2000). This
technique is accurately controlled the structure of the grafted chain. UF PAN
4.4 Physical Modification of PES 111

membranes have been functionalised by different low molecular-weight aromatic

azide derivatives consists of various hydrophobic and hydrophilic functional groups
(Ulbricht and Hicke 1993). The results showed that the protein-fouling intensity
and separation properties were virtually changed, depending on the type of func-
tional groups introduced. This was verified by increasing the membrane
hydrophilicity and charged of the active membrane layer
Grafting–from method is commonly used for modification of various polymeric
membranes (Kaeselev et al. 2002; Kilduff et al. 2000; Ma et al. 2000a, b; Pieracci
et al. 1999, 2000, 2002; Ulbricht and Belfort 1996; Ulbricht et al. 1996; Yamagishi
et al. 1995a, b; Yang and Yang 2003; Hilal et al. 2003, 2004; Taniguchi and Belfort
2004; Hu et al. 2006; Gu et al. 2009; Rahimpour et al. 2009; Yu et al. 2009a; Zhang
et al. 2009; Abu Seman et al. 2010). In this technique, polymer chains directly grow
in situ from the immobilised or grafted active groups (radicals) on the membrane
surface in the existence monomers or initiators. The majority of these research
studies have conducted on antifouling modification of the ultrafiltration and
microfiltration membranes because higher grafting density is needed in order to use
the grafted polymer layer as a selective barrier in reverse osmosis membrane (RO).
Generally, this technique may be achieved with photoinitiator and without pho-
toinitiator. Lastly, grafting-from has proven to be more feasible and versatile
method than grafting-to.
The chloromethylation of PES under milder conditions lead to create surface
benzyl chloride groups as the active sites for ATRP to adjust the hydrophobicity of
the PES membrane (Zhao et al. 2013a). Functional hydrophilic polymer brushes of
PEGMA and sodium 4-styrenesulfonate (NaStS), as well as their block copolymer
brushes, were prepared through surface-initiated ATRP from the chloromethylated
PES surfaces. PES membranes grafted with PEGMA membranes showed excellent
protein-fouling resistance to protein adsorption (Li et al. 2009a).
Apart from ATRP, other polymerization methods, such as free radical mediated
polymerization (SFRP), reversible addition-fragmentation chain transfer (RAFT)
polymerisation, and iodine-transfer polymerization have been also used to modify
of PES membranes.
Wang et al. (2014) modified PES UF membranes with halloysite nanotubes
grafted with 2-methacryloyloxyethyl phosphorylcholine (HNTs-MPC) for the
purpose of improving the antifouling performance of the membrane. HNTs have
been chemically modified with MPC through reverse atom transfer radical poly-
merization RATRP. The resulting new hybrid membranes possessed higher pure
water flux and good antifouling performance. The protein (BSA) adsorption
experiment showed that the amounts of bovine serum albumin (BSA) adsorbed on
the surface of membrane were decreased significantly. BSA ultrafiltration experi-
ment also indicated that the hybrid PES membranes have higher antifouling
property with the addition of HNTs-MPC than the virgin PES membrane. At the
same time, the long-term ultrafiltration experiment showed that the hybrid PES
membrane had an ideal stability (Wang et al. 2014).
112 4 Surface Modification of Polyethersulfone Membranes

Ozone-induced grafting of PES membranes

Due to the low concentration availability of ozone throughout the Earth’s atmo-
sphere, it has been used in a wide range of consumer and industrial applications.
Liu et al. (2008) functionalised PES ultrafiltration membranes via grafted three
hydrophilic functional polymers such as polyethylene glycol (PEG), polyvinyl
alcohol (PVA), and CHI using UV/ozone methods. Based on their results, the
surface modified PES membranes have higher surface roughness in comparison to
the pristine PES membrane. It was also shown that the modified membranes have
more hydrophilic surface and could reduce the amount of protein adsorption on
membranes. This research studies have demonstrated that PEG is the most
favourable result in modifying PES membranes for fouling mitigation among the
three hydrophilic polymers tested. This has been verified by measurements of
contact angle and protein adsorption experiment.
Redox-grafting PES membranes
Redox (oxidation-reduction reaction) is a method used in the 1980s for grafting of
nylon and cellulose and later was used to polyamide membranes. Recently, it has
been used to modify PES membranes (Belfer et al. 2000; Reddy et al. 2005). Redox
grafting describes all chemical reactions in which atoms have their oxidation
number (oxidation state) changed. Furthermore, redox grafting composed from two
concepts: reduction and oxidation (Zhao et al. 2013a). Van Der Bruggen (2009b)
states that redox initiators can be used to produce radicals under milder conditions
with minimum side chain reaction. One of the benefits of redox reaction is the
modification of the prepared membrane can be implemented in aqueous media at
ambient temperature without oxygen removal.
Redox initiation occurs when the oxidant (e.g. persulphate) and the reductant
(e.g. sulphite) exist in the reaction mixture. It can be seen that redox initiation are
used for polymerizations, which occurs at temperature below 50 °C. The redox
system is usually used K2S2O8/Na2S2O5, which have the capability to produce
radicals on the surface of membrane for further grafting. K2S2O8 represents the
oxidants, whilst K2S2O5/Na2S2O5 represents the reductants. Redox-grafting reac-
tions have been used for PA membranes. However, some research studies have
been conducted on using redox reaction as method to modify PES membranes. For
example, Reddy et al. (2005) have been modified PES membranes with acrylate
monomers (AAm and methylene bisacryl amide) via graft polymerisation induced
by a redox reaction.
Belfer et al. (2000) functionalised PES membranes using different monomers
including AAm, MAA, PEGM and SPMA with the aid of redox initiators to create
radicals on the PES membrane surface. They followed the same procedure used in
the study of Reddy et al. (2005). They concluded that when a high concentration of
monomer is used, the permeability might significantly decrease (up to 30 %) since
the grafted chains can penetrate the membrane and block the membrane pores
partially or completely.
4.4 Physical Modification of PES 113

Reddy et al. (2005) prepared PES nanofiltration membranes (MWCO < 1000)
and polyamide composite membranes (thin film membrane contains negatively
charged hydrophilic functional groups on its surface) using in situ redox poly-
merization of acrylate monomers. The resulting nanofiltration membranes were
used for dye effluent solution treatment whilst the modified membranes were
examined for desalination of brackish water without using chemical pre-treatment
to evaluate their fouling resistance performance. Reddy et al. (2005) concluded that
the treated membranes showed excellent antifouling properties for desalination of
brackish water.
Pore-filled PES membranes
Pore-filled PES membranes are a new class of membranes developed by Mika et al.
(1995). They provided pH-sensitive membrane, which consists of microfiltration
(host) porous substrate and polyelectrolyte anchored within the pores. This method
can also be used to modify PES membranes. The host substrate is porous and
physically and chemically stable, provides mechanical strength for the developed
membranes (Hu and Dickson 2007). Different polyelectrolyte can be pore filled in a
controlled manner owing to the porous structure of the host substrate, resulting in
dramatically different behaviour from the host membranes (Mika et al. 1995, 1999,
2002).
Shah et al. (2005) functionalized porous PES microfiltration membranes by the
formation of polystyrene grafts within the pores. Further activation of the grafts is
accomplished by lower concentration of sulfuric acid, resulting in no loss of
functionalised polymer during activation method. The functionalised or treated
membranes could also be employed for separation of whey protein (Cowan and
Ritchie 2007). The surface charged membrane exhibited higher selectivity (five
times) than the pristine PES membrane at pH 7.2. The selectivity was improved due
to increase reduction of beta-lactoglobulin because a reduction in molecular sieving
combined with electrostatic repulsion between the negatively charged membranes
and negatively charged b-lactoglobulin.
Molecularly imprinted PES membranes
A molecular imprinting technique is a promising technique used to create highly
recognition and catalytic sites within polymer network (Wulff 1995). Molecular
imprinting technique can be prepared by copolymerisation of cross-linker and
functional monomers into polymeric membrane matrix in the presence of a template
molecule, which results in the formation of these monomers (binding or recogni-
tions sites cavities) complementary to the template in shape, size and position of the
functional groups (Mosbach and Haupt 1998). These recognition sites enable the
polymer to rebind selectively the imprint molecules from a mixture of closely
related compounds (Zhao et al. 2013a; Alexander et al. 2006; Cormack and
Mosbach 1999; Davis et al. 1996; Mayes and Whitcombe 2005; Wulff 2002; Ye
and Mosbach 2008; Wei et al. 2006a; Whitcombe and Vulfson 2001; Byrne et al.
2008). Due to its ease of operation, stability, higher selectivity, feasibility in
114 4 Surface Modification of Polyethersulfone Membranes

different conditions, molecular imprinting technique has been extensively used in a

wide range of applications, for example, chromatography, solid phase extraction,
sensor design, adsorbents to environmental hormone, reaction catalysis and mem-
brane separation (Bergmann and Peppas 2008; Byrne et al. 2002; Ge and Turner
2008; Hillberg and Tabrizian 2008; Hilt and Byrne 2004; Wei et al. 2006a; Bossi
et al. 2007; Janiak and Kofinas 2007; Turner et al. 2006; Zhao et al. 2013a; Zhang
et al. 2006). Molecular imprinting technique has gained popularity in industry due
to its low cost and stability. Molecular imprinting technique has been developed by
two main approaches: the first approach is covalent molecularly imprinting and the
second one is non-covalent molecularly imprinting. The template is coupled to
polymerizable molecules via covalent bond in the covalent approach, whilst, the
template is mingled with functional monomers or cross-linker via non-covalent
bond in non-covalent approach. The second approach has been used significantly
due to its wide application and easiness. Byrne and Salian (2008) state that the
majority of imprinted polymers generated today have been cross-linked extremely
to minimise the flexibility of the associated binding cavities generated between
polymer chains. Therefore, the idea of the technique translating to polymeric
matrices with higher flexibility within their polymer chains was highly suspect. It is
supposed that flexibility of polymeric chains would results in fatal deficiencies in
the networks in which imprinted structures are well defined, namely template
binding affinity, capacity, and selectivity. However, experimental work in the last
decade has confirmed that this is not the case. Recently, Zhao et al. (2008) prepared
bisphenol A imprinted PES hollow fiber membrane using phase transition technique
and dry–wet-spinning method. The results showed that the transmission rate of
bisphenol A has been increased for the imprinted hollow fiber membranes in
comparison with the non-imprinted membranes because the larger amount of rad-
ical (binding) sites through the imprinted membranes. Therefore, the imprinted
membranes can be used in separation and purification applications
Ionically modified PES membranes
Ionic modification is one of the methods used to modify polymeric PES mem-
branes. Numerous research studies have been conducted to modify polymeric PES
membranes ionically, for example, (Li and Chung 2010) modified PES membranes
using ionic modification method to produce the sulfonated PES membranes with
Ag+ ion form. Silver ion modification approach and dual-layer hollow fiber spin-
ning technology has been used to functionalise PES membranes. The results of pure
gas permeance showed that the O2/N2 and CO2/CH4 selectivity was significantly
increased (9.5 and 118), respectively. Cao et al. (2010) blended PES membranes
with sulfonated PES to prepare hybrid membranes. The hybrid membranes were
then immersed in a solution of excess AgNO3. Silver ion were immobilised onto
SPES membrane surface using Vitamin C (VC) as reducing agent. The results
showed that the composite (PES/SPES)-Ag membranes have excellent bacterio-
static (growth inhibition) and anti-bacterial properties for long period of usage. In
the future, the anti-bacterial properties of the composite (PES/SPES)-Ag
4.4 Physical Modification of PES 115

membranes might be useful to extend the usage of PES in another applications such
as food processing and medical instruments industry. Li et al. (2002) used
co-extrusion and dry-jet wet-spinning phase inversion techniques to fabricate
delamination-free-dual-layer asymmetric composite hollow fiber membranes with a
defect-free dense selective skin. The modified membranes were used for applica-
tions of gas or air separation. The results of pure gas permeance showed that the O2/
N2 selectivity of the dual-layer asymmetric hollow fiber membranes at 4.6 was
relatively close to the value of the outer-layer material, 4.7.

References

Abu Seman MN, Khayet M, Bin Ali ZI, Hilal N (2010) Reduction of nanofiltration membrane
fouling by UV-initiated graft polymerization technique. J Membr Sci 355(1–2):133–141
Ajmani GS, Goodwin D, Marsh K, Fairbrother DH, Schwab KJ, Jacangelo JG, Huang H (2012)
Modification of low pressure membranes with carbon nanotube layers for fouling control.
Water Res 46(17):5645–5654
Akar N, Asar B, Dizge N, Koyuncu I (2013) Investigation of characterization and biofouling
properties of PES membrane containing selenium and copper nanoparticles. J Membr Sci
437:216–226
Akhtar S, Hawes C, Dudley L, Reed I, Stratford P (1995) Coatings reduce the fouling of
microfiltration membranes. J Membr Sci 107(3):209–218. doi:10.1016/0376-7388(95)00118-9
Akthakul A, Salinaro RF, Mayes AM (2004) Antifouling polymer membranes with subnanometer
size selectivity. Macromolecules 37(20):7663–7668. doi:10.1021/ma048837s
Alexander C, Andersson HS, Andersson LI, Ansell RJ, Kirsch N, Nicholls IA, O’Mahony J,
Whitcombe MJ (2006) Molecular imprinting science and technology: a survey of the literature
for the years up to and including 2003. J Mol Recognit 19(2):106–180
Arthanareeswaran G, Thanikaivelan P, Raajenthiren M (2008) Fabrication and characterization of
CA/PSf/SPEEK ternary blend ultrafiltration membranes. Ind Eng Chem Res 47(5):1488–1494
Bai P, Cao X, Zhang Y, Yin Z, Wei Q, Zhao C (2010) Modification of a polyethersulfone matrix
by grafting functional groups and the research of biomedical performance. J Biomater Sci
Polym Ed 21(12):1559–1572
Baker R (2012) Membrane technology and application, 3rd edn. Wiley, UK
Barzin J, Feng C, Khulbe KC, Matsuura T, Madaeni SS, Mirzadeh H (2004) Characterization of
polyethersulfone hemodialysis membrane by ultrafiltration and atomic force microscopy.
J Membr Sci 237(1–2):77–85
Batsch A, Tyszler D, Brügger A, Panglisch S, Melin T (2005) Foulant analysis of modified and
unmodified membranes for water and wastewater treatment with LC-OCD. Desalination 178
(1–3 SPEC. ISS.):63–72
Belfer S, Fainchtain R, Purinson Y, Kedem O (2000) Surface characterization by FTIR-ATR
spectroscopy of polyethersulfone membranes-unmodified, modified and protein fouled.
J Membr Sci 172(1–2):113–124
Belfort G, Davis RH, Zydney AL (1994) The behavior of suspensions and macromolecular
solutions in crossflow microfiltration. J Membr Sci 96(1–2):1–58
Bergmann NM, Peppas NA (2008) Molecularly imprinted polymers with specific recognition for
macromolecules and proteins. Prog Polym Sci (Oxf) 33(3):271–288
Berrocal MJ, Daniel Johnson R, Badr IHA, Liu M, Gao D, Bachas LG (2002) Improving the blood
compatibility of ion-selective electrodes by employing poly(MPC-co-BMA), a copolymer
containing phosphorylcholine, as a membrane coating. Anal Chem 74(15):3644–3648. doi:10.
1021/ac025604v
116 4 Surface Modification of Polyethersulfone Membranes

