HOWARD UNIVERSITY

Integrated Nano-Composite Membranes for

Biological and Organic Fouling Prevention

A Thesis
Submitted to the Faculty of the
Graduate School
of

HOWARD UNIVERSITY

in partial fulfillment of
the requirements for
the degree of

MASTER OF ENGINEERING

Department of Civil Engineering

by

Fatou N. Diagne

Washington, D.C.
August 2009

UMI Number: 1465280

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HOWARD UNIVERSITY
GRADUATE SCHOOL
DEPARTMENT OF CIVIL ENGINEERING

THESIS COMMITTEE

John P. Tharakan, Ph.D.

Graduate Professor
Chairperson

Kimberly L. Jones, Ph.D.

Graduate Associate Professor

Ahlam Shalaby, Ph.D.

Graduate Associate Professor

Kimberly L. Jones, Ph.D.

Graduate Associate Professor
Thesis Advisor

Candidate:

Fatou N. Diagne

Date of Defense: May 28, 2009

ii

ACKNOWLEDGMENT
I am indebted to many people who contributed to my education in general and to
this thesis research in particular.
I would like to thank my parents for making me the individual that I am and for
assisting me through school since kindergarten. My brother and sisters have also
provided me with invaluable emotional and spiritual support throughout this journey.
I am very grateful for the time, support, expertise and assistance received from the
Howard University Civil Engineering Department during my undergraduate and graduate
programs especially my thesis advisor Dr. Kimberly Jones, Dr. Ramamoorthy Malaisamy,
Research Associate, Dr. Shalaby and Dr. Tharakan, committee members and Ms. Lily
Wan, Research Associate.
Drs. Mitchell and Eribo from respectively the Department of Chemical
Engineering and the Department of Biology and their groups have been instrumental to
this research. Special thanks to Andy Hai-Ting and Vic Boddie for their assistance.
Finally, Thanks to my family and friends for their support and prayers.

iii

ABSTRACT
Our goal is to modify commercially available polyethersulfone (PES) membranes
with a pore size of 0.1 m in order to achieve both organic fouling and biofouling
prevention. The PES membranes were modified by the standard polyelectrolyte
multilayer

modification

method;

layers

of

polystyrenesulfonate

(PSS),

poly(diallyldimethylammonium chloride) (PDADMAC) and silver nanoparticles capped

with PSS were alternatively assembled by electrostatic deposition. Multilayers of
PDADMAC and PSS (PSS as the top layer) create a negative charge on the membrane
surface, thereby potentially increasing the electrostatic repulsion between the membrane
surface and foulants. The hydrophilic nature of the PSS increases the hydrophilicity of
the membrane, while capping silver nanoparticles onto multilayers of PDADMAC and
PSS imparts biocidal characteristics to the virgin membrane. Films were kept thin (1.5 bilayers of polyelectrolyte) in order to minimize the flux decline resulting from the
increased thickness of the modified membranes. Each layer added a thickness of about 10
nm resulting in an added thickness of 30 nm for each modified membrane. Aqueous
solutions of humic acid (20 mg/L) and of Escherichia coli (E.coli suspension (106
CFU/mL) were filtered separately through both the virgin and modified PES membranes
under stirred, batch microfiltration conditions. Filtration and cleaning studies confirm that
the modification reduces the organic and biological fouling of the commercially available
membranes and increases the flux recovery by 6.4 and 16.5 percent respectively for the
membrane modified with and without nanoparticles after cleaning with 0.2 M of sodium
hydroxide (NaOH) for the organic fouling and by 8.5 and 11.8 percent respectively for
the membranes modified with and without nanoparticles after cleaning with 200 ppm of

iv

sodium hypochlorite (NaOCl) for the biological fouling. The results show an increase in
inherent membrane resistance (Rm), as evidenced by the lower initial permeability and
flux of the modified membranes. Zeta potential measurements confirm the increased
charge at the surface of the modified membranes; such an increase is indirectly
proportional to the reduction in fouling with the more negatively charged membranes
fouling less. SEM characterization confirmed that the silver nanoparticles are evenly
embedded on the polyelectrolyte film surface with diameter on the order of 50nm; FTIR
spectra confirmed the chemical modification of the membranes.

TABLE OF CONTENTS
THESIS COMMITTEE ...................................................................................................... ii
ACKNOWLEDGMENTS ................................................................................................. iii
ABSTRACT....................................................................................................................... iii
LIST OF TABLES ........................................................................................................... viii
LIST OF FIGURES ........................................................................................................... ix
CHAPTER 1: INTRODUCTION ........................................................................................1
1.1 Problem definition .........................................................................................................1
1.2 Research Objectives & Approach ..................................................................................4
CHAPTER 2: BACKGROUND AND REVIEW OF LITERATURE ................................6
2.1 Background ....................................................................................................................6
2.2 Literature review ............................................................................................................7
2.2.1 Polyelectrolyte Multilayer Modification............................................................ 7
2.2.2 Natural Organic Matter (Humic acid) Fouling ................................................ 10
2.2.3 Biofouling ........................................................................................................ 12
2.2.4 Silver Nanoparticle as an Antimicrobial Agent ............................................... 14
CHAPTER 3: MATERIALS AND METHODS ...............................................................16
3.1 Materials ......................................................................................................................16
3.1.1 PES Membranes ............................................................................................... 16
3.1.2 Humic Acid Solution ...................................................................................... 16
3.1.3 E.coli Suspension ............................................................................................ 16
3.1.4 Polyelectrolytes ................................................................................................ 16
3.1.5 Silver Nanoparticles ......................................................................................... 16
3.2 Modification process ....................................................................................................19
3.3 Membrane characterization ..............................................................................21
3.3.1 Zeta Potential Measurements ........................................................................... 21
3.3.2 Surface Characterization FTIR-SEM ........................................................... 21
vi

3.4 Flux Experiments .........................................................................................................21

3.4.1 Filtration Setup ................................................................................................ 21
3.4.2 Filtration Protocol ........................................................................................... 21
3.4.3 Filtration Analysis ............................................................................................ 21
CHAPTER 4: RESULTS AND DISCUSSION.................................................................26
4.1 Characterization of PES membranes ...........................................................................26
4.1.1 SEM-FTIR ...................................................................................................... 26
4.1.2 Zeta Potential Measurement ............................................................................ 27
4.2 Filtration Studies .........................................................................................................29
4.2.1 Flux .................................................................................................................. 29
4.2.2 Flux Decline ..................................................................................................... 32
4.2.3 Resistances ....................................................................................................... 33
CHAPTER 5: CONCLUSION AND RECOMMENDATIONS .......................................36
5.1 Conclusion ...................................................................................................................36
5.2 Recommendations ........................................................................................................38
REFERENCES ..................................................................................................................39

vii

LIST OF TABLES
4.1

Pure Water Flux of membranes of Flux of membranes throughout

Organic fouling experiments; Units for PWF are ml/cm2/min .30

4.2

Pure Water Flux of membranes throughout biofouling experiments;

Units for PWF are ml/cm2/min .....31

4.3

Membrane Resistances throughout the organic fouling experiment.

