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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
by
Fatou N. Diagne
Washington, D.C.
August 2009
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HOWARD UNIVERSITY
GRADUATE SCHOOL
DEPARTMENT OF CIVIL ENGINEERING
THESIS COMMITTEE
Candidate:
Fatou N. Diagne
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),
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
vii
LIST OF TABLES
4.1
4.2
4.3
4.4
4.5
viii
LIST OF FIGURES
1.1
2.2
3.1
3.1
Poly(ethersulfone) structure...................................................................................16
3.2
3.3
3.4
3.5
3.6.a
3.6.b
3.7
4.1
4.2
4.3
4.4
4.5
4.6
ix
4.7
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.
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.
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.
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.
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.
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
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
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
15
O
O
S
O
16
(PSS)
and
poly-(diallyldimethylammonium
chloride)
17
PSS
PDADMAC
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]
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.
20
biofouling and organic fouling holding respectively 3 L and 20 L. The filtration setup is
shown schematically in Figure 3.6.a.
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
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
P
J o
Rt =
1
P 1
J f J o
[8]
24
Rr =
P 1
1
Jr Jo
Ri =
1
P 1
Ji Jo
Figure 3.7 Top Virgin Membrane; Middle Fouled membrane (reversible + irreversible fouling);
Bottom Cleaned membrane (irreversible fouling)
25
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
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.
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
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
4.14 0.014
3.51 0.014
4.66 0.012
7.15 0.02
7.01 0.07
7.29 0.04
0.3 0.67
3.70 1.7
12.2 0.45
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
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
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)
4.12
4.79
4.71
52.0
58.0
58.7
37.5
31.3
41.1
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)
4.12
4.79
4.71
26.1
25.6
27.8
3.24
3.5
4.87
0.57
0.015
0.18
VM
MM
MM (np)
-32.1
-52.6
-51.8
8.33 0.36
7.17 0.26
7.28 0.07
6.43 0.21
6.57 0.23
5.75 0.06
22.8 0.85
8.30 0.036
16.4 1.7
1.21
0.43
0.92
7.29 0.04
7.15 0.02
7.01 0.07
12.2 0.45
0.30 0.67
3.70 1.7
0.57
0.015
0.18
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
There are several conclusions that can be drawn from this study:
1-
2-
3-
4-
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 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 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
39
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