Bhattacharya A, Misra BN (2004) Grafting: a versatile means to modify polymers: techniques,

factors and applications. Prog Polym Sci (Oxf) 29(8):767–814
Blanco JF, Nguyen QT, Schaetzel P (2001) Novel hydrophilic membrane materials: sulfonated
polyethersulfone Cardo. J Membr Sci 186(2):267–279. doi:10.1016/S0376-7388(01)00331-3
Boributh S, Chanachai A, Jiraratananon R (2009) Modification of PVDF membrane by chitosan
solution for reducing protein fouling. J Membr Sci 342(1–2):97–104. doi:10.1016/[Link].
2009.06.022
Bossi A, Bonini F, Turner APF, Piletsky SA (2007) Molecularly imprinted polymers for the
recognition of proteins: the state of the art. Biosens Bioelectron 22(6):1131–1137
Bottino A, Capannelli G, Monticelli O, Piaggio P (2000) Poly(vinylidene fluoride) with improved
functionalization for membrane production. J Membr Sci 166(1):23–29
Brink LES, Elbers SJG, Robbertsen T, Both P (1993) The anti-fouling action of polymers
preadsorbed on ultrafiltration and microfiltration membranes. J Membr Sci 76(2–3):281–291
Bryjak M, Gancarz I, Poźniak G (1999) Surface evaluation of plasma-modified polysulfone (Udel
P-1700) films. Langmuir 15(19):6400–6404
Byrne ME, Salian V (2008) Molecular imprinting within hydrogels II: progress and analysis of the
field. Int J Pharm 364(2):188–212. doi:10.1016/[Link].2008.09.002
Byrne ME, Oral E, Hilt JZ, Peppas NA (2002) Networks for recognition of biomolecules:
molecular imprinting and micropatterning poly (ethylene glycol)-containing films. Polym Adv
Technol 13(10–12):798–816
Byrne M, Hilt J, Peppas N (2008) Recognitive biomimetic networks with moiety imprinting for
intelligent drug delivery. Biomed Mater Res 84A:137–147
Cao X, Tang M, Liu F, Nie Y, Zhao C (2010) Immobilization of silver nanoparticles onto
sulfonated polyethersulfone membranes as antibacterial materials. Colloids Surf B 81(2):555–
562. doi:10.1016/[Link].2010.07.057
Castro Vidaurre EF, Achete CA, Simão RA, Habert AC (2001) Surface modification of porous
polymeric membranes by RF-plasma treatment. Nucl Instrum Methods Phys Res, Sect B 175–
177:732–736
Chae SR, Ahn YT, Kang ST, Shin HS (2006) Mitigated membrane fouling in a vertical submerged
membrane bioreactor (VSMBR). J Membr Sci 280(1–2):572–581
Chen H, Belfort G (1999) Surface modification of poly(ether sulfone) ultrafiltration membranes by
low-temperature plasma-induced graft polymerization. J Appl Polym Sci 72(13):1699–1711
Chen Y, Zhang Y, Zhang H, Liu J, Song C (2013) Biofouling control of halloysite
nanotubes-decorated polyethersulfone ultrafiltration membrane modified with chitosan-silver
nanoparticles. Chem Eng J 228:12–20
Cho D, Kim S, Huh Y, Kim D, Cho S, Kim B (2004) Effects of surface modification of the
membrane in the ultrafiltation of waste water. Macromol Res 12:553–558
Chu LY, Wang S, Chen WM (2005) Surface modification of ceramic-supported polyethersulfone
membranes by interfacial polymerization for reduced membrane fouling. Macromol Chem
Phys 206(19):1934–1940. doi:10.1002/macp.200500324
Chu LQ, Tan WJ, Mao HQ, Knoll W (2006) Characterization of UV-induced graft polymerization
of poly(acrylic acid) using optical waveguide spectroscopy. Macromolecules 39(25):8742–
8746
Cormack PAG, Mosbach K (1999) Molecular imprinting: recent developments and the road ahead.
React Funct Polym 41(1):115–124
Cowan S, Ritchie S (2007) Modified polyethersulfone (PES) ultrafiltration membranes for
enhanced filtration of whey proteins. Sep Sci Technol 42(11):2405–2418. doi:10.1080/
01496390701477212
Dang HT, Narbaitz RM, Matsuura T (2008) Double-pass casting: a novel technique for developing
high performance ultrafiltration membranes. J Membr Sci 323(1):45–52
Daraei P, Madaeni SS, Ghaemi N, Khadivi MA, Astinchap B, Moradian R (2013a) Enhancing
antifouling capability of PES membrane via mixing with various types of polymer modified
multi-walled carbon nanotube. J Membr Sci 444:184–191
References 117

Daraei P, Madaeni SS, Ghaemi N, Khadivi MA, Astinchap B, Moradian R (2013b) Fouling
resistant mixed matrix polyethersulfone membranes blended with magnetic nanoparticles:
study of magnetic field induced casting. Sep Purif Technol 109:111–121
Dattatray S, Wavhal D, Fisher E (2005) Modification of polysulfone ultrafiltration membranes by
CO2 plasma treatment. Desalination 172:198–205
Davis ME, Katz A, Ahmad WR (1996) Rational catalyst design via imprinted nanostructured
materials. Chem Mater 8(8):1820–1839
Deng B, Yang X, Xie L, Li J, Hou Z, Yao S, Liang G, Sheng K, Huang Q (2009) Microfiltration
membranes with pH dependent property prepared from poly(methacrylic acid) grafted
polyethersulfone powder. J Membr Sci 330(1–2):363–368
Devrim Y, et al (2009) Preparation and characterization of sulfonated polysulfone/titanium dioxide
composite membranes for proton exchange membrane fuel cells. Int J Hydrogen Energ 34
(8):3467–3475
Dong B, Jiang H, Manolache S, Wong ACL, Denes FS (2007) Plasma-mediated grafting of poly
(ethylene glycol) on polyamide and polyester surfaces and evaluation of antifouling ability of
modified substrates. Langmuir 23(13):7306–7313
Dong C, He G, Li H, Zhao R, Han Y, Deng Y (2012) Antifouling enhancement of poly(vinylidene
fluoride) microfiltration membrane by adding Mg(OH) 2 nanoparticles. J Membr Sci 387–388
(1):40–47
Du JR, Peldszus S, Huck PM, Feng X (2009) Modification of poly(vinylidene fluoride)
ultrafiltration membranes with poly(vinyl alcohol) for fouling control in drinking water
treatment. Water Res 43(18):4559–4568. doi:10.1016/[Link].2009.08.008
Duan L, Huang W, Zhang Y (2015) High-flux, antibacterial ultrafiltration membranes by facile
blending with N-halamine grafted halloysite nanotubes. RSC Adv 5(9):6666–6674. doi:10.
1039/c4ra14530e
Edmondson S, Osborne V, Huck W (2004a) Chemical Soc Rev 35:14
Edmondson S, Osborne VL, Huck WTS (2004b) Polymer brushes via surface-initiated
polymerizations. Chem Soc Rev 33(1):14–22
Emrick TS, Breitenkamp K, Revanur R, Freeman BD, McCloskey (2008) B. Chem. Abstr 149,
54430; U.S. Patent Appl. 2008/0142454
Fan Z, Wang Z, Sun N, Wang J, Wang S (2008) Performance improvement of polysulfone
ultrafiltration membrane by blending with polyaniline nanofibers. J Membr Sci 320(1–2):
363–371
Fang B, Ling Q, Zhao W, Ma Y, Bai P, Wei Q, Li H, Zhao C (2009) Modification of
polyethersulfone membrane by grafting bovine serum albumin on the surface of
polyethersulfone/poly(acrylonitrile-co-acrylic acid) blended membrane. J Membr Sci 329(1–
2):46–55
Fang BH, Cheng C, Li LL, Cheng J, Zhao WF, Zhao CS (2010) Surface modification of
polyethersulfone membrane by grafting bovine serum albumin. Fibers and Polymers 11
(7):960–966
Filho AAMF, Gomes AS (2006) Copolymerization of styrene onto polyethersulfone films induced
by gamma ray irradiation. Polym Bull 57:415–21
Freeman, BD Pinnau I (2004) In Advanced Materials for Membrane Separations; Pinnau I,
Freeman BD, (eds) ACS Symp Ser 876; American
Fritzsche AK (1986) Effect of ionizing radiation on styrene/acrylonitrile copolymer hollow fiber
membranes. J Appl Polym Sci 32(2):3541–3550
Galjaard G, Buijs P, Beerendonk E, Schoonenberg F, Schippers JÇ (2001) Pre-coating (EPCE®)
UF membranes for direct treatment of surface water. Desalination 139(1–3):305–316. doi:10.
1016/S0011-9164(01)00324-1
Gancarz I, Poźniak G, Bryjak M (1999a) Modification of polysulfone membranes 1. CO2 plasma
treatment. Eur Polymer J 35(8):1419–1428
Gancarz I, Pozniak J, Bryjak M, Frankiewicz A (1999b) Modification of polysulfone membranes.
2. Plasma grafting and plasma polymerization of acrylic acid. Acta Polymerica 50 (9):317–326
118 4 Surface Modification of Polyethersulfone Membranes

Gancarz I, Poźniak G, Bryjak M, Tylus W (2002) Modification of polysulfone membranes 5.

Effect of n-butylamine and allylamine plasma. Eur Polymer J 38(10):1937–1946
Gancarz I, Bryjak J, Bryjak M, Poźniak G, Tylus WLS (2003) Plasma modified polymers as a
support for enzyme immobilization 1. Allyl alcohol plasma. Eur Polym J 39(8):1615–1622
Ge Y, Turner APF (2008) Too large to fit? Recent developments in macromolecular imprinting.
Trends Biotechnol 26(4):218–224
Gu JS, Yu HY, Huang L, Tang ZQ, Li W, Zhou J, Yan MG, Wei XW (2009) Chain-length
dependence of the antifouling characteristics of the glycopolymer-modified polypropylene
membrane in an SMBR. J Membr Sci 326(1):145–152
Gupta BB, Blanpain P, Jaffrin MY (1992) Permeate flux enhancement by pressure and flow
pulsations in microfiltration with mineral membranes. J Membr Sci 70(2–3):257–266. doi:10.
1016/0376-7388(92)80111-V
Gupta S, Yogesh Singh K, Bhattacharya A (2009) Studies on permeation of Bovine Serum
Albumin (BSA) through photo-modified functionalized asymmetric membrane. J Macromol
Sci Part A Pure Appl Chem 46(1):90–96. doi:10.1080/10601320802515506
Ha HY, Nam SW, Lim TH, Oh IH, Hong SA (1996) Properties of the TiO2 membranes prepared
by CVD of titanium tetraisopropoxide. J Membr Sci 111(1):81–92
Hai FI, Yamamoto K, Fukushi K, Nakajima F (2008) Fouling resistant compact hollow-fiber
module with spacer for submerged membrane bioreactor treating high strength industrial
wastewater. J Membr Sci 317(1–2):34–42
Haruvy Y, Gratzel M, RaJbenbach LA (1988) Radlolytlc method of preparation of semiconductor
assemblies supported on polymenc membranes. Rad1at Phys Chem 31:843–852
He XC, Yu HY, Tang ZQ, Liu LQ, Yan MG, Gu JS, Wei XW (2009) Reducing protein fouling of
a polypropylene microporous membrane by CO2 plasma surface modification. Desalination
244(1–3):80–89
Higuchi A, Sugiyama K, Yoon BO, Sakurai M, Hara M, Sumita M, Sugawara SI, Shirai T (2003)
Serum protein adsorption and platelet adhesion on pluronic™-adsorbed polysulfone
membranes. Biomaterials 24(19):3235–3245. doi:10.1016/S0142-9612(03)00186-8
Hilal N, Al-Khatib L, Atkin BP, Kochkodan V, Potapchenko N (2003) Photochemical
modification of membrane surfaces for (bio)fouling reduction: a nano-scale study using
AFM. Desalination 158(1–3):65–72
Hilal N, Kochkodan V, Al-Khatib L, Levadna T (2004) Surface modified polymeric membranes to
reduce (bio)fouling: a microbiological study using E. coli. Desalination 167(1–3):293–300
Hilal N, Ogunbiyi OO, Miles NJ, Nigmatullin R (2005) Methods employed for control of fouling
in MF and UF membranes: a comprehensive review. Sep Sci Technol 40(10):1957–2005
Hillberg AL, Tabrizian M (2008) Biomolecule imprinting: developments in mimicking dynamic
natural recognition systems. ITBM-RBM 29(2–3):89–104
Hilt JZ, Byrne ME (2004) Configurational biomimesis in drug delivery: Molecular imprinting of
biologically significant molecules. Adv Drug Deliv Rev 56(11):1599–1620
Hu K, Dickson JM (2007) Development and characterization of poly(vinylidene fluoride)-poly
(acrylic acid) pore-filled pH-sensitive membranes. J Membr Sci 301(1–2):19–28
Hu M, Yang Q, Xu Z (2006) Enhancing the hydrophilicity of polyproplylene microporous
membranes by the grafting of 2-hydroxyl metharylate via synergistic effect of photoinitiators.
Membrane Science 285:196–205
Huang J, Zhang K, Wang K, Xie Z, Ladewig B, Wang H (2012) Fabrication of
polyethersulfone-mesoporous silica nanocomposite ultrafiltration membranes with antifouling
properties. J Membr Sci 423–424:362–370
Hvid KB, Nielsen PS, Stengaard FF (1990) Preparation and characterization of a new ultrafiltration
membrane. J Membr Sci 53(3):189–202. doi:10.1016/0376-7388(90)80014-D
Hwang TS, Park JW (2003) UV-induced graft polymerization of polypropylene-g-glycidyl
methacrylate membrane in the vapor phase. Macromol Res 11(6):495–500
Iojoiu C, Maréchal M, Chabert F, Sanchez JY (2005) Mastering sulfonation of aromatic
polysulfones: crucial for membranes for fuel cell application. Fuel Cells 5(3):344–354. doi:10.
1002/fuce.200400082
References 119