VM- Virgin membrane; MM- modified membrane;
MM(NP) - Modified with nanoparticles............................................................34

4.4

Membrane Resistances throughout the biofouling experiment.

VM Virgin membrane; MM Modified membranes;
MM (NP) Modified with nanoparticles......34

4.5

Summary of significant results for organic and biological fouling...34

viii

LIST OF FIGURES
1.1

Classification of pressure driven membranes based

on their pore size, molecular weight and particles retained............6

2.2

Alternate Deposition of Polyelectrolytes and

Capped Silver nanoparticles6

3.1

Fouling Mechanisms in membrane separations ..7

3.1

Poly(ethersulfone) structure...................................................................................16

3.2

Model Structure of Humic Acid ...........................................................................17

3.3

Chemical Structure of Polyelectrolytes

left-PDADMAC; right-PSS ......18

3.4

Possible mechanisms of antimicrobial activities

exhibited by nanomaterials........19

3.5

Layer by layer deposition of nanoparticles

top-without nanoparticles; bottom-with nanoparticles .20

3.6.a

Filtration Setup for biofouling studies...22

3.6.b

Filtration Protocol for biofouling studies ......23

3.7

Top Virgin Membrane; Middle Fouled membrane

(reversible + irreversible fouling); Bottom
Cleaned membrane (irreversible) fouling .....................................................25

4.1

SEM Pictures of Unmodified Membrane. Light areas

depict pores in membrane surface areas........26

4.2

SEM Pictures of Modified Membranes. Silver

nanoparticles are depicted by purple areas........27

4.3

FTIR spectra of 0.1 m PES membranes......................................................28

4.4

Zeta potential of the unmodified and modified membranes

* with silver nanoparticles ....29

4.5

PWF of membranes before organic fouling (45 min @ 10 psi).........................31

4.6

PWF of membranes after cleaning (45 min @ 10 psi,

0.2 M NaOH, 1h)...................................................31

ix

4.7

Left PWF of membranes after biofouling and

cleaning (40 min @ 10 psi, 200 PPM NaOCl 1h)......32

CHAPTER 1: INTRODUCTION
1.1 Problem Definition
Fouling is inevitable in membrane processes but improvements can be made to the
physical and chemical properties of the membrane to considerably reduce fouling
potential and improve performance recovery after cleaning. Polyelectrolyte multilayer
modification is investigated in this study to determine its effect on both organic fouling
by humic acid and biofouling by Escherichia coli (E. coli hereafter).
Fouling of membranes is the deposition and accumulation of particulates rejected at
the surface and within the pores of the membranes during filtration. Fouling mitigation is
essential to the sustainable use of membrane technology as fouling has a direct negative
effect on the membrane performance. Fouling decreases flux and increases membrane
resistance, energy consumption and maintenance costs. A membrane is fouled when
suspended and or dissolved substances have deposited on its external surfaces, on or
within its pores during the process [8]. There are four major types of fouling which
include organic fouling, biofouling, colloidal fouling and crystalline fouling (scaling)
[41]. Colloidal fouling results from the deposition of particulates whereas crystalline
fouling results from the deposition of minerals. The focus of this study is on organic
fouling which consists of the accumulation of naturally occurring organic matter and
biofouling which consists of the accumulation and growth of microbiological matter.
Both fouling types are detrimental to the economical use of membranes as the matter that
accumulates at the surface and within the membrane pores alters the properties of the
membranes, increases resistance and significantly reduces the flux. The fouling cannot be
reversed until the process is stopped and even when reversed fouling permanently alters

membrane properties [8], driving maintenance and energy cost up thereby increasing the
overall cost of membrane technology.
Pressure driven membrane applications encompass diverse industries including, but
not limited to, water processes, biotechnology, food and drug, chemical and
pharmaceutical, oil and gas and the shipping industry. Pressure driven membranes are
defined as separation structures with a thickness very small relative to its lateral
dimensions that commonly undergo selective mass transfer under a pressure driving force
[8]. These membranes can be classified by many characteristics including the size of
particulates they reject, their driving forces, their morphology and surface properties.
Particulate size is used to classify microfiltration and ultrafiltration membranes.
Nanofiltration membranes are characterized by a combination of particulate size and
solute passage.

Reverse Osmosis membranes are characterized by solute passage.

Estimates based solely on size are as follows:

-

Microfiltration membranes reject dissolved or solid particulates larger than 100

nm

Ultrafiltration membranes reject dissolved or solid particulates larger than 10 nm

Nanofiltration membranes reject dissolved or solid particulates larger than 1 nm,

including divalent ions

Reverse Osmosis membranes reject most dissolved and solid particulates,

including monovalent ions.

Figure 1.1 Classification of pressure driven membranes based on their pore size, molecular weight
and the particulate retained. Microfiltration membranes used in this study were 0.1 micron and
were subjected to a pressure of 10 psi.

Modifying the surface of fouling-prone membrane was found to be a good way to

circumventing the issue. Many techniques have been reported successful for membrane
surface modifications including multilayer deposition, plasma treatment, ion implantation
and UV graft polymerization [1-4]. Polyelectrolyte multilayer modification, first
introduced by Decher et al. (1991) is the approach selected for this study. This method is
recognized as the most versatile and simple of all the nano-dimensional multilayered
films namely the Langmuir-Blodgett approach, spin coating and polyelectrolyte
multilayer modification [4-5]. Polyelectrolyte multilayer deposition notably modifies the
properties of the membrane and its interactions by adding and/or increasing its surface
charge, by blocking its pores and by changing its morphology. This method has the
potential to impart antifouling properties to membranes without altering their structure all
the while maintaining or increasing overall flux.

In this study we investigated the performance of nano-composite membranes

created using the polyelectrolyte modification technique. Modified polyethersulfone
membranes were compared to commercially available polyethersulfone membranes (PES)
in terms of their biological and organic fouling potential, their permeability and their
surface characteristics. This investigation is novel in that it proposes a modified
membrane for the mitigation of both biological and organic fouling.
1.2 Research Objectives and Approach
The overall goal of this research is to create membranes with improved fouling
resistance and flux resulting in sustainable, easy to maintain, economical thin film
structures suitable for diverse applications. Altering the surface-solute interactions
between the membrane surface and the filtered solutions is expected to decrease
accumulation of natural organic matter as well as microorganisms, prevent the growth of
microorganisms, which would reduce pore blocking and increase flux and overall
membrane performance. This study is a qualitative investigation of the effect of
polyelectrolyte and silver nanoparticles modification on commercially available
membranes during organic and biological fouling. Membranes will be tested against two
solutions: humic acid solution, model organic solution and a E coli suspension, model
biological solution.
To achieve our goal, three membranes were studied: a commercially available membrane
and two modified membranes. The two modifications consisted of the alternate
deposition of oppositely charged polyelectrolytes with different top layers: one coated
with a strong negative polyelectrolyte (PSS) and the other with silver nanoparticles
capped with the same polyelectrolyte (PSS). Both modified membranes were compared

to the neutral commercially available membrane in terms of their overall performance.