Iwa T, Kumazawa H, Bae SY (2004) Gas permeabilities of NH3-plasma-treated polyethersulfone

membranes. J Appl Polym Sci 94(2):758–762
Jamshidi Gohari R, Halakoo E, Nazri NAM, Lau WJ, Matsuura T, Ismail AF (2014) Improving
performance and antifouling capability of PES UF membranes via blending with highly
hydrophilic hydrous manganese dioxide nanoparticles. Desalination 335(1):87–95
Janiak DS, Kofinas P (2007) Molecular imprinting of peptides and proteins in aqueous media.
Anal Bioanal Chem 389(2):399–404
Ji J (1996) Fabrication and photochemical surface modification of photoreactive thin-film
composite membranes and model development for thin film formation by interfacial
polymerization. McMaster University
Kaeselev B, Pieracci J, Belfort G (2001) Photoinduced grafting of ultrafiltration membranes:
comparison of poly(ether sulfone) and poly(sulfone). J Membr Sci 194(2):245–261. doi:10.
1016/S0376-7388(01)00544-0
Kaeselev B, Kingshott P, Jonsson G (2002) Influence of the surface structure on the filtration
performance of UV-modified PES membranes. Desalination 146(1–3):265–271
Kang G, Liu M, Lin B, Cao Y, Yuan Q (2007) A novel method of surface modification on
thin-film composite reverse osmosis membrane by grafting poly(ethylene glycol). Polymer 48
(5):1165–1170
Kang GD, Cao YM (2014) Application and modification of poly (vinylidene fluoride) (PVDF)
membranes—A review. J Membrane Sci 463:145–165
Keszler B, Kovács G, Tóth A, Bertóti I, Hegyi M (1991) Modified polyethersulfone membranes.
J Membr Sci 62(2):201–210
Khayet M, Suk DE, Narbaitz RM, Santerre JP, Matsuura T (2003) Study on surface modification
by surface-modifying macromolecules and its applications in membrane-separation processes.
J Appl Polym Sci 89(11):2902–2916. doi:10.1002/app.12231
Khulbe KC, Feng C, Matsuura T (2010a) The art of surface modification of synthetic polymeric
membranes. J Appl Polym Sci 115(2):855–895
Khulbe KC, Feng CY, Matsuura T (2010b) Surface modification of synthetic polymeric
membranes for filtration and gas separation. Recent Pat Chem Eng 3(1):1–16
Kilduff JE, Mattaraj S, Pieracci JP, Belfort G (2000) Photochemical modification of poly(ether
sulfone) and sulfonated poly(sulfone) nanofiltration membranes for control of fouling by
natural organic matter. Desalination 132(1–3):133–142
Kim KS, Lee KH, Cho K, Park CE (2002) Surface modification of polysulfone ultrafiltration
membrane by oxygen plasma treatment. J Membr Sci 199(1):135–145
Kochkodan V, Hilal N (2015) A comprehensive review on surface modified polymer membranes
for biofouling mitigation. Desalination 356:187–207. doi:10.1016/[Link].2014.09.015
Kouwonou Y, Malaisamy R, Jones KL (2008) Modification of PES membrane: reduction of
biofouling and improved flux recovery. Sep Sci Technol 43(16):4099–4112. doi:10.1080/
01496390802414726
Kroll S, Meyer L, Graf AM, Beutel S, Glökler J, Döring S, Klaus U, Scheper T (2007)
Heterogeneous surface modification of hollow fiber membranes for use in micro-reactor
systems. J Membr Sci 299(1–2):181–189
Kull KR, Steen ML, Fisher ER (2005) Surface modification with nitrogen-containing plasmas to
produce hydrophilic, low-fouling membranes. J Membr Sci 246(2):203–215
Kuroda S, Mita I, Obata K, Tanaka S (1990) Degradation of aromatic polymers: part IV-Effect of
temperature and light intensity on the photodegradation of polyethersulfone. Polym Degrad
Stab 27(3):257–270
La YH, McCloskey BD, Sooriyakumaran R, Vora A, Freeman B, Nassar M, Hedrick J, Nelson A,
Allen R (2011) Bifunctional hydrogel coatings for water purification membranes: improved
fouling resistance and antimicrobial activity, J Membr Sci 372:285–291
Lai JY, Chang TC, Wu ZJ, Hsieh TS (1986) Vinyl monomer irradiation-grafted nylon 4
membranes. J Appl Polym Sci 32(4):4709–4718
Le-Clech P, Cao Z, Wan PY, Wiley DE, Fane AG (2006a) The application of constant temperature
anemometry to membrane processes. J Membr Sci 284(1–2):416–423
120 4 Surface Modification of Polyethersulfone Membranes

Le-Clech P, Chen V, Fane TAG (2006b) Fouling in membrane bioreactors used in wastewater
treatment. J Membr Sci 284(1–2):17–53
Le-Clech P, Marselina Y, Stuetz R, Chen V (2006c) Fouling visualisation of soluble microbial
product models in MBRs. Desalination 199(1–3):477–479
Lee D, Kim H, Kim S (2004) Surface modification of polymeric membranes by UV grafting. In:
Separation Amfm (ed) ACS Symposium Series 876. American Chemical Society, Washington,
pp 281–299
Li Y, Chung TS (2010) Silver ionic modification in dual-layer hollow fiber membranes with
significant enhancement in CO2/CH4 and O2/N2 separation. J Membr Sci 350(1–2):226–231.
doi:10.1016/[Link].2009.12.032
Li DF, Chung TS, Wang R, Liu Y (2002) Fabrication of fluoropolyimide/polyethersulfone
(PES) dual-layer asymmetric hollow fiber membranes for gas separation. J Membr Sci 198
(2):211–223
Li L, Yan G, Wu J (2009a) Modification of polysulfone membranes via surface initiated atom
transfer radical polymerization and their antifouling properties Applied polymer science
111:1942–1946
Li SD, Wang CC, Chen CY (2009a) Water electrolysis for H2 production using a novel bipolar
membrane in low salt concentration. J Membr Sci 330(1–2):334–340
Li L, Yan G, Wu J, Yu X, Guo Q (2009b) Surface-initiated atom-transfer radical polymerization
from polyethersulfone membranes and their antifouling properties. e-Polymers, 26
Li L, Yan G, Wu J, Yu X, Guo Q (2009c) Surface-initiated atom-transfer radical polymerization
from polyethersulfone membranes and their use in antifouling. e-Polymers, 1–10
Li X, Kita H, Zhu H, Zhang Z, Tanaka K (2009e) Synthesis of long-term acid-stable zeolite
membranes and their potential application to esterification reactions. J Membr Sci 339(1–
2):224–232
Li ZL, Zhang YZ, Wang XJ, Li HB (2009f) Pervaporation and its applications in dehydration of
hydrazine fuels. Hanneng Cailiao/Chinese J Energ Mater 17(1):107–112
Li L, Yin Z, Li F, Xiang T, Chen Y, Zhao C (2010) Preparation and characterization of poly
(acrylonitrile-acrylic acid-N-vinyl pyrrolidinone) terpolymer blended polyethersulfone mem-
branes. J Membr Sci 349(1–2):56–64
Li F, Meng J, Ye J, Yang B, Tian Q, Deng C (2014) Surface modification of PES ultrafiltration
membrane by polydopamine coating and poly(ethylene glycol) grafting: morphology, stability,
and anti-fouling. Desalination 344:422–430
Liang L, Rieke PC, Fryxell GE, Liu J, Engehard MH, Alford KL (2000) Temperature-sensitive
surfaces prepared by UV photografting reaction of photosensitizer and N-Isopropylacrylamide.
J Phys Chem B 104(49):11667–11673
Lin YF, Tung KL, Tzeng YS, Chen JH, Chang KS (2012) Rapid atmospheric plasma spray coating
preparation and photocatalytic activity of macroporous titania nanocrystalline membranes.
J Membr Sci 389:83–90
Liu SX, Kim JT (2011) Characterization of surface modification of polyethersulfone membrane.
J Adhes Sci Technol 25(1–3):193–212
Liu SX, Kim JT, Kim S (2008) Effect of polymer surface modification on polymer-protein
interaction via hydrophilic polymer grafting. J Food Sci 73(3):E143–E150
Liu Z, Deng X, Wang M, Chen J, Zhang A, Gu Z, Zhao C (2009) BSA-modified polyethersulfone
membrane: preparation, characterization and biocompatibility. J Biomater Sci Polym Ed 20
(3):377–397
Luo ML, Zhao JQ, Tang W, Pu CS (2005) Hydrophilic modification of poly(ether sulfone)
ultrafiltration membrane surface by self-assembly of TiO2 nanoparticles. Appl Surf Sci 249(1–
4):76–84
Luo M, Wen Q, Liu J, Liu H, Jia Z (2011) Fabrication of SPES/nano-TiO2 composite ultrafiltration
membrane and its anti-fouling mechanism. Chin J Chem Eng 19(1):45–51
Ma H, Bowman CN, Davis RH (2000a) Membrane fouling reduction by backpulsing and surface
modification. J Membr Sci 173(2):191–200
References 121

Ma SD, Sun HY, Huang G, Zhu X (2000b) Effect of marine fouling creatures on corrosion of
carbon steel. J Chin Soc Corros Prot 20(3):181–182
Ma W, Zhang J, Wang X, Wang S (2007) Effect of PMMA on crystallization behavior and
hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in
semi-dilute solutions. Appl Surf Sci 253(20):8377–8388
Maartens A, Jacobs EP, Swart P (2002) UF of pulp and paper effluent: membrane
fouling-prevention and cleaning. J Membr Sci 209(1):81–92. doi:10.1016/S0376-7388(02)
00266-1
Madaeni SS, Zinadini S, Vatanpour V (2011) A new approach to improve antifouling property of
PVDF membrane using in situ polymerization of PAA functionalized TiO2 nanoparticles.
J Membr Sci 380(1–2):155–162
Majeed S, Fierro D, Buhr K, Wind J, Du B, Boschetti-de-Fierro A, Abetz V (2012) Multi-walled
carbon nanotubes (MWCNTs) mixed polyacrylonitrile (PAN) ultrafiltration membranes.
J Membr Sci 403–404:101–109
Malaisamy R, Berry D, Holder D, Raskin L, Lepak L, Jones KL (2010) Development of reactive
thin film polymer brush membranes to prevent biofouling. J Membr Sci 350(1–2):361–370.
doi:10.1016/[Link].2010.01.011
Mansourpanah Y, Madaeni SS, Adeli M, Rahimpour A, Farhadian A (2009) Surface modification
and preparation of nanofiltration membrane from polyethersulfone/polyimide blend-use of a
new material (polyethyleneglycol-triazine). J Appl Polym Sci 112(5):2888–2895. doi:10.1002/
app.29821
Mansourpanah Y, Madaeni SS, Rahimpour A, Kheirollahi Z, Adeli M (2010) Changing the
performance and morphology of polyethersulfone/polyimide blend nanofiltration membranes
using trimethylamine. Desalination 256(1–3):101–107. doi:10.1016/[Link].2010.02.006
Martín A, Arsuaga JM, Roldán N, de Abajo J, Martínez A, Sotto A (2015) Enhanced ultrafiltration
PES membranes doped with mesostructured functionalized silica particles. Desalination
357:16–25. doi:10.1016/[Link].2014.10.046
Mayes AG, Whitcombe MJ (2005) Synthetic strategies for the generation of molecularly imprinted
organic polymers. Adv Drug Deliv Rev 57(12):1742–1778
McCloskey BD, Park HB, Ju H, Rowe BW, Miller DJ, Freeman BD (2012) A bioinspired
fouling-resistant surface modification for water purification membranes. J Membr Sci 413–
414:82–90
Mika AM, Childs RF, Dickson JM, McCarry BE, Gagnon DR (1995) A new class of
polyelectrolyte-filled microfiltration membranes with environmentally controlled porosity.
J Membr Sci 108(1–2):37–56
Mika AM, Childs RF, Dickson JM (1999) Chemical valves based on poly(4-vinylpyridine)-filled
microporous membranes. J Membr Sci 153(1):45–56
Mika AM, Childs RF, Dickson JM (2002) Salt separation and hydrodynamic permeability of a
porous membrane filled with pH-sensitive gel. J Membr Sci 206(1–2):19–30
Millesime L, Amiel C, Chaufer B (1994a) Ultrafiltration of lysozyme and bovine serum albumin
with polysulfone membranes modified with quaternized polyvinylimidazole. J Membr Sci 89
(3):223–234. doi:10.1016/0376-7388(94)80104-5
Millesime L, Amiel C, Chaufer B (1994b) Ultrafiltration of lysozyme and bovine serum albumin
with polysulfone membranes modified with quaternized polyvinylimidazole. J Membrane Sci
Journal of membrane Science 89:223–234
Mishra SP, Vijaya (2007) Removal behavior of hydrous manganese oxide and hydrous stannic
oxide for Cs(I) ions from aqueous solutions. Sep Purif Technol 54(1):10–17
Mittal KL (2009) Surface modification techniques. In: Polymer Surface Modification. CRC Press,
Leiden
Moghimifar V, Raisi A, Aroujalian A (2014) Surface modification of polyethersulfone
ultrafiltration membranes by corona plasma-assisted coating TiO2 nanoparticles. J Membr
Sci 461:69–80
122 4 Surface Modification of Polyethersulfone Membranes

Mohd Yusof AH, Ulbricht M (2008) Polypropylene-based membrane adsorbers via photo-initiated
graft copolymerization: optimizing separation performance by preparation conditions. J Membr
Sci 311(1–2):294–305
Mosbach K, Haupt K (1998) Some new developments and challenges in noncovalent molecular
imprinting technology. J Mol Recognit 11(1–6):62–68
Mu LJ, Zhao WZ (2009) Hydrophilic modification of polyethersulfone porous membranes via a
thermal-induced surface crosslinking approach. Appl Surf Sci 255(16):7273–7278. doi:10.
1016/[Link].2009.03.081
Nair AK, Isloor AM, Kumar R, Ismail AF (2013) Antifouling and performance enhancement of
polysulfone ultrafiltration membranes using CaCO3 nanoparticles. Desalination 322:69–75
Nunes SP, Sforça ML, Peinemann KV (1995) Dense hydrophilic composite membranes for
ultrafiltration. J Membr Sci 106(1–2):49–56. doi:10.1016/0376-7388(95)00076-O
Nyström M (1989) Fouling of unmodified and modified polysulfone ultrafiltration membranes by
ovalbumin. J Membr Sci 44(2–3):183–196. doi:10.1016/S0376-7388(00)83351-7
Pal S, Ghatak SK, De S, DasGupta S (2008) Evaluation of surface roughness of a plasma treated
polymeric membrane by wavelet analysis and quantification of its enhanced performance. Appl
Surf Sci 255(5 PART 1):2504–2511
Pang R, Li X, Li J, Lu Z, Sun X, Wang L (2014) Preparation and characterization of ZrO2/PES
hybrid ultrafiltration membrane with uniform ZrO2 nanoparticles. Desalination 332:60–66.
doi:10.1016/[Link].2013.10.024
Parida KM, Kanungo SB, Sant BR (1981) Studies on MnO2-I. Chemical composition,
microstructure and other characteristics of some synthetic MnO2 of various crystalline
modifications. Electrochim Acta 26(3):435–443
Park JY, Acar MH, Akthakul A, Kuhlman W, Mayes AM (2006) Polysulfone-graft-poly(ethylene
glycol) graft copolymers for surface modification of polysulfone membranes. Biomaterials 27
(6):856–865
Peeva PD, Million N, Ulbricht M (2012) Factors affecting the sieving behavior of anti-fouling
thin-layer cross-linked hydrogel polyethersulfone composite ultrafiltration membranes.
J Membr Sci 390–391:99–112
Peyravi M, Rahimpour A, Jahanshahi M (2012) Thin film composite membranes with modified
polysulfone supports for organic solvent nanofiltration. J Membr Sci 423–424:225–237
Pieracci J, Crivello JV, Belfort G (1999) Photochemical modification of 10 kDa polyethersulfone
ultrafiltration membranes for reduction of biofouling. J Membr Sci 156(2):223–240
Pieracci J, Wood DW, Crivello JV, Belfort G (2000) UV-assisted graft polymerization of
N-vinyl-2-pyrrolidinone onto poly(ether sulfone) ultrafiltration membranes: Comparison of dip
versus immersion modification techniques. Chem Mater 12(8):2123–2133
Pieracci J, Crivello JV, Belfort G (2002a) Increasing membrane permeability of UV-modified poly
(ether sulfone) ultrafiltration membranes. J Membr Sci 202(1–2):1–16
Pieracci J, Crivello JV, Belfort G (2002b) UV-assisted graft polymerization of
N-vinyl-2-pyrrolidinone conto poly(ether sulfone) ultrafiltration membranes using selective
UV wavelengths. Chem Mater 14(1):256–265
Pinnau I, Freeman BD (2000) Formation and modification of polymeric membranes: overview.
ACS symposium
Poźniak G, Gancarz I, Tylus W (2006) Modified poly(phenylene oxide) membranes in
ultrafiltration and micellar-enhanced ultrafiltration of organic compounds. Desalination 198
(1–3):215–224
Prihandana GS, Ito H, Nishinaka Y, Kanno Y, Miki N (2012) Polyethersulfone membrane coated
with nanoporous parylene for ultrafiltration. J Microelectromech Syst 21(6):1288–1290.
doi:10.1109/JMEMS.2012.2224643
Puro L, Mänttäri M, Pihlajamäki A, Nyström M (2006) Characterization of modified nanofiltration
membranes by octanoic acid permeation and FTIR analysis. Chem Eng Res Des 84(2A):87–96
Qiu C, Xu F, Nguyen QT, Ping Z (2005) Nanofiltration membrane prepared from cardo
polyetherketone ultrafiltration membrane by UV-induced grafting method. J Membr Sci 255(1–
2):107–115
References 123

Qiu C, Nguyen QT, Ping Z (2007) Surface modification of cardo polyetherketone ultrafiltration
membrane by photo-grafted copolymers to obtain nanofiltration membranes. J Membr Sci 295
(1–2):88–94
Rahimpour A (2011a) Preparation and modification of nano-porous polyimide (PI) membranes by
UV photo-grafting process: Ultrafiltration and nanofiltration performance. Korean J Chem Eng
28(1):261–266
Rahimpour A (2011b) UV photo-grafting of hydrophilic monomers onto the surface of
nano-porous PES membranes for improving surface properties. Desalination 265(1–3):93–101
Rahimpour A, Madaeni SS (2010) Improvement of performance and surface properties of
nano-porous polyethersulfone (PES) membrane using hydrophilic monomers as additives in
the casting solution. J Membr Sci 360(1–2):371–379
Rahimpour A, Madaeni SS, Taheri AH, Mansourpanah Y (2008) Coupling TiO2 nanoparticles
with UV irradiation for modification of polyethersulfone ultrafiltration membranes. J Membr
Sci 313(1–2):158–169
Rahimpour A, Madaeni SS, Zereshki S, Mansourpanah Y (2009) Preparation and characterization
of modified nano-porous PVDF membrane with high antifouling property using UV
photo-grafting. Appl Surf Sci 255(16):7455–7461
Rahimpour A, Madaeni SS, Ghorbani S, Shockravi A, Mansourpanah Y (2010a) The influence of
sulfonated polyethersulfone (SPES) on surface nano-morphology and performance of
polyethersulfone (PES) membrane. Appl Surf Sci 256(6):1825–1831. doi:10.1016/[Link].
2009.10.014
Rahimpour A, Madaeni SS, Mansourpanah Y (2010b) Fabrication of polyethersulfone
(PES) membranes with nano-porous surface using potassium perchlorate (KClO4) as an
additive in the casting solution. Desalination 258(1–3):79–86
Rahimpour A, Madaeni SS, Mansourpanah Y (2010c) Nano-porous polyethersulfone
(PES) membranes modified by acrylic acid (AA) and 2-hydroxyethylmethacrylate (HEMA)
as additives in the gelation media. J Membr Sci 364(1–2):380–388
Rajagopalan M, Ramamoorthy M, Doraiswamy RM (2004) Cellulose acetate and polyethersulfone
blend ultrafiltration membranes. Part I. Preparation and characterizations. Polym Adv Technol
15:149–157
Ran F, Nie S, Zhao W, Li J, Su B, Sun S, Zhao C (2011) Biocompatibility of modified
polyethersulfone membranes by blending an amphiphilic triblock co-polymer of poly(vinyl
pyrrolidone)-b-poly(methyl methacrylate)-b-poly(vinyl pyrrolidone). Acta Biomater 7
(9):3370–3381
Rana D, Matsuura T (2010) Surface modifications for antifouling membranes. Chem Rev 110
(4):2448–2471
Razali NF, Mohammad AW, Hilal N, Leo CP, Alam J (2013) Optimisation of
polyethersulfone/polyaniline blended membranes using response surface methodology
approach. Desalination 311:182–191
Razmjou A, Mansouri J, Chen V (2011a) The effects of mechanical and chemical modification of
TiO2 nanoparticles on the surface chemistry, structure and fouling performance of PES
ultrafiltration membranes. J Membr Sci 378(1–2):73–84
Razmjou A, Mansouri J, Chen V, Lim M, Amal R (2011b) Titania nanocomposite polyether-
sulfone ultrafiltration membranes fabricated using a low temperature hydrothermal coating
process. J Membr Sci 380(1–2):98–113
Razmjou A, Resosudarmo A, Holmes RL, Li H, Mansouri J, Chen V (2012) The effect of modified
TiO2 nanoparticles on the polyethersulfone ultrafiltration hollow fiber membranes.
Desalination 287:271–280
Reddy AVR, Mohan DJ, Bhattacharya A, Shah VJ, Ghosh PK (2003) Surface modification of
ultrafiltration membranes by preadsorption of a negatively charged polymer: I. Permeation of
water soluble polymers and inorganic salt solutions and fouling resistance properties. J Membr
Sci 214(2):211–221
124 4 Surface Modification of Polyethersulfone Membranes

Reddy AVR, Trivedi JJ, Devmurari CV, Mohan DJ, Singh P, Rao AP, Joshi SV, Ghosh PK (2005)
Fouling resistant membranes in desalination and water recovery. Desalination 183(1–3):
301–306
Reuben BG, Perl O, Morgan NL, Stratford P, Dudley LY, Hawes C (1995) Phospholipid coatings
for the prevention of membrane fouling. J Chem Technol Biotechnol 63(1):85–91
Revanur R, McCloskey B, Breitenkamp K, Freeman B, Emrick T (2007a) Macromolecules
40:3624
Revanur R, McCloskey B, Breitenkamp K, Freeman BD, Emrick T (2007b) Reactive amphiphilic
graft copolymer coatings applied to poly(vinylidene fluoride) ultrafiltration membranes.
Macromolecules 40(10):3624–3630. doi:10.1021/ma0701033
Ridgway HF, Rigby MG, Argo DG (1984) Adhesion of a Mycobacterium sp. to cellulose diacetate
membranes used in reverse osmosis. Appl Environ Microbiol 47(1):61–67
Rosenberger S, Krüger U, Witzig R, Manz W, Szewzyk U, Kraume M (2002) Performance of a
bioreactor with submerged membranes for aerobic treatment of municipal waste water. Water
Res 36(2):413–420
Saha NK, Balakrishnan M, Ulbricht M (2009) Fouling control in sugarcane juice ultrafiltration
with surface modified polysulfone and polyethersulfone membranes. Desalination 249
(3):1124–1131. doi:10.1016/[Link].2009.05.013
Saito K, Ito M, Yamagishi H, Furusaki S, Sugo T, Okamoto J (1989) Novel hollow fiber
membrane for the removal of metal ion during permeation: preparation by radiation-induced
cografting of a crosslinking agent with reactive monomer. Ind Eng Chem Res 28(12):1808–
1812
Sata T (1993) Properties of composite membranes formed from ion-exchange membranes and
conducting polymers. 4. Change in membrane resistance during electrodialysis in the presence
of surface-active agents. J Phys Chem 97(26):6920–6923
Saxena N, Prabhavathy C, De S, DasGupta S (2009) Flux enhancement by argon-oxygen plasma
treatment of polyethersulfone membranes. Sep Purif Technol 70(2):160–165
Schulze A, Marquardt B, Kaczmarek S, Schubert R, Prager A, Buchmeiser MR (2010) Electron
beam-based functionalization of poly(ethersulfone) membranes. Macromol Rapid Commun 31
(5):467–472
Seman MNA, Khayet M, Hilal N (2012) Comparison of two different UV-grafted nanofiltration
membranes prepared for reduction of humic acid fouling using acrylic acid and
N-vinylpyrrolidone. Desalination 287:19–29. doi:10.1016/[Link].2010.10.031
Shah TN, Goodwin JC, Ritchie SMC (2005) Development and characterization of a microfiltration
membrane catalyst containing sulfonated polystyrene grafts. J Membr Sci 251(1–2):81–89
Shannon M, Bohn P, Elimelech M, Georgiadis J, Maries B, Mayes A (2008) Science and
technology for water purification in the coming decades. Nature 452(7185):301–310
Sheikholaslami R (1999) Composite fouling - inorganic and biological: a review. Environ Prog 18
(2):113–122
Sheikholeslami R (1999) Fouling mitigation in membrane processes. Desalination 123(1):45–53
Shi H, Shi D, Yin L, Luan S, Zhao J, Yin J (2010a) Synthesis of amphiphilic
polycyclooctene-graft-poly(ethylene glycol) copolymers by ring-opening metathesis polymer-
ization. React Funct Polym 70(7):449–455
Shi Q, Su Y, Ning X, Chen W, Peng J, Jiang Z (2010b) Graft polymerization of methacrylic acid
onto polyethersulfone for potential pH-responsive membrane materials. J Membr Sci 347(1–
2):62–68
Shi Q, Su Y, Ning X, Chen W, Peng J, Jiang Z (2011) Trypsin-enabled construction of anti-fouling
and self-cleaning polyethersulfone membrane. Bioresour Technol 102(2):647–651. doi:10.
1016/[Link].2010.08.030
Shi F, Ma Y, Ma J, Wang P, Sun W (2013) Preparation and chacterization of PVDF/TiO2 hybrid
membranes with ionic liquid modified nano-TiO2 particles. J Membr Sci 427:259–269
Song YQ, et al (2000) Surface modification of polysulfone membranes by lowtemperature
plasma-graft poly(ethylene glycol) onto polysulfone membranes. J Appl Polym Sci 78(5):979–
985.
References 125

Sotto A, Boromand A, Zhang RX, Luis P, Arsuaga JM, Kim J et al (2011) Effect of nanoparticle
aggregation at low concentrations of TiO(2) on the hydrophilicity, morphology, and fouling
resistance of PES–TiO(2) membranes. J Colloid Interf Sci 363:540–50
Speaker, LM Chem Abstr (1986) 105, 232980j; U.S. Patent 4,554,076, 1985.
Steen ML, Jordan AC, Fisher ER (2002) Hydrophilic modification of polymeric membranes by
low temperature H2O plasma treatment. J Membr Sci 204(1–2):341–357
Su BH, Fu P, Li Q, Tao Y, Li Z, Zao HS, Zhao CS (2008) Evaluation of polyethersulfone highflux
hemodialysis membrane in vitro and in vivo. J Mater Sci—Mater Med 19(2):745–751
Su Q, Pan B, Wan S, Zhang W, Lv L (2010) Use of hydrous manganese dioxide as a potential
sorbent for selective removal of lead, cadmium, and zinc ions from water. J Colloid Interface
Sci 349(2):607–612
Susanto H, Ulbricht M (2007) Photografted thin polymer hydrogel layers on PES ultrafiltration
membranes: characterization, stability, and influence on separation performance. Langmuir 23
(14):7818–7830
Susanto H, Ulbricht M (2008) High-performance thin-layer hydrogel composite membranes for
ultrafiltration of natural organic matter. Water Res 42(10–11):2827–2835
Susanto H, Balakrishnan M, Ulbricht M (2007) Via surface functionalization by photograft
copolymerization to low-fouling polyethersulfone-based ultrafiltration membranes. J Membr
Sci 288(1–2):157–167
Taffarel SR, Rubio J (2010) Removal of Mn2+ from aqueous solution by manganese oxide coated
zeolite. Miner Eng 23(14):1131–1138
Taniguchi M, Belfort G (2004) Low protein fouling synthetic membranes by UV-assisted surface
grafting modification: Varying monomer type. J Membr Sci 231(1–2):147–157
Taniguchi M, Kilduff JE, Belfort G (2003) Low fouling synthetic membranes by UV-assisted graft
polymerization: Monomer selection to mitigate fouling by natural organic matter. J Membr Sci
222(1–2):59–70
Tari SSM, Ali N, Mamat M (2010) Scrutinizing the consequence of surface modification on
membrane stability and resistivity towards fouling. In: CSSR 2010–2010 international
conference on science and social research, pp741–745
Teng SX, Wang SG, Gong WX, Liu XW, Gao BY (2009) Removal of fluoride by hydrous
manganese oxide-coated alumina: Performance and mechanism. J Hazard Mater 168(2–
3):1004–1011
Tripathi BP, Dubey NC, Choudhury S, Stamm M (2012) Antifouling and tunable amino
functionalized porous membranes for filtration applications. J Mater Chem 22(37):19981–
19992
Tripathi BP, Dubey NC, Stamm M (2014) Polyethylene glycol cross-linked sulfonated
polyethersulfone based filtration membranes with improved antifouling tendency. J Membr
Sci 453:263–274. doi:10.1016/[Link].2013.11.007
Turner NW, Jeans CW, Brain KR, Allender CJ, Hlady V, Britt DW (2006) From 3D to 2D: a
review of the molecular imprinting of proteins. Biotechnol Prog 22(6):1474–1489
Tyszler D, Zytner RG, Batsch A, Brügger A, Geissler S, Zhou H, Klee D, Melin T (2006) Reduced
fouling tendencies of ultrafiltration membranes in wastewater treatment by plasma modifica-
tion. Desalination 189(1-3 SPEC. ISS.):119–129
Ulbricht M, Belfort G (1996) Surface modification of ultrafiltration membranes by low
temperature plasma II. Graft polymerization onto polyacrylonitrile and polysulfone.
J Membr Sci 111(2):193–215
Ulbricht M, Hicke H (1993) Photomodification of ultrafiltration membranes, 1. Photochemical
modification of polyacrylonitirle ultrafiltration membranes with aryl azides. Angew Makromol
Chem 210:69–95
Ulbricht M, Riedel M, Marx U (1996) Novel photochemical surface functionalization of
polysulfone ultrafiltration membranes for covalent immobilization of biomolecules. J Membr
Sci 120(2):239–259
126 4 Surface Modification of Polyethersulfone Membranes