Surface characterization included Scanning Electron Microscopy (SEM) and Fourier
Transform Infrared (FTIR) Spectroscopy and Electrokinetic analyzer (EKA). Each of
these characterization studies confirmed the changes affected to the membrane surface.
The rationale behind this study is based on three hypotheses:

The Donnan Exclusion theory states that two negatively charged particles will
repel one another due to electrostatic interactions. Based on this theory, the
negatively charged membrane surface will repel negatively charged humic
substances.

Sulfonic groups present in the polyelectrolytes deposited on the membranes will

impart hydrophilicity to the modified membranes. Membranes modified using
polyelectrolytes will be more hydrophilic than unmodified membranes.

Silver nanoparticles will aid in reducing membranes biofouling by controlling the

microbial activity on the fouled membrane. Modification with polyelectrolytes
and silver nanoparticles will impart not only hydrophilicity but also biocidal
characteristics to the membranes.

Figure 1.1 is an illustration of the rationale where membranes modified to have a

negative surface charge repel negatively charged humic substances thereby reducing
humic acid fouling. Also, membranes modified to have silver nanoparticles at the surface
as well as a negative surface charge reduce biological fouling by limiting the deposition
and growth of microorganisms. .

Figure 1.2 Alternate Deposition of Polyelectrolytes and Capped Silver Nanoparticles resulting in two
different membranes a negatively charged membranes, a silver nanoparticle integrated negatively
charged membrane.

CHAPTER 2: BACKGROUND AND REVIEW OF LITERATURE

2.1 Background
Fouling of membranes is inevitable but many efforts are being made to minimize
this problem. Extensive research has been conducted to understand fouling causes,
mechanisms, and consequences. When solutions are filtered through any membrane,
rejected particulates accumulate at the membranes surface or within its pores. Particles
may also floc together and form a stronger layer at the surface potentially forming a cake
which limits flow through the membrane. Chemicals in the solution may also modify the
membrane pores consequently narrowing or etching them (See figure 2.1). Those
alterations of the membrane characteristics increase the cost of the filtration process as

energy, operations and maintenance cost increase as productivity decreases. Membrane

surface modification has been proposed as a successful technique to reduce and
sometimes prevent fouling. In this study, we contribute to the body of knowledge in this
field by investigating a novel modification technique which will not only circumvent
organic fouling but also biofouling. Such improved membranes have many potential
applications in the water and wastewater industries, food industry, medical and
pharmaceutical industries to name a few.

Figure 2.1 Fouling Mechanisms in Membrane Separations [9]

2.2 Literature review

2.2.1 Polyelectrolyte Multilayer Modification
Many surface modifications have been proposed to improve commercially
available membranes and making membrane technology more accessible to all. Some,
but not all, prevalent membrane modification techniques include thin film modification,
UV grafting, ion implantation and plasma modification [1-5]. These modifications impart

new physical and/or chemical characteristics that affect the selectivity, efficiency and
lifetime of the membranes.
Thin film fabrication is very attractive in that it can be done on many different
substrates in the nanometer range. Thin films are generally assembled using the following
techniques: the Langmuir-Blodgett method, spin coating and the polyelectrolyte
multilayer deposition (PEM) [4-5].
The polyelectrolyte multilayer deposition approach has been defined as an
alternate deposition of polycations and polyanions on various substrates. This approach
was introduced by Decher et al., (1991) and offered a simple, versatile and controllable
approach. The experiments are controllable because the different parameters including
temperature, pH, ionic strength, and salt concentration [6] in polyelectrolyte solution can
be easily modified in order to alter the final membrane properties [5-7]. As stated above,
the thin films are built layer by layer by exposing the surface to oppositely charged
polyelectrolyte solutions. Such mechanisms are made possible by the electrostatic
interactions, hydrogen bonding, van der Waals forces and hydrophobic-hydrophobic
interactions [1]. Also, charge compensation and reversal enables the incorporation of
multiple bilayers - a bilayer is formed when two layers of opposite charge have been
deposited successively. Additionally, the charge on these membranes is that of the top
layer and is often due to over compensation of charge. The choice of polymer solution
depends on the potential applications of the membranes as the polymer solution
determines the charge, structure and overall applicability of the membrane. Many
polymers have been used to modify membranes including polyelectrolytes, dyes, protein
and clays [10]. Polyelectrolytes can be used in different combinations of strong strong,

weak weak, strong weak. PSS, PDADMAC, PAH respectively strong polyanion,
strong and weak polycation are the most common polyeletctrolytes used [44]. The
polyelectrolyte used to modify the membrane is determined by the potential application
of the membrane. For example, PEM modified films have been proposed for the electro
optical field, water and wastewater treatment field, cosmetic and pharmaceutical field and
in biomaterials [4-5, 42]
Grigoriev, et al., (2009) reported successful fabrication and characterization of
polyelectrolyte nanoparticle (iron oxide) embedded thin films. The nanocomposite
membranes were characterized in terms of their thickness relative to the number of layer
deposited. The membrane roughness increased as the number of layers deposited
increased. Also, the integration of nanoparticles increased the roughness of the surface.
Bruening, et al., (2005) successfully modified commercially available PES
nanofiltration membranes into high flux membranes with very high selectivity of glucose
over sucrose and of chloride over sulfate. The modified membranes also displayed a high
sulfate rejection.
Laurent, et al., (1997) investigated the interpenetration of multilayers of PSS and
poly(butanylviologen) . They reported that it takes four bilayers to isolate two active
redox layers. They also found that charge percolation is explained by the hopping
between the viologen groups.
Wong, et al., (2009) performed thorough characterizations of PSS/PDADMAC
modified microgels in order to assess the impact of the different parameters namely the
ionic strength, the salt concentration and the molecular weight. They found that PSS
terminated microgels were more sensitive to temperature than PDADMAC terminated

gels; also, the gels increased in size as the salt concentration increased; and, finally, the
molecular weight had no effect on the size of the gel.
Gittins, et al., (2001) fabricated nanoparticles coated capsules tailored to fit
different applications by manipulating the polyelectrolyte type, ionic strength and the
characteristic of the nanoparticles.
Fabio, et al., (2009) reported on the effect of time of deposition on the
modification of films using citrate encapsulated gold (Au) nanoparticles, a polyviologen
derivative and a cationic redox polyelectrolyte. They recommended shorter deposition
times as longer deposition times resulted in nanoparticles aggregation.

2.2.2 Natural Organic Matter (NOM) Fouling

Natural organic matter (NOM) is ubiquitous in the ecosystem. NOM in natural
waters is mainly composed of humic substances and is a very complex structure that
often needs to be modeled for research purposes. Natural organic matter fouling
constrains effective and efficient implementation of membrane technology. NOM
accumulated at the membrane surface deteriorates membrane properties, increases energy,
operation and maintenance cost and shortens membrane life [45-47, 49-54, 56-58]. NOM,
in presence of chlorine, may lead to the formation of disinfectant byproducts which are
potential carcinogens [48]. There are four major fouling types classified by the foulant
characteristics, hence filtered solutions containing organic matter lead to NOM fouling,
solutions containing microorganisms causes biofouling, solutions containing minerals
causes crystalline fouling, finally, solutions containing colloids causes colloidal fouling.
NOM fouling is one of the most common of all four fouling types. The abundance of

10

NOM in natural waters makes organic fouling of most filtration processes inevitable.
NOM derived from the degradation of plants and animal residues [11-12, 47] is mainly
found in the form of humic substances which are further categorized as humin, humic
acids and fulvic acids. Humin represents the substances insoluble in both acidic and basic
environments while humic acid is soluble at pH 2 and fulvic acid is soluble at any pH [12,
55]. Humic acid constitutes the majority of humic substances present in natural water and
in wastewater and is often negatively charged because of the dissociation of carboxylic
acids and hydroxyl functional groups [13]. This negative charge of the humic acid is of
particular interest to this study as the membranes in this study will be imparted a negative
charge which will affect the transport of the humic solution through the membrane.
Charge repulsion is expected due to the negative charges of the membrane surface and
humic substances. Successful natural organic matter mitigations have been widely
documented in the literature [35-41].
Combe, et al., (1999) modified cellulose acetate membranes by annealing,
oxidation and hydrolysis to study adsorption of humic acid onto the membranes.
Hydrophylicity of membranes was increased, however, it was found that pre - adsorption
of an anionic polymer (vinyl acetate/acrylic acid copolymer) was necessary to reduce
adsorption of foulants on the modified membranes.
Yuan, et al., (1999) investigated the flux decline rate and extent during the
filtration of commercially available humic acids through microfiltration membranes.
Such humic acids were studied in terms of their molecular weight distribution and their
effect on fouling. Humic substances deposited on the membranes were also characterized
using a scanning electron microscope (SEM). They observed that the initial fouling of

11

membranes is due to the convective deposition of large aggregates followed by the

aggregation of macromolecular humic acids.
Carroll, et al., (2001) grafted charged and un-charged hydrophilic polymers onto a
polypropylene hollow fiber increasing the membrane permeability thereby reducing
fouling. The modified membranes was used for fouling during extended periods with
minimal flux decline.
2.2.3 Biofouling
Biofouling is a very serious limitation to many processes and is mainly due to the
ubiquitous presence of microorganisms in our environment. Biofouling is due to the
deposition of microorganisms on surfaces and their subsequent growth on any surface.
Viable bacteria bound to the surface continue to grow, multiply and may even relocate
making biofouling the most complex type of fouling [15]. The attachment of these
bacteria to the surface is very complex and is still being investigated. Several parameters
impact biofouling including but not limited to the surface properties, solution chemistry
and hydrodynamic factors. An approach to circumvent biofouling is to prevent the
deposition and accumulation of microorganisms by modifying the membranes surface
properties. Various surfaces have been modified to limit the deposition of
microorganisms and potentially kill those bound to the surface [15-19]. Functional groups
such as silver, chitosan, ammonium groups, photocatalytic TiO2 and ethylene glycol
oligomers are utilized to prevent biofouling via surface modification [14] [16-19]. These
chemical compounds are believed to have antibacterial properties which they impart to
the surface thereby reducing and possibly eliminating bacterial activity.

12

Previous work from our lab has involved the UV graft modification of
polyethersulfone (PES) membranes using Acrylic Acid and AETMA as the graft
monomers [60-61]. AA and AETMA modified membranes were more resistant to
biofouling by E. coli and more hydrophilic than unmodified membranes with AETMAmodified membranes performing better than both the AA modified and the unmodified
membrane.
Hyun, et al., (2006) reported that membranes coated with poly (ethylene glycol)
PEG containing comb polymers inhibited the fouling of polysulfone ultrafiltration
membranes by biomaterials namely microbes, bovine serum albumin and alginic acid.
Modified membranes showed a higher flux recovery when compared to uncoated
membranes.
Kull, et al., (2005) favorably compared their microporous polyethersulfone
membranes modified using nitrogen based plasma treatment to commercially available
membranes. Modified membranes showed a higher flux recovery, less protein (bovine
serum albumin BSA) fouling potential and a higher pure water flux .
Kim, et al., (2003) used TiO2 nanoparticles to mitigate biofouling. The
introduction of nanoparticles prevented the fouling of the modified thin film composite
(TFC) membranes by E. coli and increased the fouling resistance compared to the
commercial membranes.
Hilal, et al., (2004) showed, using E. coli as a model foulant, that polyvinilidene
fluoride

(PVDF)

microfiltration

membrane

integrated

with

gDMAEM

polyethyleneimine had less affinity to biofouling than unmodified membranes.

13

and

Although the above modifications were reported successful, our study was
focused on the modification of membrane surface using silver which has been used
effectively for centuries [62].
2.2.4 Silver Nanoparticles as an Antimicrobial Agent
A wealth of information is available on the antibacterial effect of silver. Silver in
various forms is particularly effective for burn wounds but has been used to treat water,
venereal diseases, fistulae from salivary glands, to promote crust formation on the surface
of wounds, and as eye drops [21]. Silver is used in various forms including metal, zeolite,
sulfadiazine and nanoparticles, which all release silver ions in order to inhibit bacterial
activity. An attractive feature of silver coating is its toxicity which is as low on humans
as it is high on a wide spectrum of bacteria including E coli. Silver has been used as an
antimicrobial agent in many products including kitchen appliances, medical devices and
purification systems [62]. Silver nanoparticles are known for their pronounced
antibacterial properties as well as optical, magnetic, catalytic and electrochemical
properties. Their different applications include but are not limited to biosensors, electro
optical devices, biological imaging and data storage media [33]. The versatility of the
polyelectrolyte multilayer deposition technique enables the controlled formation of silver
coatings on various substrates. It appears that silver in various forms releases silver ions
which damage the bacteria upon ingestion, produce reactive oxygen species, or prevent
DNA replication in the bacteria cell. Silver ions upon penetrating the bacterial cell
degrade the polysaccharide molecules, accumulate in pits, increase the bacterias
membrane permeability and inactivate respiratory enzyme [22-24]. Many researchers
have reported increased bactericidal activity on silver integrated surfaces.