Ulbricht M, Riedel M (1998) Ultrafiltration membrane surfaces with grafted polymer ‘tentacles’:
Preparation, characterization and application for covalent protein binding. Biomaterials 19
(14):1229–1237
Van Der Bruggen B (2009a) Chemical modification of polyethersulfone nanofiltration membranes:
a review. J Appl Polym Sci 114(1):630–642
Van Der Bruggen B (2009b) Comparison of redox initiated graft polymerisation and sulfonation
for hydrophilisation of polyethersulfone nanofiltration membranes. Eur Polymer J 45(7):1873–
1882. doi:10.1016/[Link].2009.04.017
Venault A, Liu YH, Wu JR, Yang HS, Chang Y, Lai JY, Aimar P (2014) Low-biofouling
membranes prepared by liquid-induced phase separation of the PVDF/polystyrene-b-poly
(ethylene glycol) methacrylate blend. J Membr Sci 450:340–350
Wang Y, Su Y, Sun Q, Ma X, Ma X, Jiang Z (2006a) Improved permeation performance of
Pluronic F127-polyethersulfone blend ultrafiltration membranes. J Membr Sci 282(1–2):44–51
Wang YQ, Su YL, Ma XL, Sun Q, Jiang ZY (2006b) Pluronic polymers and polyethersulfone
blend membranes with improved fouling-resistant ability and ultrafiltration performance.
J Membr Sci 283(1–2):440–447
Wang YQ, Wang T, Su YL, Peng FB, Wu H, Jiang ZY (2006c) Protein-adsorption-resistance and
permeation property of polyethersulfone and soybean phosphatidylcholine blend ultrafiltration
membranes. J Membr Sci 270(1–2):108–114
Wang H, Yang L, Zhao X, Yu T, Du Q (2009a) Improvement of hydrophilicity and blood
compatibility on polyethersulfone membrane by blending sulfonated polyethersulfone. Chin J
Chem Eng 17(2):324–329. doi:10.1016/S1004-9541(08)60211-6
Wang Z, Wu Z, Tang S (2009b) Extracellular polymeric substances (EPS) properties and their
effects on membrane fouling in a submerged membrane bioreactor. Water Res 43(9):2504–
2512
Wang D, Zou W, Li L, Wei Q, Sun S, Zhao C (2011) Preparation and characterization of
functional carboxylic polyethersulfone membrane. J Membr Sci 374(1–2):93–101. doi:10.
1016/[Link].2011.03.021
Wang Z, Wang H, Liu J, Zhang Y (2014) Preparation and antifouling property of polyethersulfone
ultrafiltration hybrid membrane containing halloysite nanotubes grafted with MPC via RATRP
method. Desalination 344:313–320
Wavhal DS, Fisher ER (2002a) Hydrophilic modification of polyethersulfone membranes by low
temperature plasma-induced graft polymerization. J Membr Sci 209(1):255–269
Wavhal DS, Fisher ER (2002b) Modification of porous poly(ether sulfone) membranes by
low-temperature CO2-plasma treatment. J Polym Sci Part B: Polym Phys 40(21):2473–2488
Wavhal DS, Fisher ER (2003) Membrane surface modification by plasma-induced polymerization
of acrylamide for improved surface properties and reduced protein fouling. Langmuir 19
(1):79–85
Wei J, Helm GS, Corner-Walker N, Hou X (2006) Desalination, 192, 252
Wei S, Jakusch M, Mizaikoff B (2006a) Capturing molecules with template materials—analysis
and rational design of molecularly imprinted polymers. Anal Chim Acta 578:50–58
Wei X, Wang R, Li Z, Fane AG (2006b) Development of a novel electrophoresis-UV grafting
technique to modify PES UF membranes used for NOM removal. J Membr Sci 273(1–2):47–
57. doi:10.1016/[Link].2005.11.049
Whitcombe M, Vulfson E (2001) Imprinted polymers. Adv Mater 13:467–478
Wu J, Huang X (2008) Effect of dosing polymeric ferric sulfate on fouling characteristics, mixed
liquor properties and performance in a long-term running membrane bioreactor. Sep Purif
Technol 63(1):45–52
Wu G, Gan S, Cui L, Xu Y (2008) Preparation and characterization of PES/TiO2 composite
membranes. Appl Surf Sci 254(21):7080–7086
Wulff G (1995) Molecular imprinting in crosslinked materials with the aid of molecular templates
—a way towards aritificial antibodies. Angew chemInt ED Engl 34:1812–1832
Wulff G (2002) Enzyme-like catalysis by molecularly imprinted polymers. Chem Rev 102(1):1–27
References 127

Xi W, Rong W, Zhansheng L, Fane A (2006) Development of a novel electrophoresis-UV grafting

technique to modify PES UF membranes for NOm removal. Membr Sci 273:47–57
Xiang T, Wang LR, Ma L, Han ZY, Wang R, Cheng C, Xia Y, Qin H, Zhao CS (2014) From
commodity polymers to functional polymers. Scientific Reports 3. doi:10.1038/srep04604
Xie Y, Li SS, Jiang X, Xiang T, Wang R, Zhao CS (2015) Zwitterionic glycosyl modified
polyethersulfone membranes with enhanced anti-fouling property and blood compatibility.
J Colloid Interface Sci 443:36–44. doi:10.1016/[Link].2014.11.053
Xu FJ, Kang ET, Neoh KG (2005) UV-induced coupling of 4-vinylbenzyl chloride on
hydrogen-terminated Si(100) surfaces for the preparation of well-defined polymer-Si hybrids
via surface-initiated ATRP. Macromolecules 38(5):1573–1580. doi:10.1021/ma049225a
Yamagishi H, Crivello JV, Belfort G (1995a) Development of a novel photochemical technique for
modifying poly(arylsulfone) ultrafiltration membranes. J Membr Sci 105(3):237–247
Yamagishi H, Crivello JV, Belfort G (1995b) Evaluation of photochemically modified poly
(arylsulfone) ultrafiltration membranes. J Membr Sci 105(3):249–259
Yan S, Maeda H, Kusakabe K, Morooka S (1994) Thin palladium membrane formed in support
pores by metal-organic chemical vapor deposition method and application to hydrogen
separation. Ind Eng Chem Res 33(3):616–622
Yan MG, Liu LQ, Tang ZQ, Huang L, Li W, Zhou J, Gu JS, Wei XW, Yu HY (2008) Plasma
surface modification of polypropylene microfiltration membranes and fouling by BSA
dispersion. Chem Eng J 145(2):218–224
Yang B, Yang W (2003) Photografting modification of PET nuclepore membranes. Macromol
Sci A Pure Appl Chem 40:309–320
Yang W, Cicek N, Ilg J (2006) State-of-the-art of membrane bioreactors: worldwide research and
commercial applications in North America. J Membr Sci 270(1–2):201–211
Yang YF, Wan LS, Xu ZK (2009a) Surface hydrophilization for polypropylene microporous
membranes: a facile interfacial crosslinking approach. J Membr Sci 326(2):372–381. doi:10.
1016/[Link].2008.10.011
Yang YF, Wan LS, Xu ZK (2009b) Surface hydrophilization of microporous polypropylene
membrane by the interfacial crosslinking of polyethylenimine. J Membr Sci 337(1–2):70–80.
doi:10.1016/[Link].2009.03.023
Ye L, Mosbach K (2008) Molecular imprinting: synthetic materials as substitutes for biological
antibodies and receptors. Chem Mater 20(3):859–868
Yin J, Coutris N, Huang Y (2012) Experimental investigation of aligned groove formation on the
inner surface of polyacrylonitrile hollow fiber membrane. J Membr Sci 394–395:57–68
Ying L, Kang ET, Neoh KG (2002) Covalent immobilization of glucose oxidase on microporous
membranes prepared from poly(vinylidene fluoride) with grafted poly(acrylic acid) side chains.
J Membr Sci 208(1–2):361–374
Yu HY, Hu MX, Xu ZK, Wang JL, Wang SY (2005) Surface modification of polypropylene
microporous membranes to improve their antifouling property in MBR: NH3 plasma treatment.
Sep Purif Technol 45(1):8–15
Yu HY, Xu ZK, Xie YJ, Liu ZM, Wang SY (2006) Flux enhancement for polypropylene
microporous membrane in a SMBR by the immobilization of poly(N-vinyl-2-pyrrolidone) on
the membrane surface. J Membr Sci 279(1–2):148–155
Yu HY, He XC, Liu LQ, Gu JS, Wei XW (2007) Surface modification of polypropylene
microporous membrane to improve its antifouling characteristics in an SMBR: N2 plasma
treatment. Water Res 41(20):4703–4709
Yu HY, Liu LQ, Tang ZQ, Yan MG, Gu JS, Wei XW (2008a) Mitigated membrane fouling in an
SMBR by surface modification. J Membr Sci 310(1–2):409–417
Yu HY, Liu LQ, Tang ZQ, Yan MG, Gu JS, Wei XW (2008b) Surface modification of
polypropylene microporous membrane to improve its antifouling characteristics in an SMBR:
air plasma treatment. J Membr Sci 311(1–2):216–224
128 4 Surface Modification of Polyethersulfone Membranes

Yu H, Cao Y, Kang G, Liu J, Li M, Yuan Q (2009a) Enhancing antifouling property of

polysulfone ultrafiltration membrane by grafting zwitterionic copolymer via UV-initiated
polymerization. J Membr Sci 342(1–2):6–13
Yu LY, Xu ZL, Shen HM, Yang H (2009b) Preparation and characterization of PVDF-SiO2
composite hollow fiber UF membrane by sol-gel method. J Membr Sci 337(1–2):257–265
Yu H, et al (2013) Development of a hydrophilic PES ultrafiltration membrane containing
SiO2@N-Halamine nanoparticles with both organic antifouling and antibacterial properties.
Desalination. 326:69–76.
Yun S, Ted Oyama S (2011) Correlations in palladium membranes for hydrogen separation: a
review. J Membr Sci 375(1–2):28–45
Yune PS, Kilduff JE, Belfort G (2011) Fouling-resistant properties of a surface-modified poly
(ether sulfone) ultrafiltration membrane grafted with poly(ethylene glycol)-amide binary
monomers. J Membr Sci 377(1–2):159–166. doi:10.1016/[Link].2011.04.029
Zhan J, Liu Z, Wang B, Ding F (2004) Modification of a membrane surface charge by a low
temperature plasma induced grafting reaction and its application to reduce membrane fouling.
Sep Sci Technol 39(13):2977–2995
Zhang H, Ye L, Mosbach K (2006) Non-covalent molecular imprinting with emphasis on its
application in separation and drug development. Mol Recognit 19:248–259
Zhang M, Nguyen QT, Ping Z (2009) Hydrophilic modification of poly (vinylidene fluoride)
microporous membrane. J Membr Sci 327(1–2):78–86
Zhang J, Zhang M, Zhang K (2014) Fabrication of poly(ether sulfone)/poly(zinc acrylate)
ultrafiltration membrane with anti-biofouling properties. J Membr Sci 460:18–24
Zhao B, Brittain WJ (2000) Polymer brushes: surface-immobilized macromolecules. Prog Polym
Sci (Oxf) 25(5):677–710
Zhao C, Liu X, Rikimaru S, Nomizu M, Nishi N (2003) Surface characterization of polysulfone
membranes modified by DNA immobilization. J Membr Sci 214(2):179–189
Zhao ZP, Li J, Wang D, Chen CX (2005) Nanofiltration membrane prepared from polyacrylonitrile
ultrafiltration membrane by low-temperature plasma: 4. Grafting of N-vinylpyrrolidone in
aqueous solution. Desalination 184(1–3):37–44
Zhao K, Cheng G, Huang J, Ying X (2008) Rebinding and recognition properties of
protein-macromolecularly imprinted calcium phosphate/alginate hybrid polymer microspheres.
React Funct Polym 68(3):732–741
Zhao W, Huang J, Fang B, Nie S, Yi N, Su B, Li H, Zhao C (2011) Modification of
polyethersulfone membrane by blending semi-interpenetrating network polymeric nanoparti-
cles. J Membr Sci 369(1–2):258–266
Zhao C, Xue J, Ran F, Sun S (2013a) Modification of polyethersulfone membranes—a review of
methods. Prog Mater Sci 58(1):76–150
Zhao W, Mou Q, Zhang X, Shi J, Sun S, Zhao C (2013b) Preparation and characterization of
sulfonated polyethersulfone membranes by a facile approach. Eur Polymer J 49(3):738–751
Zhao S, Yan W, Shi M, Wang Z, Wang J, Wang S (2015) Improving permeability and antifouling
performance of polyethersulfone ultrafiltration membrane by incorporation of ZnO-DMF
dispersion containing nano-ZnO and polyvinylpyrrolidone. J Membr Sci 478:105–116. doi:10.
1016/[Link].2014.12.050
Zhou R, Ren PF, Yang HC, Xu ZK (2014) Fabrication of antifouling membrane surface by poly
(sulfobetaine methacrylate)/polydopamine co-deposition. J Membr Sci 466:18–25
Zhu LP, Xu L, Zhu BK, Feng YX, Xu YY (2007a) Preparation and characterization of improved
fouling-resistant PPESK ultrafiltration membranes with amphiphilic PPESK-graft-PEG
copolymers as additives. J Membr Sci 294(1–2):196–206
References 129

Zhu LP, Zhang XX, Xu L, Du CH, Zhu BK, Xu YY (2007b) Improved protein-adsorption
resistance of polyethersulfone membranes via surface segregation of ultrahigh molecular
weight poly(styrene-alt-maleic anhydride). Colloids Surf B 57(2):189–197
Zhu L, Wang J, Zhu B, Xu Y (2008a) Molecular design and synthesis of amphiphilic copolymers,
and the performances of their blend membranes. Acta Polymerica Sinica 4:309–317
Zhu LP, Yi Z, Liu F, Wei XZ, Zhu BK, Xu YY (2008b) Amphiphilic graft copolymers based on
ultrahigh molecular weight poly(styrene-alt-maleic anhydride) with poly(ethylene glycol) side
chains for surface modification of polyethersulfone membranes. Eur Polymer J 44(6):1907–
1914
Zhu J, Guo N, Zhang Y, Yu L, Liu J (2014) Preparation and characterization of negatively charged
PES nanofiltration membrane by blending with halloysite nanotubes grafted with poly (sodium
4-styrenesulfonate) via surface-initiated ATRP. J Membr Sci 465:91–99
Zinadini S, Zinatizadeh AA, Rahimi M, Vatanpour V, Zangeneh H (2014) Preparation of a novel
antifouling mixed matrix PES membrane by embedding graphene oxide nanoplates. J Membr
Sci 453:292–301
Chapter 5
Membrane Characterization Techniques

Membrane characterization is critical at various stages in the lifecycle of a mem-

brane. At the research and development stage, it forms a critical element of the
iterative design-synthesise-test-evaluate process, while in operating the characteri-
zation of membranes is more limited and usually relates to determining whether
cleaning/regeneration is required, or eventually membrane replacement. Membrane
characterization is critical at various stages in the lifecycle of a membrane. At
the research and development stage, it forms a critical element of the iterative
design-synthesise-test-evaluate process, while in operating the characterization of
membranes is more limited and usually relates to determining whether cleaning/
regernation is required, or eventually membrane replacement. Finally, membranes
are also characterised in postmortems, which give critical insight into membrane
failure and help propose modifications to membrane preparations or operation. This
chapter provides a critical review of membrane characterization, particularly PES
characterization and some related comments on membrane stability.