14

Li, et al., (2008) presented a literature review comparing different materials

including chitosan, silver nanoparticles, fullerenes, carbon nanotubes, TiO2 and ZnO.
They understand the nanotechnology based water systems as potential alternatives to
conventional water treatment and recommend the development of better coating
techniques through nanoparticles functionalization and incorporation of nanoparticles in
existing water treatment processes.
Sondi, et al., (2004) studied the effect of silver nanoparticles on E coli. They
report that silver nanoparticles in agar plates completely inhibit microorganisms whereas
they only delay growth when present in liquid medium. They concluded that silver
nanoparticles efficiently mitigate biofouling and could potentially lead to the manufacture
of innovative bactericides.
Zodrow, et al., (2009) presented polysulfone silver impregnated membranes with
antibacterial and antiviral properties. Silver impregnated membranes, according to the
authors, are great alternatives for biofouling mitigation.
Li, et al., (2006) proposed a multilayer film coated with polyelectrolytes and
embedded silver ions, which have the potential to kill bacteria on contact. The two level
coating strategy they introduced consist of the deposition of polyelectrolytes and
nanoparticles and allows better control over the surface chemistry.

15

CHAPTER 3: MATERIALS AND METHODS

3.1 Materials
3.1.1 Membranes
Different supports are considered for the polyelectrolyte multilayer deposition
method. Polyethersulfone (PES) (See Figure 3.1) membranes with pore size of 0.1 m
from GE Osmonics were used as support membrane in this study. The PES polymer used
to manufacture these membranes has different sulfonic functional groups and phenyl
groups. Oxygen in the sulfonic group is believed to participate in the hydrogen bonding
and hydrophobic interactions involved in the polyelectrolyte multilayer modification
technique. Although the PES has a relatively low negative charge, it is considered neutral
as the charge is shielded by hydration [31]. The PES membranes are particularly suitable
for water treatment applications because of the wide chemical compatibility, good
resistance to oxidants, aging resistance and environmental endurance [3].

O
O

S
O

Figure3.1 Poly (ethersulfone) structure

3.1.2 Humic Acid solution

Humic acid from Aldrich Chemical Co. (Milwaukee, WI) was selected as the
foulant in this study and was used without further purification. A solution of 20 mg/L of
humic acid was filtered through both unmodified and modified membranes. Figure 3.2 is
one of the many models proposed for the structure of humic acid in the environment.

16

Figure 3.2 Model Structure of Humic Acid (Stevenson 1982)

3.1.3 Escherichia coli (E. coli) Suspension

Microorganisms, similarly to natural organic matter, are ubiquitous in the environment.
Coliform bacteria are gram-negative, aerobic and non-spore-forming and include
Escherichia, Citrobacter, Enterobachter and Klebsiella. These bacteria often originate
from fecal sources and typically inhabit soil and wastewaters from which they make their
ways to potable water sources. E.coli was chosen as the model indicator for this study as
it is often found in living species and has been suggested as an indicator that is easily
distinguishable from the other indicators in the fecal coliform group [32]. E.coli
suspension of 106 Colony-Forming Units/mL (hereafter CFU/mL) was diluted from a
stock of 109 CFU/mL which was prepared from a Luria-Bertani (LB) broth culture of E.
coli grown overnight. The stock solution was diluted in a Phosphate Buffer Saline (PBS)
buffer consisting of a solution of 80 g NaCl, 14.4 g NaHPO4 , 2.4 g KH2PO4, and 2.0 g
KCl at a pH of 7.5 (+/- 0.1).
3.1.4 Polyelectrolytes
Poly-(styrenesulfonate)

(PSS)

and

poly-(diallyldimethylammonium

chloride)

(PDADMAC) were chosen in this study. PSS is a negatively charged strong

17

polyelectrolyte while PDADMAC is a positively charged strong polyelectrolyte. Both

chemicals were purchased from Aldrich Chemicals Co. (Milwaukee, WI) and used
without further treatment. Polyelectrolyte solutions containing 0.02 M of the
corresponding polymer and 0.5 M NaCl were prepared in a constant volume ratio of 1:1
and used in the modification process described below. Figure 3.3 displays the chemical
structures of both monomer units of the polyelectrolytes.

PSS

PDADMAC

Figure 3.3 Chemical Structure of Polyelectrolytes left-PDADMAC; right-PSS

3.1.5 Silver Nanoparticles

The bactericidal properties of silver nanoparticles were studied in these
experiments by comparing the growth of bacteria on modified and unmodified
membranes. The silver nanoparticles used in this study were stabilized in citrate medium,
ranged between 40 50 nm in size and had a concentration of 0.001 M. The particles
were then dispersed in a 0.02 M of PSS, solution which was then deposited in the top
layer of the prepared multilayer thin films. The silver nanoparticles are believed to

18

interact with the bacteria in three ways: they may interact directly with the cells by
stopping the electron transport, they may damage and enter the cell or they may produce
secondary products which will in turn damage the microbial cell as shown on Figure 3.4
[22-24].

Figure 3.4 Possible mechanisms of antimicrobial activities exhibited by silver nanoparticles [22]

3.2 Modification process

Membranes received as a flat sheet were cut in coupons and soaked in milliQ
water for at least eight hours during which the water was changed every 2 hours to
remove the chemical coating added during production to preserve the membranes
integrity. The membrane coupon was then placed in a holder which exposed the effective
membrane area of 13.4 cm2 to polyelectrolytes solutions. The commercially available
membrane coupons were modified into two different membranes with one having PSS as
a top layer and the other with PSS capped nanoparticles as the top layer. During the
modification process, the polyelectrolyte solutions were alternately deposited on the
support in three steps which lasted 3 minutes each in the following order: negatively
19

charged PSS followed by the positively charged PDADMAC followed by either another
layer of PSS or a layer of negatively charged silver nanoparticles capped with PSS. Each
layer serves as a surface primer for the next oppositely charged layer. The membrane
surface was thoroughly rinsed with MilliQ water for 1 minute between each deposition
step. The modified membrane was then ready for use in filtration studies and membrane
structure characterizations. Figure 3.5 is a step by step graphic of both modification
processes with and without nanoparticles. The top graphic is an illustration of the
modification process of the membranes with polyeletrolytes and without nanoparticles
whereas the bottom graphic represents the modification of membranes with not only
polyelectolytes but also capped silver nanoparticles at the top surface.