5.1 Introduction

After introducing new components into the membrane matrix using different
chemical or physical strategies, the structure and morphology of the membranes
may relatively change. Therefore, after surface modification process of membranes,
characterisation of membranes is a paramount step to confirm if the alterations
of membrane structure, and membrane morphology and membrane performance
are applicable. There are three types of characterization of membranes:

© Springer Nature Singapore Pte Ltd. 2017 131

B. Ladewig and M.N.Z. Al-Shaeli, Fundamentals of Membrane Bioreactors,
Springer Transactions in Civil and Environmental Engineering,
DOI 10.1007/978-981-10-2014-8_5
132 5 Membrane Characterization Techniques

(1) characterisation of composition, (2) characterisation of morphology and struc-

ture, and (3) characterisation of performance (Zhao et al. 2013).

5.2 Composition Characterization

After modification the membrane surface and introducing new components into its
matrix, the bulks or compositions of membrane surfaces membrane may change to
some extents. This change can be detected by different means as described below.

5.3 Fourier Transform Infrared Spectroscopy (FTIR)

Fourier transform infrared spectroscopy (FTIR) is an effective tool used to identify

material chemistry and produce an infrared spectrum of absorption, photoconduc-
tivity, mission or Raman scattering of a solid, liquid or gas. A FTIR spectrometer
detects high spectral resolution data over a wide spectral range. This is a significant
advantage over dispersive spectrometer, which measures intensity over a narrow
range of wavelengths at a time. FTIR deals with the vibration of various types of
molecular bonds at different frequencies. When exposing material into infrared
radiation, the molecules would absorb some of the infrared energy. This could
happen when the radiation frequency provides energy in an accurate amount, which
is required by one of the bonds in the molecules. In Membranes, many research
studies have been conducted to characterise the chemical structure of the modified
PES membranes using ATR-FTIR as analytical tool (Pieracci et al. 1999; Fontyn
et al. 1986b; Millesime et al. 1994). For example, (Fontyn et al. 1986a) investigated
the chemical characterisation of PES and PVDF ultrafiltration membranes using
spectroscopic strategies. They state that FTIR can be utilised as a tool to evaluate
PES/PVDF membrane component after introducing new additives into their
membrane matrix. In a research study conducted by (Millesime et al. 1994), PES
membranes were coated with polyvinyl imidazole (PVI) and then quaternized using
a cross-linking agent bearing Bisphenol A group. The thickness of PVI was cal-
culated using ATR-FTIR spectroscopy. (Pieracci et al. 1999) modified commercial
PES membranes (10 KDa) by photografting of three hydrophilic monomers
(N-vinyl-2-pyrrolidinone (NVP), N-vinylcaprolactam (NVC), and N-vinylforma-
mide (NVF). They used ATR-FTIR in their study to confirm the occurrence of
photochemical grafting of the hydrophilic monomers onto the surface of PES UF
membranes as shown in Figs. 5.1 and 5.2.
As shown in Fig. 5.1, Compared with neat PES membranes (10 KDa), there is a
wide peak between 3200–3600 cm−1, ascribed to the stretch of OH group in all the
modified membranes. (Pieracci et al. 1999) also state that after irradiation process,
the amount of hydroxyl groups formed on the surface of membrane has been
linearly increased with irradiation time (1, 3, 5, 7 and 10 min).
5.3 Fourier Transform Infrared Spectroscopy (FTIR) 133

Fig. 5.1 FTIR/ATR spectra with a germanium crystal (45°) of the surface of a Pristine PES, b a
PES membrane irradiated for 1 min, c a PES membrane irradiated for 3 and 5 min d a PES
membrane irradiated for 7 min e a PES membrane irradiated for 10 min (Pieracci et al. 1999)

Fig. 5.2 FTIR/ATR spectra with a germanium crystal (45°) of the surface of PES: a unmodified,
b PES membrane modified with 1 wt% N-vinyl-2-pyrrolidinone (NVP) and irradiated for 3 min,
c PES membrane modified with 0.75 wt% N-vinylformamide (NVF) and 10 min of irradiation, and
d PES membrane modified with 0.1 wt% N-vinylcaprolactam (NVC) and 5 min of irradiation
(Pieracci et al. 1999)
134 5 Membrane Characterization Techniques

As shown in Fig. 5.2, compared to the pristine PES, there is an absorbance band,
appearing at approximately 1678 cm−1, assigned to the amide I carbonyl stretch of
the NVP five-membered lactam ring and NVC seven-membered ring. The amide I
carbonyl band of NVF was shifted down to *1645 cm−1 because the carbonyl
group was not within a ring structure. The occurrence of amide I carbonyl stretch
bands in all three spectra confirmed that the monomers had been successfully
grafted onto the surface of the PES membrane. To sum up, FTIR-ATR is not very
surface sensitive due to the large penetration depth, although it is vey common
technique used to characterise or analyse the membrane surface quickly.

5.4 Nuclear Magnetic Resonance (NMR)

NMR is one of the principal techniques used to achieve detailed information about
the chemical structure, topology of molecules. In membranes, it is rarely used to
directly characterise the chemical structure of the surface-modified membranes.
However, it is usually used to characterise the structure of the modifying agent
(Zhao et al. 2011a; Brayfield et al. 2008; Yi et al. 2010b; Gaina et al. 2011).
(Yi et al. 2010b) have been modified PES membranes with amphiphilic polysul-
fone-graft-poly (ethylene glycol) methyl ether methacrylate (PSF-g-POEM). NMR
was used to characterise the amphiphilic additive (PSF-g-POEM).

5.5 X-ray Photoelectron Spectroscopy (XPS)

X-ray photoelectron spectroscopy (XPS) (known as electron microscopy) is a

highly quantitative spectroscopic technique used to characterise the chemical dis-
tribution and structure composition of the uppermost atomic surface of the samples
(Hester et al. 1999; Liu and Kim 2011). It can be also used to recognise the
elemental composition, chemical state (which is very important for the main ele-
ments of polymer such as C, O, N, S and F) and electronic state of the elements. In
membranes, it is also used for characterising the modified PES membranes
(Mosqueda-Jimenez et al. 2006; Chu et al. 2005; Liu et al. 2009a; Liu and Kim
2011; Wu and Yang 2006; Wei et al. 2012; Li et al. 2005).
Lin et al. (2015) synthesised tris(2,4,6-trimethoxyphenyl) poly(phenylene oxide)-
methylene quaternary-phosphonium-bromide (TPPOQP-Br) and triethyl poly(phe-
nylene oxide)-methylene quaternary-phosphonuim-bromide (TPPOQA-Br). XPS
test have been conducted to verify the effects of TPPOQP-Br and TPPOQA-Br on
BPPO UF membranes. The results indicated that the composite membranes
(BPPO/TPPOQP-Br) showed an increase in the concentration of TPPOQP-Br from
the top surface to the bottom surface. Conversely, an opposite concentration gradient
of TPPOQA-Br was observed for BPPO/TPPOQA-Br composite membranes.
5.6 Thermal Gravitational Analysis (TGA) 135

5.6 Thermal Gravitational Analysis (TGA)

Generally, thermal gravitational analysis is an analytical technique, which is used to

measure weight changes in a material as a function of temperature (with constant
heating rate) or time (with constant mass loss or constant temperature) under a
controlled atmosphere. It is mainly used to evaluate the thermal stability of material
and its composition. In membrane field, TGA has been commonly used to evaluate
the thermal stability of membranes or thermal degradation behaviour of membranes.
Zhang et al. (2014) modified PES UF membranes with Poly (zinc acrylate)
(PZA) to tune the hydrophilicity and improve the anti-biofouling properties of
membranes. They used TGA to prove the presence PZA within the membrane
matrix.

5.7 Differential Scanning Calorimetry (DSC)

DSC is an analytical technique, which is used thoroughly to measure the difference

in the amount of heat required to increase the temperature of a sample and reference
as a function of temperature. In membrane fields, many researchers have used DSC
for different purposes, for example, (Bolong et al. 2009; Yi et al. 2010b; Li et al.
2005) used DSC in their study to find the miscibility between PES and the additives
via analysing the glass transition temperature of the polymers. For sample prepa-
ration, membrane samples were cut into shape; accuracy amount of membrane
sample was measured in digital balance (weight should less than 10 mg). The
membrane sample was then folded and placed into preweighed aluminium crucible
(pan) and after that kept sample as thin as possible and covered as much as the pan
bottom as possible. Then, place the lid on the pan and both the lid and the pan (with
sample inside) assembly were placed in the well of the lower crimping die.
Thereafter firmly press down on the plunger and then remove the pan with tweezers
and make sure that the sample has been completely encapsulated in the pan. The
sample was measured under nitrogen atmosphere.
To sum up, FTIR, NMR, XPS, TGA and DSC are very important tools used to
indicate the alteration on the membrane surface after surface modification using
chemical or physical methods.
However, introducing new components into PES matrix to modify its surface
may not only result in chemical or physical alterations, but also affect the membrane
morphology and structure of membrane. Therefore, characterization the structure
and morphology of PES membrane after surface modification is very important.
136 5 Membrane Characterization Techniques

5.8 Energy-Dispersive X-ray Spectroscopy (EDS)

Energy-dispersive-ray spectroscopy (EDS) elemental microanalysis in conjunction

with scanning electron microscope (SEM) has been extensively used for charac-
terising the distribution of elements on the surface of samples. It has a major
advantage in that the spatial resolution can be quite high and SEM images are
obtained for the same area being analysed, so that information regarding both the
surface features/feature size can be combined with knowledge of the elemental
composition.
Characterisation of morphology and structure
Direct visualisation of structural features with the aid of microtechnique has the
advantage of being a model-free method, which generate abundant, practical and
direct information about the membrane. Microtechnique has been commonly used
to characterise the structure and morphology of the untreated and treated mem-
branes. Microtechniques include Scanning Electron Microscopy (SEM), Atomic
Force Microscopy (AFM) and so on.

5.9 Scanning Electron Microscopy (SEM)

SEM has been considered as a powerful characterisation tool used commonly by

many researchers to characterise membrane properties quantitatively (i.e. porosity,
pore size, pore shape, and pore density) and qualitatively (i.e. visual or direct
observation). It has been practically used for 30 years and many innovations and
advancement are continuously added to it. Many journal articles have been pub-
lished on using SEM to characterise membrane surface properties (PES or PVDF
membranes) including porosity, pore size, pore size distribution, pore density, pore
shape, surface roughness and fouling (Liu et al. 2009b; Mu and Zhao 2009;
Mansourpanah et al. 2009a, b, 2010; Mosqueda-Jimenez et al. 2004; Zhao et al.
2011a, b; Razmjou et al. 2011; Kochan et al. 2010; Dejeu et al. 2009; Rahimpour
2011; Rahimpour et al. 2008; Yi et al. 2010a, b; Wei et al. 2012; Li et al. 2005;
Peeva et al. 2012). SEM has advantages and limitations. The advantages are: 1)
characterise the membrane by providing practical and direct structural information
about the membrane, leading to impressive analytical output. Thus, SEM has
become a powerful technique of characterisation not only for research but also for
quality and product. The limitations of SEM are: (1) SEM is extremely restricted to
examine very small area (2) SEM requires the membrane samples to be dried before
testing. In some samples, drying generates undesirable structure collapse. (Mu and
Zhao 2009) used thermal-induced surface cross-linking method to modify PES
porous membranes. They used poly (ethylene glycol) diacrylate (PEGDA) (hy-
drophilic additive) as hydrophilic modifier. Characterising the morphology of PES
membranes is conducted by SEM as present schematically in Fig. 5.3.
5.9 Scanning Electron Microscopy (SEM) 137

Fig. 5.3 SEM images of the pristine and modified PES membranes: a pristine PES membrane;
b–d the modified PES membranes with the mass gain of 115.4, 253.1, 345.6 lg/cm2, respectively.
(1) denotes the separation surface, (2) is the cross-section (Mu and Zhao 2009)
138 5 Membrane Characterization Techniques

As can be seen from Fig. 5.3, pristine PES membrane (A1) showed a micro-
filtration porous surface. The pore size of membrane surface is (0.2–0.4 lm) and
the cross-section (A2) of PES membrane typically showed network structure. After
membrane modification, the cross-linker modifier PEGDA decreases the pore size
on surface of membrane. Increasing mass gain (115.4, 253.1, 345.6 lg/cm2) leads
to the gradual decrease of both pore size and number because of the coverage of
cross-linking layer. No pore is approximately noted on the surface of the membrane
when the mass gain value is 345.6 µg/cm2. No pronounced difference is found in
the cross-section morphologies between neat PES membranes (A1) and the treated
PES membranes (B2, C2) with lower mass gains. However, with higher mass gain,
the cross-section morphology of the treated PES membrane (D2) looks to be denser,
indicating that the modification may reach membrane bulk.
In another research study, (Rahimpour et al. 2008) modified PES with TiO2
nanoparticles using UV irradiation method. Scanning electron microscopy was
conducted to characterise membrane properties (i.e. pore size and porosity). They
concluded that porosity and pore size of the treated PES membrane was higher than
the virgin PES membrane.
Field emission scanning electron microscopy (FESEM) is another analytical
technique used to investigate the structures of the molecular surface. In membranes,
due to higher resolution than other microscopic techniques (e.g. SEM), it is also
used to inspect membrane surface (e.g. surface porosity, pore size and its distri-
bution) and cross-sectional morphologies (Bolong et al. 2009). The cross-sectional
regions of membranes can be prepared by fracturing the membranes in liquid
nitrogen. Then, samples were mounted either onto the plate of the specimen sample
holder (stub) (for surface observation) or side stage of the specimen sample holder
(for cross-section observation) using conductive double side tape, then sputter
coated the samples with different coating metals (platinum, gold, iridium and
gold-palladium). The coated samples were scrutinised using FESEM with different
resolution and different magnification.
Conversely, Transmission Electron Microscopy (TEM) is another technique
used to inspect finer detail even as small than a single column of atoms. In
membrane, it is seldom utilised to characterise PES membranes after modifications.
The advantage of TEM is its outstandingly higher resolution (less than 1 nm level).