Figure 3.5 Layer by layer deposition of nanoparticles top-without nanoparticles; bottom-with

nanoparticles

20

3.3 Membrane characterization

3.3.1 Zeta Potential Measurement
Zeta potential of the membranes, virgin and modified, were measured using an
electrokinetic analyzer (EKA) purchased from Anton Paar GmbH (Graz, Austria). The
instrument is reported to a current intensity of 10 mA and a voltage of 4V and is based on
the streaming potential, conductivity, electrolyte composition, pH and pressure. It is also
based on the electrical double layer at the solid liquid interface. The streaming potential,
which the zeta potential is derived from, is determined via electrodes when an electrolyte
solution flows in contact with a charged solid surface [34].
3.3.2 Surface characterization: FTIR - SEM
Bonds and chemical (i.e. sulfonic and carboxylic) groups were identified using
Attenuated Total Reflectance - Fourier Transform Infrared (ATR - FTIR) to confirm the
chemical modification imparted on the commercially available membranes.
SEM pictures were taken to confirm the deposition of silver nanoparticles on the
membrane surface and to investigate its morphology. SEM is generally carried out to
determine the surface morphology, characteristics, pore sizes and distribution.
3.4 Flux experiments
3.4.1 Filtration Setup
Filtration studies were performed on the modified membranes in order to compare the
permeability of the membranes. The filtration set up consisted of a 50 ml dead end
Amicon stirred cell (model 8050) purchased from Millipore Corp. (Bedford, MA), a
nitrogen tank, a graduated cylinder, two stainless steel pressure reservoirs for the
21

biofouling and organic fouling holding respectively 3 L and 20 L. The filtration setup is
shown schematically in Figure 3.6.a.

Figure 3.6.a Filtration Setup for fouling studies

3.4.2 Filtration protocol

Pure water flux was measured at a pressure of 10 psi to determine the initial
permeability of both unmodified and modified membranes (Initial PWF is Jo). The
fouling solutions were then filtered through the membrane separately placed in a dead
end filtration cell.
The 20 mg/L humic acid solution was filtered for two hours or until steady state
was reached (note: flux during fouling is Jf). Following this step the pure water flux of
the fouled membranes was measured after the membranes were hydraulically cleaned in
milliQ water (PWF of fouled membranes is Jf). The fouled membranes were then
unloaded and chemically cleaned using a 0.2 M of sodium hydroxide (NaOH). During

22

chemical cleaning, membranes were placed in a stirred cell for 1 hour. After the chemical
cleaning, the membranes were reloaded in the stirred cell to measure the pure water flux
(PWF of cleaned membrane is Ji).
For the biofouling experiments, a 106 CFU/mL of E. coli suspension was used as
the model biological foulant. The solution was filtered through the membranes for two
hours or until steady state was reached. Microorganisms on the fouled membranes were
allowed to grow on agar plates incubated at 37oC for 24 hours. The membranes were then
hydraulically and chemically cleaned using 200 ppm of sodium hypochlorite (NaOCl) for
respectively 30 minutes and 1 hour under stirred cell condition. The pure water flux of
the membranes was measured after each cleaning step. Both filtration protocols are
shown schematically in Figure 3.6.b.

Figure 3.6.b Filtration Protocol for Fouling Studies; Top- Organic Fouling Protocol;
Bottom Biological Fouling Protocol

23

3.4.3 Flux analysis

The fluxes recorded during the experiments were normalized using the following
equation:

Jf
Jo

Jn =
Where Jn = normalized flux,
Jf = flux at steady state,
Jo = Initial flux

The flux reduction of each membrane was computed using the following equation:
J% =

PWF f PWFo
PWFo

* 100

Where J% = Flux reduction

PWFf = pure water flux after fouling and cleaning
PWFo = pure water flux before fouling
Membrane resistances were determined using flow rates recorded during the
fouling experiments. Below is a description of the calculations used to determine the
membrane resistances.
Rm =

P
J o

Where Rm= Inherent Membrane resistance

Jo= Pure water flux of clean membrane
= Dynamic viscosity of the fluid
P = Transmembrane Pressure

Rt =

1
P 1

J f J o
[8]

Where Rt =Total Membrane Resistance

Jf = Pure Water Flux during Fouling
Jo= Pure water flux of clean membrane

24

Rr =

P 1
1

Jr Jo

Where Rr =Reversible Membrane Resistance

Jr = Pure Water Flux of Fouled Membrane
Jo= Pure water flux of clean membrane

Ri =

1
P 1

Ji Jo

Where Ri =Irreversible Membrane Resistance

Ji = Pure Water Flux of Cleaned Membrane
Jo= Pure water flux of clean membrane
The reversible membrane is derived from the pure water flux measured after
hydraulic cleaning which removes loosely adherent foulants. Chemical cleaning removes
the foulant that could not be removed using pure water flux. The flux through the
recovered membrane then determines the irreversible membrane resistance due to the
foulant deposited at the surface or within the membrane pores that could not be removed
by either hydraulic or chemical cleaning (Figure 3.7). The total resistance is the
resistance of the membrane to flow before the fouled membranes have been cleaned and
include the inherent membrane resistance, the reversible membrane resistance and the
irreversible membrane resistance.

Figure 3.7 Top Virgin Membrane; Middle Fouled membrane (reversible + irreversible fouling);
Bottom Cleaned membrane (irreversible fouling)

25

CHAPTER 4: RESULTS AND DISCUSSION

4.1 Characterization of PES membranes
4.1.1 SEM - FTIR

The surface topography of the modified and unmodified membranes was imaged
with SEM (Figures 4.1 and 4.2). The images confirmed that the silver was well dispersed
on the membrane surface with an average particle size of 50 nm which corresponds to the
size of the nanoparticles in the original citrate stabilized solution. The integrity of the
membranes and the nanoparticles remained intact during the modification procedure. A
few aggregates were observed on the surface of the membrane. In general, aggregation is
not preferable, as aggregates may block the pores of the membrane; a small percentage of
the silver nanoparticle aggregates appear large enough to partially block some of the
pores of the membrane. Note, however, that most of the pores remain open and available
for flow.

Figure 4.1 SEM of unmodified PES membrane. Light areas depict pores in membrane surface.

26

Figure 4.2 SEM of modified membranes. Membranes are modified with 1.5 bilayers of PDADMAC
and silver nanoparticle-capped PSS. Silver nanoparticles are depicted by purple areas.

FTIR spectra of unmodified and modified membranes are presented in Figure 4.3
as evidence of the chemical modification of the membranes. The spectra have peaks at
1028 cm-1 corresponding to the symmetric sulfonic stretch of PSS [1]. The presence of
this peak is an indication of the chemical changes imparted to the membranes by the
deposition of the polyelectrolyte solutions and of the nanoparticles. The polyelectrolyte
groups added to the structure of the membrane rendered the surface more hydrophilic,
thereby increasing permeability. The peaks at 1028 cm-1 were not as intense on the
membranes modified with silver nanoparticles, when compared to the membranes
modified with polyelectrolytes only. UV irradiation with intensity of 27 mW/cm2 at 300
nm wavelength was conducted in order to determine if irradiation would improve
deposition of silver nanoparticles. UV irradiated membranes appeared to have a stronger
sulfonic peak as shown on Figure 4.3. Further experiments will be needed to evaluate the
effect of the UV on the fouling of the membranes.

27

0.25
PES-Virgin

0.2

PES-MPE-NP-No UV
PES-MPE-NP-30 sec UV
PES-MPE-NP-2 min UV

A b so rb an ce u n its

0.15

0.1

0.05

-0.05

1000

1500

2000

2500

-1

Wavenumbers, cm

Figure 4.3 FTIR Spectra of 0.1 m PES membranes. Left Modified with 1.5 PDADMAC/PSS
bilayers, no silver nanoparticles; Right unmodified and modified with 1.5 PDADMAC/PSS bilayer
with silver nanoparticles with and without UV irradiation.

4.1.2

Zeta Potential Measurements

The zeta potential of the membranes was derived from the streaming potential
using the Helmholtz-Smoluchowsky equation. The zeta potential mean values were -32.1,
-51.8 and -52.6 mV, respectively for the virgin membrane, polyelectrolyte silver
modified membranes and the polyelectrolyte modified membrane. The polyelectrolyte
modification increased the negative zeta potential of the membrane; however the addition
of silver nanoparticles did not significantly affect the net zeta potential (Figure 4.4). The
increase in negativity after polyelectrolyte modification is an advantage in preventing
fouling due to stronger repulsive action between the negatively charged membrane

28

surface and the negatively charged humic acid compounds at pH values relevant in water
treatment.

Figure 4.4 Zeta potential of the unmodified and modified membranes - * film with silver
nanoparticles. Streaming potential measurements were taken at pH 5.4, with 0.001 M KCl.

4.2 Filtration studies

4.2.1 Flux

Low pure water flux is one of the major drawbacks of membrane separation as it
reduces the overall productivity of the process. Surface modification sometimes leads to
an even further decrease in flux which may be due to the reduction in pore size of the
membrane and the chemical modification of the membrane surface (increased ionic
strength and thickness). Maintaining the flux of the membranes during modification was
very important in this study. The polyelectrolyte layers were kept to 1.5 bilayers to
minimize the thickness of the additional polyelectrolyte layer. Increasing membrane
thickness would increase the inherent membrane resistance and decrease flux for a given
pressure. The initial pure water flux (Jo) was lower for the polyelectrolyte-modified
membranes possibly due to a slightly higher inherent membrane resistance (resulting

29

from a thicker effective membrane) and to the physical pore blockage (resulting from the
silver nanoparticle aggregates). Lower initial flux in modified membranes (Reddy, et al.,
(2003) is not desirable but the effects can be offset by decreased fouling and flux decline,
which would result in higher recovery and more efficient overall performance. Thus,
comparisons were made of initial permeability (as measured by pure water flux, PWF)
and PWF after fouling and cleaning the membrane. These comparisons allow for a better
comparison of overall membrane performance than simply the initial permeability.
The initial pure water flux values were slightly lower for the modified membranes
compared to the virgin membrane as indicated on Tables 4.1 and 4.2 and Figures 4.6 and
4.7. The flux of the virgin membrane began to decline after 20 minutes (Figure 4.5), and
the virgin membrane had a higher overall flux decline when comparing the original pure
water flux to the pure water flux after fouling and chemical cleaning of the membrane.
Table 4.1 Pure Water Flux of virgin, polyelectrolyte modified and polyelectrolyte + NP modified
membranes for organic fouling experiments; Units for PWF are ml/cm2/min. 20 mg/L humic acid
feed solution filtered for 45 minutes at 10 psi.

Modified w/o NP

Modified w/ NP

Virgin

PWF No fouling

7.17 0.26

7.28 0.07

8.33 0.36

PWF /Organic fouling + hydraulic

0.95 0.002

0.75 0.05

0.83 0.56

6.57 0.23

5.75 0.06

6.43 0.21

8.3 0.036

16.4 1.7

22.8 0.85

cleaning
PWF / Organic fouling + chemical
cleaning (0.2 M NaOH)
Flux Decline (%) / between no fouling
and chemically cleaned

30

Figure 4.5 PWF of virgin, polyelectrolyte modified and polyelectrolyte + NP modified membranes
before organic fouling (20 mg/L humic acid filtered for 45 min @ 10 psi). Error for data as shown in
Table 4.1

Figure 4.6 PWF of membranes after cleaning (0.2 M NaOH, 1hour). Foulant solution: 20 mg/L humic
acid feed solution filtered for 45 minutes at 10 psi. Error for data as shown in Table 4.1
Table 4.2 Pure Water Flux of membranes throughout biofouling experiments; Units for PWF are
ml/(cm2*min), 106 cells/mL E. coli feed solution filtered for 45 min at 10 psi

Modified w/o NP

Modified w/ NP

Virgin

PWF No fouling

7.17 0.26

7.28 0.07

8.33 0.36

PWF /Biofouling + hydraulic cleaning

4.14 0.014

3.51 0.014

4.66 0.012

PWF / Biofouling + chemical cleaning

7.15 0.02

7.01 0.07

7.29 0.04

Flux Decline (%) / between no fouling

0.3 0.67

3.70 1.7

12.2 0.45

and chemically cleaned

31

Figure 4.7 PWF of membranes after cleaning (200ppm NaOCl 1h) Foulant solution is 106cells/mL E.
coli feed solution filtered for 45 min at 10 psi. Error for data as shown in Table 4.2

4.2.2 Flux decline

The flux decline of the fouled and cleaned membranes was compared to assess the impact
of the modification on flux recovery. Before the foulant was brought in contact with the
membrane, the pure water flux was measured, then the foulant (organic or biological)
was filtered through the membrane for 2 hours at 10 psi, followed by chemical cleaning
for 1 hour. Following chemical cleaning the foulant solution was replaced with water to
measure the final flux through the membrane. The term flux decline is used here to
describe the difference between the original pure water flux and the final flux.
Flux decline was more severe for the virgin membrane than for the modified
membranes. The polyelectrolyte-modified membranes with and without nanoparticles
had a flux decline of 8.3 and 16.4 % respectively for the organic fouling and 0.3 and
3.7 % respectively for the biofouling while the virgin membrane flux decline was 22.8 %

32

for the organic fouling experiments and 12.2 % for the biofouling experiments (Tables
4.1, 4.2).
The polyelectrolyte - modified membranes had a lower flux decline and a higher
final flux during the organic fouling and a final flux similar to that of the unmodified
membrane for the biological fouling. This behavior is likely due to the higher negative
surface charge of the polyelectrolyte-modified membranes as evidenced by the zeta
potential (Figure 4.4) and the presence of hydrophilic sulfonic groups at the membrane
surface.
The lower sulfonic stretch evidenced by the FTIR spectra (Figure 4.3) and the
deposition of silver nanoparticles deposited at the surface evidenced by the SEM (Figure
4.2) explain the lower permeability of the membranes modified with silver nanoparticles.
The silver nanoparticles partially block some of the membrane pores, reducing the flux
through the membrane. These results are in accordance with the irreversible resistance
values reported in subsequent sections that the modified membranes were restored to a
higher permeability than the virgin membrane.
4.2.3 Resistances