5.10 Atomic Force Microscopy

Atomic force microscopy (AFM) is a versatile tool used to characterise the surfaces
physically. It is a form of scanning probe microscopy (SPM) with a very high
resolution; up to the order of fractions of a nanometer and it is more than 1000 times
better than the optical diffraction limit. The AFM is considered as one of the
5.10 Atomic Force Microscopy 139

foremost tools for imaging, measuring, and manipulating matter at the nano-scale.
In the membrane, AFM has been used to characterise ultrafiltration membranes and
to a lesser degree characterise microfiltration membranes. AFM is also used to
measure the pore size, porosity, pore size distribution, aggregate size and nodule
size at the membrane surface. In recent years, AFM was also used to study the
adhesion properties of membrane surfaces using force measurement (force mode).
And colloidal probe technique to quantify the interaction force acting between

Fig. 5.4 AFM topography, phase image, and cross-sectional roughness of thin-film composites
by interfacial polymerization: a virgin PES membrane, b film composite with PVA, c film
composite with PEG, and d film composite with chitosan. The root mean square roughness is
(a) 2.1 nm, (b) 1.2 nm, (c) 1.5 nm, and (d) 2.0 nm. Image size was 2
2 µm (Liu et al. 2009a)
140 5 Membrane Characterization Techniques

surface and probe is used, in which micrometre-sized spheres are attached to the
AFM cantilever. Hydrophilic membranes are strongly interacting with hydrophilic
probe as indicated by a large phase shift, whereas the hydrophobic membranes give
only a small phase shift (Rana and Matsuura 2010).
There are three modes to operate AFM: (1) contact mode (static mode) (2) tap-
ping mode (3) noncontact mode. Tapping and noncontact mode (which are also
called dynamic modes) are usually used to characterise the surface topography and
phase image of PES membranes (Mansourpanah et al. 2009a, 2010; Razmjou et al.
2011; Liu et al. 2009a; Abu Seman et al. 2010; Rahimpour 2011; Wu and Yang
2006; Tur et al. 2012).
Liu et al. (2009a) grafted PES membranes by three hydrophilic polymers
(Polyvinyl alcohol (PVA), Polyethylene glycol (PEG) and chitosan) through
interfacial grafting technique; then they characterise the virgin and modified PES
membranes by AFM (see Fig. 5.4). As presented in Fig. 5.4, pristine PES mem-
branes clearly exhibited ridge-and-valley structure. The bar indicated the vertical
deviations in the surface of membrane, so the white area represents the highest
level, whilst the dark region represents the lowest level. PES membrane surface
seemed to be heterogeneous (not homogenous), while the surface-modified PES
membranes showed more or less surface roughness than the pristine PES
membrane.
Low et al. (2014) synthesised two-dimensional zeolitic imidazolate framework
with leaf-shaped morphology (ZIF-L) and blend it with PES UF membranes. AFM
test was conducted to verify the effects of ZIF-L on the roughness of modified
membranes. The results showed that the roughness values in the projected area of
1
1 lm decreased from 5.99 to 3.55 nm as 0.5 % of ZIF-L was added to the
casting solution. It was well documented that lower surface roughness lead to
higher antifouling properties, as foulants were likely to be absorbed in the valleys of
the membranes with rough surface (Vrijenhoek et al. 2001).

5.11 Characterization of Membrane Performance

Characterization of membrane performance after surface modification is paramount.

The characteristics of modified membranes include hydrophilicity/hydrophobicity,
permeability (flux) and selectivity, antifouling properties and so forth.

5.12 Hydrophilicity/Hydrophobicity of Membranes

Hydrophilicity is one of the most important aspects to characterise membrane

performance. Water contact angle measurement is widely used to assess the
hydrophilicity and the wetting properties of the membrane surface. However, the
measurement value cannot accurately act as the indicator comparing different
5.12 Hydrophilicity/Hydrophobicity of Membranes 141

membranes as this value does not solely rely on surface hydrophilicity but also
porosity, surface roughness, pore size and pore size distribution of the membranes
(Rana and Matsuura 2010). Nevertheless, the static contact angle changes with the
age of the water drop which can be a better index for surface hydrophilicity (Zhao
et al. 2008c). Clearly, the higher hydrophilic porous membrane not only has a
smaller water contact angle but also a rapid decrease rate of static contact angle.
The techniques that are used to measure contact angle include statistic sessile drop
method (Mansourpanah et al. 2009a, 2010; Zhao et al. 2011a; Cao et al. 2010;
Bolong et al. 2009; Liu et al. 2009a; Pieracci et al. 1999; Rahimpour et al. 2008; Yi
et al. 2010a; Wei et al. 2012; Pazokian et al. 2011) and captive air bubble technique
(Pieracci et al. 1999; Tur et al. 2012). To ensure the accuracy, several determina-
tions at different locations were tested for each membrane sample and an average
was taken.
Many researchers have been used as contact angle measurement in their study to
investigate the hydrophilicity of PES membranes (Mu and Zhao 2009;
Mansourpanah et al. 2009a, b, 2010; Mosqueda-Jimenez et al. 2006; Van der
Bruggen 2009; Zhao et al. 2011a, b; Bolong et al. 2009; Chu et al. 2005; Liu et al.
2009a; Pieracci et al. 1999; Rahimpour et al. 2008; Gaina et al. 2011; Liu and Kim
2011; Wu and Yang 2006; Wei et al. 2012; Yi et al. 2010a; Tur et al. 2012;
Pazokian et al. 2011). They concluded that introduction of hydrophilic components
into PES membrane could decrease the water contact angles. However, many
researchers noted that the contact angles kept changing after the water was dropped
on the PES membrane surface. (Bolong et al. 2009) attribute it to evaporation effect
and recommended that the measurements should be made as faster as possible (less
than 10 s) to reduce evaporation effect. (Mu and Zhao 2009) also observed that the
water contact angle of the virgin PES membrane was significantly declined from
about 89 °C at the drop time of 0th second to 66 °C at 185th seconds. They
ascribed this phenomenon to the permeation of water drop into membrane pore.

5.13 Permeability and Selectivity of Membranes

The permeability of membrane is very crucial step after modification of membranes,

which many researchers are preferred. The permeation of modified membranes is
often verified by measurement of water (flux) or measurement of gas flux (Susanto
and Ulbricht 2007; Mansourpanah et al. 2009a, b, 2010; Mosqueda-Jimenez et al.
2006; Van der Bruggen 2009; Zhao et al. 2011a, b; Chu et al. 2005; Pieracci et al.
1999; Saha et al. 2009; Rahimpour 2011; Rahimpour et al. 2008; Wei et al. 2012;
Peeva et al. 2012; Tur et al. 2012). The alteration and recovery of water perme-
ability for stimulus-response membranes were also conducted under various envi-
ronmental stimuli (e.g. ionic strength, pH, temperature).
142 5 Membrane Characterization Techniques

To obtain steady flux, the membrane must be pre-compacted first by DDI water
for at least 1 h before calculation flux to completely make sure the water is
immersed into the membranes (Zhao et al. 2011b). Constant transmembrane
pressure mode is usually used to determine the membrane permeation.
Polyethylene glycols (PEGs) with different molecular weights (e.g.
20,35,100,200,300,400 KDa and so on), poly (ethylene oxide) with different
molecular weights or bovine serum albumin (BSA) are commonly three-marker
macromolecule used to characterise the selectivity of the polymeric membranes
(Mu and Zhao 2009; Pieracci et al. 1999; Yi et al. 2010b; Huang et al. 2011). They
also used to determine the solute rejection and molecular weight cut-off (MWCO).
MWCO of membranes is the lowest molecular weight of the marker macromolecule
(e.g. PEG) at a rejection of 90 % in the measurements. Pre-size of membranes is
determined based on the MWCO using the following equation.
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
g
r ¼ 0:026 nm MWCOð Þ  0:03 nm
gmol

5.14 Antifouling Properties

Membrane fouling is a repugnant problem in all membrane processes, particularly

membrane bioreactors. Therefore, the modification of membranes is very important
step toward increasing the antifouling properties of membranes. Moreover, char-
acterisation of antifouling properties after surface modification is very necessary.
Flux and BSA (foulant) decline highlights the severity of antifouling. Thus, flux
and protein are solute used as index for antifouling property (Mu and Zhao 2009;
Pieracci et al. 1999; Yi et al. 2010b; Huang et al. 2011). Therefore, antifouling
properties of membranes are related to the nature of material, surface hydrophilicity,
surface charge and the roughness of membrane surface. As a general rule, mem-
branes with higher hydrophilic and smoother surface usually have higher
antifouling property. Furthermore, in some cases, static BSA adsorption test was
also conducted to figure out the amount of protein adsorbed onto membrane surface
after modification and to verify the improvement of antifouling property (Yi et al.
2010b). Static protein adsorption could also be used for evaluating membrane blood
compatibility.

5.15 Anticoagulation Properties of Membranes

After modify PES membrane to improve its surface, characterisation of anticoag-

ulation and other biological properties is necessary because PES has been widely
used in various application, particularly biomedical field and wastewater treatment.
5.15 Anticoagulation Properties of Membranes 143

Plasma recalcification time (PRT), thromboplastic time (APTT), activated partial

prothrombin time (PT) and the whole blood clotting time (WBCT) are frequently
used as anticoagulation indices (Li et al. 2010, 2012; Zhao et al. 2011b; Huang
et al. 2011). Additionally, albumin, cytocompatibility, platelet adhesion and fibrin
adsorption are also biological indices used as biomaterials for modified PES
membranes.

5.16 Membrane Stability

Membrane stability is a very important aspect after membrane modification. Long

lifetime of the treated membrane during usage or application is the concern of many
researchers to verify whether the modification process is applicable. Surprisingly,
few research studies have been conducted on the stability of membrane after surface
modification.

5.17 Stability After Physical Modification of PES

Membrane

Yi et al. (2011) examined the stability of the modified PES membranes by washing
them with water at temperature 60 °C for period 75 days after modification of
polyethersulfone membranes with poly (propylene glycol) (PPG) (1000, 4000 and
8000 KDa). The stability of poly (propylene glycol) in membranes is confirmed by
contact angle measurements. Two reasons have been suggested for the stability of
PPG group into polymeric PES membrane: First, due to the characteristic of PPG
(e.g. homopolymer, insoluble in water, Mw = 740 g/gmol), PPG is remained in
membranes when membranes contact with water. The second reason is the good
interaction (compatibility) between PES and PPG due to the bulky hydrophobic
groups of PPG, which is assumed to be responsible for this interaction when the
amphiphilic polymer PPG is added to the dope solution. Furthermore, the solubility
parameters of PPG and PES are approximate (19.9 (MPa)0.5 and 20.7 (MPa)0.5
respectively) and this approximate solubility parameter will lead to effective
interaction between PPG and PES when they are blended into membranes (Sung
and Lin 1997; Niemelä et al. 1996; Yi et al. 2011).
Susanto and Ulbricht (2009) scrutinised the stability of the hydrophilic additives
(PEG, PVP, pluronic) in the polymeric PES membrane network by washing the
modified membranes physically in water at temperatures 20 and 40 °C and
chemically in sodium hypochlorite solution (400 mg/L) for 10 days. As shown in
Fig. 5.5, contact angle measurement showed that there is a significant increase in
water contact angle of PES when PEG is used, indicating that PEG has thoroughly
low stability in membranes. The reason for that is PEG is homopolymer,
water-soluble polymer and can be leached out from the hydrophobic PES
144 5 Membrane Characterization Techniques

Fig. 5.5 Stability investigated by measuring the contact angle as a function of time (Susanto and
Ulbricht 2009)

membranes during phase inversion process. (Susanto and Ulbricht 2009) also
observed that IR absorbance for all the additives is slightly decreased (PEG, PVP,
pluronic) as presented in Fig. 5.6. As it can be seen none of the additives above was
entirely stable in the PES membrane. However, irrespective this loss, significant
surface modification could still be seen as noted by either the existence of new peak
5.17 Stability After Physical Modification of PES Membrane 145

Fig. 5.6 Stability test investigated by measuring the IR absorbance of hydrophilic functional
additive as a function of incubating time (Susanto and Ulbricht 2009)
146 5 Membrane Characterization Techniques

for PES–PVP or increase in transmittance for PES–PEG and PES–Pluronic even

after incubating for 10 days in all studied potential cleaning agents.

5.18 Stability After Chemical Modification of PES

Membrane

Wei et al. (2012) modified PES membranes using CF4 plasma process. Then, the
stability of the surface-treated PES hollow fibre membrane was scrutinised. A direct
contact membrane distillation experiment was conducted using hot salt solution
(NaCl) as feed at temperature 60.5 °C. The membrane module was tested in total
54 h for 9 days, 6 h per day. During the test period, the membrane module was in
contact with both feed and distillate. As can be seen in Fig. 5.7 the evaluation of
long life stability membrane showed that the membrane permeation (water flux) is
approximately stable and salt rejection was nearly 100 %.
Schulze et al. (2012) modified different types of polymer PES, PVDF, poly-
sulfone and polyacrylonitrile membranes with aqueous solution of small molecules
(having hydrophilic groups, e.g. sulfonic acid, carboxylic acid, phosphonic acid,
alcohols, amine and zwitterionic components) and treated by low-energy electron
beam ion approach. The high stability of the modification showed permanent
membrane functionalities that are chemically attached.
Susanto and Ulbricht (2007) prepared polymeric PES membranes with high
antifouling-resistant. Two hydrophilic monomers including poly (ethylene glycol)
methacrylate (PEGMA) and N,N-dimethyl-N-(2-methacryloyloxyethyl-N-
(3-sulfopropyl) ammonium betaine (SPE), with and without using cross-linker
monomer (N,N′-methylene bisacrylamide) (MBAA) have been grafted onto PES
membranes using photografting method. The stability of the grafted monomer was
evaluated chemically in sodium hypochlorite solution (NaOCl) (chemical agent).