Resistances of the membranes were calculated from flux measurements taken

throughout the filtration experiments (Section 3.4.3). Unmodified membranes have a
lower inherent membrane resistance and a higher irreversible membrane resistance than
modified membranes as shown in Table 4.3 and 4.4. The higher inherent resistances of
the modified membranes are due to the reduction in size of the membrane pores due to
pore blockage (by silver nanoparticles) and thicker effective membrane as a result of
modification. Although the bilayers were limited to 1.5 bilayers, the polyelectrolytes

33

increased the membrane thickness. The higher irreversible resistance (Ri) values for the
unmodified membranes in Table 4.3 and 4.4 suggest that the organic and biological
substrates filtered through the membranes fouled the unmodified membranes more
significantly than they fouled the modified membranes. Finally, the irreversible
resistances were < 1 m-1 for the polyelectrolyte-modified membranes and the
polyelectrolyte silver modified membranes.
Table 4.3 Membrane Resistances for the organic fouling experiment (units are m-1). VM- Virgin
membrane; MM- polyelectrolyte modified membrane; MM(NP) - Modified with 50 nm nanoparticles
and polyelectrolytes. Feed solution was 20 mg/L humic acid filtered for 120 min at 10 psi.

Resistances (m-1)

VM

MM

MM (NP)

Inherent Membrane Resistance, Rm

4.12

4.79

4.71

Total resistance of the membrane, Rt

52.0

58.0

58.7

Reversible Membrane Resistance, Rr

37.5

31.3

41.1

Irreversible Membrane Resistance, Ri

1.21

0.43

0.92

34

Table 4.4 Membrane Resistances for the biofouling experiment (units are m-1). VM- Virgin
membrane; MM- polyelectrolyte modified membrane; MM(NP) - Modified with 50 nm nanoparticles
and polyelectrolytes. Feed solution was 106 CFU/mL E. coli filtered for 120 min at 10 psi.

VM

MM

MM (NP)

Inherent Membrane Resistance, Rm

4.12

4.79

4.71

Total resistance of the membrane, Rt

26.1

25.6

27.8

Reversible Membrane Resistance, Rr

3.24

3.5

4.87

Irreversible Membrane Resistance, Ri

0.57

0.015

0.18

4.2.3 Results Summary

Table 4.5 Summary of Significant Results for Organic and Biological Fouling

VM

Zeta Potential (mV)

MM

MM (np)

-32.1

-52.6

-51.8

Initial Flux - ml/(cm2/min)

8.33 0.36

7.17 0.26

7.28 0.07

Final Flux (Organic) - ml/(cm2/min)

6.43 0.21

6.57 0.23

5.75 0.06

Flux Decline (Organic) -%

22.8 0.85

8.30 0.036

16.4 1.7

1.21

0.43

0.92

Final Flux (Biological) - ml/(cm2/min)

7.29 0.04

7.15 0.02

7.01 0.07

Flux Decline (Biological) - %

12.2 0.45

0.30 0.67

3.70 1.7

0.57

0.015

0.18

Irreversible Membrane Resistance

(Organic) - (m-1)

Irreversible Membrane Resistance

(Biological) - (m-1)

35

The results summary indicates that the modified membranes have lower flux
decline and lower irreversible membrane resistances than the unmodified membranes.
Thus, the modified membranes fouled less than the unmodified membranes. The
polyelectrolyte - modified membranes without nanoparticles also had a higher flux than
the unmodified membranes during the organic fouling. The membranes are more resistant
to the biofouling possibly because of the size of the pores relative to the size of the humic
substances and the size of the E. coli. Indeed the humic substances may block the pores
of the membranes whereas the E. coli in the range of 0.4-0.5 m cannot block the pores.

36

CHAPTER 5: CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion

There are several conclusions that can be drawn from this study:
1-

The polyelectrolytes and the capped nanoparticles were successfully

deposited on the membrane surface as indicated by the SEM and FTIR
analysis. The zeta potential of the modified membrane without and
with nanoparticles were computed to be -52.6 and -51.8 compared to 32.1 mV for the unmodified membrane which also shows that the
silver nanoparticles do not neutralize the negative charge of the
membrane surface.

2-

The modified membranes without nanoparticles had a higher final flux

than the unmodified membranes during the organic fouling and a
slightly lower final flux during the biofouling as indicated by the pure
water flux measurements. The modified membranes with nanoparticles
had a lower final flux during both organic and biological fouling.

3-

The modified membranes have a lower flux decline than the

unmodified membranes. At the end of the fouling experiments, the
membranes modified with polyelectrolytes without and with
nanoparticles had a percent flux reduction of respectively 8.3% and
16.4% for the organic fouling, 0.3% and 3.7% for the biofouling
compared to 22.8% and 12.2% for the unmodified membrane. The
lower flux decline of the modified membranes is due to the
hydrophilic nature of the polyelectrolyte film deposited on the surface.
37

4-

The modified membranes were less susceptible to irreversible organic

and biological fouling as measured by the filtration studies specifically
the computed membrane irreversible resistances. The modified
membrane without and with nanoparticles showed an irreversible
resistance of respectively 0.4m-1 and 0.9 m-1

during the organic

fouling, 0.015 m-1 and 0.18 m-1 for the biofouling compared to 1.2 m1

and 0.57 m-1 for the unmodified membrane during the organic and

the biological fouling experiments.

5-

The organic fouling was reduced due to higher negative surface charge
(as indicated by zeta potential) of the modified membrane while lower
biofouling was due to the hydrophilicity of the polyelectrolytes and
bactericidal property of silver nanoparticles.

6-

The unmodified membranes and membranes modified without

nanoparticles were more permeable than the nanoparticles modified
membranes by 10 and 12 percent respectively for the organic fouling
and 1.83 and 4.08 percent for biofouling. This lower permeability of
the silver-nanoparticles modified membranes may be due to the pore
blockage and inhibition of the sulfonic groups resulting from the
deposition of silver nanoparticles.

The modification technique investigated in this study was simple and allowed control of
the surface charge of the membrane. It is a very attractive approach to the mitigation of
both biofouling and organic fouling. Membranes used in this study were successfully
modified and performed better in terms of irreversible fouling and flux decline than the

38

unmodified membranes. Fouling is inevitable; however, reducing fouling of membranes

will make them more sustainable, easier to maintain and more economical.
5.2 Recommendations

1. The surface modification studies should be scaled up to pilot studies on an actual

plant to ensure that it is as effective as it has been proven on the lab scale.
2. Consider the effect of the nanoparticles on the environment. It would be wise to
follow the studies currently conducted on the impact of nanotechnology and nanoderived products on the ecosystem

39

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