Fig. 5.7 Stability

performance of the
surface-modified PES hollow
fiber membrane. Hot NaCl
solution: 4 wt% NaCl,
temperature 60.5 ± 0.2 °C,
2.0 m/s. Cold distillate water:
20 ± 0.5 °C, 0.68 m/s
(Wei et al. 2012)
5.18 Stability After Chemical Modification of PES Membrane 147

Fig. 5.8 Normalized

absorbance intensity (by
subtracting the absorbance
of the base membrane) at
wave numbers of 1725 cm−1
for PEGMA- and 1727 cm−1
for SPE-modified PES
membranes after soaking in
sodium hypochlorite solution
(Susanto and Ulbricht 2007)

As shown in Fig. 5.8, ATR-IR absorbance for the introduced ester groups (relative
to groups in the PES backbone) remained constant after incubating for certain
period. (Susanto and Ulbricht 2007) also stated that such results are also verified by
measurements of contact angle and by elemental analyses (XPS). Furthermore,
(Susanto and Ulbricht 2007) argued that although numerous research studies had
stated previously that NaOCl could degrade the polymeric polysulfone or
polyethersulfone polymeric membranes, the results of their study research obvi-
ously indicated that either no loss or hydrolysis of the grafted monomer layers
happened within 8 days, verifying that the active layer of the photografted com-
posite membranes is chemically stable.

References

Abu Seman MN, Khayet M, Bin Ali ZI, Hilal N (2010) Reduction of nanofiltration membrane
fouling by UV-initiated graft polymerization technique. J Membr Sci 355(1–2):133–141
Bolong N, Ismail AF, Salim MR, Rana D, Matsuura T (2009) Development and characterization of
novel charged surface modification macromolecule to polyethersulfone hollow fiber membrane
with polyvinylpyrrolidone and water. J Membr Sci 331(1–2):40–49
Brayfield CA, Marra KG, Leonard JP, Tracy Cui X, Gerlach JC (2008) Excimer laser channel
creation in polyethersulfone hollow fibers for compartmentalized in vitro neuronal cell culture
scaffolds. Acta Biomater 4(2):244–255. doi:10.1016/[Link].2007.10.004
Cao X, Tang M, Liu F, Nie Y, Zhao C (2010) Immobilization of silver nanoparticles onto
sulfonated polyethersulfone membranes as antibacterial materials. Colloids Surf, B 81(2):555–
562. doi:10.1016/[Link].2010.07.057
Chu LY, Wang S, Chen WM (2005) Surface modification of ceramic-supported polyethersulfone
membranes by interfacial polymerization for reduced membrane fouling. Macromol Chem
Phys 206(19):1934–1940
Dejeu J, Lakard B, Fievet P, Lakard S (2009) Characterization of charge properties of an
ultrafiltration membrane modified by surface grafting of poly(allylamine) hydrochloride.
J Colloid Interface Sci 333(1):335–340. doi:10.1016/[Link].2008.12.069
148 5 Membrane Characterization Techniques

Fontyn M, Bijsterbosch B, Van’t Riet K (1986a) Chemical characterization of ultrafiltration

membranes by spectroscopic techniques. J Membr Sci 36:141–145
Fontyn M, Bijsterbosch B, Van’t Riet K (1986b) Chemical characterization of ultrafiltration
membranes by spectroscopic techniques. J Membr Sci 36:141–145
Gaina C, Gaina V, Ionita D (2011) Chemical modification of chloromethylated polysulfones via
click reactions. Polym Int 60(2):296–303. doi:10.1002/pi.2948
Hester JF, Banerjee P, Mayes AM (1999) Preparation of protein-resistant surfaces on poly
(vinylidene fluoride) membranes via surface segregation. Macromolecules 32(5):1643–1650
Huang J, Xue J, Xiang K, Zhang X, Cheng C, Sun S, Zhao C (2011) Surface modification of
polyethersulfone membranes by blending triblock copolymers of methoxyl poly(ethylene
glycol)-polyurethane-methoxyl poly(ethylene glycol). Colloids Surf, B 88(1):315–324. doi:10.
1016/[Link].2011.07.008
Kochan J, Wintgens T, Wong JE, Melin T (2010) Properties of polyethersulfone ultrafiltration
membranes modified by polyelectrolytes. Desalination 250(3):1008–1010. doi:10.1016/[Link].
2009.09.092
Li Y, Chung TS, Kulprathipanja S (2005) Enhanced gas separation performance in polyether-
sulfone (Pes)-modified zeolite mixed matrix membranes. In: Proceedings of AIChE annual
meeting conference, p 2062
Li L, Yin Z, Li F, Xiang T, Chen Y, Zhao C (2010) Preparation and characterization of poly
(acrylonitrile-acrylic acid-N-vinyl pyrrolidinone) terpolymer blended polyethersulfone mem-
branes. J Membr Sci 349(1–2):56–64
Li L, Xiang T, Su B, Li H, Qian B, Zhao C (2012) Effect of membrane pore size on the
pH-sensitivity of polyethersulfone hollow fiber ultrafiltration membrane. J Appl Polym Sci 123
(4):2320–2329. doi:10.1002/app.34902
Lin X, et al (2015) Composite ultrafiltration membranes from polymer and its quaternary
phosphonium-functionalized derivative with enhanced water flux. J Membr Sci 482:67–75
Liu SX, Kim JT (2011) Characterization of surface modification of polyethersulfone membrane.
J Adhes Sci Technol 25(1–3):193–212. doi:10.1163/016942410X503311
Liu SX, Kim JT, Kim S, Singh M (2009a) The effect of polymer surface modification via
interfacial polymerization on polymer-protein interaction. J Appl Polym Sci 112(3):1704–
1715. doi:10.1002/app.29606
Liu Z, Deng X, Wang M, Chen J, Zhang A, Gu Z, Zhao C (2009b) BSA-modified
polyethersulfone membrane: preparation, characterization and biocompatibility. J Biomater
Sci Polym Ed 20(3):377–397. doi:10.1163/156856209X412227
Low Z-X, Razmjou A, Wang K, Gray S, Duke M, Wang H (2014) Effect of addition of
two-dimensional ZIF-L nanoflakes on the properties of polyethersulfone ultrafiltration
membrane. J Membr Sci 460:9–17. doi:10.1016/[Link].2014.02.026
Mansourpanah Y, Madaeni SS, Adeli M, Rahimpour A, Farhadian A (2009a) Surface modification
and preparation of nanofiltration membrane from polyethersulfone/polyimide blend-use of a
new material (polyethyleneglycol-triazine). J Appl Polym Sci 112(5):2888–2895. doi:10.1002/
app.29821
Mansourpanah Y, Madaeni SS, Rahimpour A, Farhadian A, Taheri AH (2009b) Formation of
appropriate sites on nanofiltration membrane surface for binding TiO2 photo-catalyst:
performance, characterization and fouling-resistant capability. J Membr Sci 330(1–2):297–306
Mansourpanah Y, Madaeni SS, Rahimpour A, Kheirollahi Z, Adeli M (2010) Changing the
performance and morphology of polyethersulfone/polyimide blend nanofiltration membranes
using trimethylamine. Desalination 256(1–3):101–107. doi:10.1016/[Link].2010.02.006
Millesime L, Amiel C, Chaufer B (1994) Ultrafiltration of lysozyme and bovine serum albumin
with polysulfone membranes modified with quaternized polyvinylimidazole. J Membr Sci J
Membr Sci 89:223–234
Mosqueda-Jimenez DB, Narbaitz RM, Matsuura T (2004) Manufacturing conditions of
surface-modified membranes: effects on ultrafiltration performance. Sep Purif Technol 37
(1):51–67. doi:10.1016/[Link].2003.07.003
References 149

Mosqueda-Jimenez DB, Narbaitz RM, Matsuura T (2006) Effects of preparation conditions on the
surface modification and performance of polyethersulfone ultrafiltration membranes. J Appl
Polym Sci 99(6):2978–2988. doi:10.1002/app.22993
Mu LJ, Zhao WZ (2009) Hydrophilic modification of polyethersulfone porous membranes via a
thermal-induced surface crosslinking approach. Appl Surf Sci 255(16):7273–7278. doi:10.
1016/[Link].2009.03.081
Niemelä S, Leppänen J, Sundholm F (1996) Structural effects on free volume distribution in glassy
polysulfones: molecular modelling of gas permeability. Polymer 37(18):4155–4165. doi:10.
1016/0032-3861(96)00241-8
Pazokian H, Jelvani S, Mollabashi M, Barzin J, Azizabadi Farahani G (2011) ArF laser surface
modification of polyethersulfone film: Effect of laser fluence in improving surface biocom-
patibility. Appl Surf Sci 257(14):6186–6190. doi:10.1016/[Link].2011.02.028
Peeva PD, Million N, Ulbricht M (2012) Factors affecting the sieving behavior of anti-fouling
thin-layer cross-linked hydrogel polyethersulfone composite ultrafiltration membranes.
J Membr Sci 390–391:99–112
Pieracci J, Crivello JV, Belfort G (1999) Photochemical modification of 10 kDa polyethersulfone
ultrafiltration membranes for reduction of biofouling. J Membr Sci 156(2):223–240
Rahimpour A (2011) UV photo-grafting of hydrophilic monomers onto the surface of nano-porous
PES membranes for improving surface properties. Desalination 265(1–3):93–101
Rahimpour A, Madaeni SS, Taheri AH, Mansourpanah Y (2008) Coupling TiO2 nanoparticles
with UV irradiation for modification of polyethersulfone ultrafiltration membranes. J Membr
Sci 313(1–2):158–169
Rana D, Matsuura T (2010) Surface modifications for antifouling membranes, Chem. Rev.
110:2448–2471
Razmjou A, Mansouri J, Chen V (2011) The effects of mechanical and chemical modification of
TiO2 nanoparticles on the surface chemistry, structure and fouling performance of PES
ultrafiltration membranes. J Membr Sci 378(1–2):73–84
Saha NK, Balakrishnan M, Ulbricht M (2009) Fouling control in sugarcane juice ultrafiltration
with surface modified polysulfone and polyethersulfone membranes. Desalination 249
(3):1124–1131. doi:10.1016/[Link].2009.05.013
Schulze A, Marquardt B, Went M, Prager A, Buchmeiser MR (2012) Electron beam-based
functionalization of polymer membranes. Water Sci Technol 65(3):574–580. doi:10.2166/wst.
2012.890
Sung PH, Lin CY (1997) Polysiloxane modified epoxy polymer network—II. Dynamic
mechanical behavior of multicomponent graft-IPNs (epoxy/polysiloxane/polypropylene gly-
col). Eur Polymer J 33(3):231–233
Susanto H, Ulbricht M (2007) Photografted thin polymer hydrogel layers on PES ultrafiltration
membranes: characterization, stability, and influence on separation performance. Langmuir 23
(14):7818–7830
Susanto H, Ulbricht M (2009) Characteristics, performance and stability of polyethersulfone
ultrafiltration membranes prepared by phase separation method using different macromolecular
additives. J Membr Sci 327(1–2):125–135. doi:10.1016/[Link].2008.11.025
Tur E, Onal-Ulusoy B, Akdogan E, Mutlu M (2012) Surface modification of polyethersulfone
membrane to improve its hydrophobic characteristics for waste frying oil filtration: radio
frequency plasma treatment. J Appl Polym Sci 123(6):3402–3411. doi:10.1002/app.34400
Van der Bruggen B (2009) Comparison of redox initiated graft polymerisation and sulfonation for
hydrophilisation of polyethersulfone nanofiltration membranes. Eur Polymer J 45(7):1873–
1882. doi:10.1016/[Link].2009.04.017
Vrijenhoek EM, Hong S, Elimelech M (2001) Influence of membrane surface properties on initial
rate of colloidal fouling of reverse osmosis and nanofiltration membranes. J Membr Sci 188
(1):115–128. doi:10.1016/S0376-7388(01)00376-3
150 5 Membrane Characterization Techniques

Wei X, Zhao B, Li XM, Wang Z, He BQ, He T, Jiang B (2012) CF 4 plasma surface modification
of asymmetric hydrophilic polyethersulfone membranes for direct contact membrane
distillation. J Membr Sci 407–408:164–175. doi:10.1016/[Link].2012.03.031
Wu TM, Yang SH (2006) Surface characterization and barrier properties of plasma-modified
polyethersulfone/layered silicate nanocomposites. J Polym Sci, Part B: Polym Phys 44
(22):3185–3194. doi:10.1002/polb.20961
Yi Z, Zhu LP, Xu YY, Li XL, Yu JZ, Zhu BK (2010a) F127-based multi-block copolymer
additives with poly(N, N-dimethylamino-2-ethyl methacrylate) end chains: the hydrophilicity
and stimuli-responsive behavior investigation in polyethersulfone membranes modification.
J Membr Sci 364(1–2):34–42. doi:10.1016/[Link].2010.07.045
Yi Z, Zhu LP, Xu YY, Zhao YF, Ma XT, Zhu BK (2010b) Polysulfone-based amphiphilic
polymer for hydrophilicity and fouling-resistant modification of polyethersulfone membranes.
J Membr Sci 365(1–2):25–33. doi:10.1016/[Link].2010.08.001
Yi Z, Zhu L, Xu Y, Jiang J, Zhu B (2011) Polypropylene glycol: the hydrophilic phenomena in the
modification of polyethersulfone membranes. Ind Eng Chem Res 50(19):11297–11305. doi:10.
1021/ie201238c
Zhang J, Zhang M, Zhang K (2014) Fabrication of poly(ether sulfone)/poly(zinc acrylate)
ultrafiltration membrane with anti-biofouling properties. J Membr Sci 460:18–24
Zhao C, Xue J, Ran F, Sun S (2013a) Modification of polyethersulfone membranes—a review of
methods. Prog Mater Sci 58(1):76–150
Zhao W, He C, Wang H, Su B, Sun S, Zhao C (2011a) Improved antifouling property of
polyethersulfone hollow fiber membranes using additive of poly(ethylene glycol) methyl
ether-b-poly(styrene) copolymers. Ind Eng Chem Res 50(6):3295–3303. doi:10.1021/
ie102251v
Zhao W, Huang J, Fang B, Nie S, Yi N, Su B, Li H, Zhao C (2011b) Modification of
polyethersulfone membrane by blending semi-interpenetrating network polymeric nanoparti-
cles. J Membr Sci 369(1–2):258–266
Zhao, Yong-Hong, Qian, Yan-Ling, Zhu, Bao-Ku, et al (2008c) ‘Modification of porous poly
(vinylidene fluoride) membrane using amphiphilic polymers with different structures in phase
inversion process’, J Membr Sci 310(1–2):567–76