Synthesis and Characterization of a Porous Cellulose

Acetate Membrane for Water Treatment Using Readily

Available Chemicals and Instrumentation
By
BS 7th (Inorganic Chemistry) Session 2019-23
And
BS ADS (Inorganic Chemistry) Session 2021-23
Submitted To: Dr. M. Ali Khan

Institute 0f Chemical Sciences, BZU,

MULTAN.

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 List of Contents Page

ABSTRACT 3
Chapter 1 Introduction 4
1.1 Traditional Techniques For Water Treatment 6

1.2 Historical Background 7

1.3 Types of Membranes 8
1.4 Classification of Membranes 8
1.5 Reverse Osmosis and Nanofiltration Membranes 10
1.6 Ceramic Membranes 16
1.7 Ion Exchange Membranes 18
1.8 Cellulose Based Membranes 21
Chapter 2 Experimental Work 25
2.1 Material Used 25
2.2 Chemicals Used 25
2.3 Synthesis Of Cellulose Acetate 26
2.4 Characterization Of Cellulose Acetate 29
2.5 Procedure For Production Of The Membrane 30
Chapter 3 Characterization 34
3.1 SEM Microscopy 34
3.2 FT-IR Spectroscopy 35
3.3 Raman Spectra 36
Chapter 4 Results And Discussion 37
Conclusion 39
References 39

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 Access to safe and clean drinking water is still a global problem. In developing
countries, about 80% of illnesses are linked to poor water and sanitation conditions. The
present study investigates the easy, cheap, most efficient and effective method of synthesis of
porous cellulose acetate membrane for the treatment of degraded water. Cellulose acetate was
used as polymeric substance and dissolved in acetone to make a polymeric suspension.
Calcium carbonate and glycerol was added in polymeric suspension to form dispersion which
is used to make membrane. Later, membrane was analyzed under SEM, FTIR followed by
Raman Spectroscopy. Analytical techniques confirmed the unique texture of the membrane
with pore diameter of approximately 1-5µm. Functional testing of the membrane using water
color and food coloring was also done which has given wonderful results as the synthesis of
the membrane was successful.

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Chapter 01

INTRODUCTION

Of all the water that exists on our planet, roughly 97% is saltwater and less than 3% is
freshwater. The distribution of water on the Earth’s surface is extremely uneven. Of
freshwater, 69% resides in glaciers, 30% underground, and less 1% is located in lakes, rivers,
and swamps. Looked at another way, only 1% of the water on the Earth’s surface is usable by
humans, and 99% of the usable quantity is situated underground. A sharp statistics of minor
water resources are listed below:

 Glaciers and other ice: 2.15 percent

 Groundwater: 0.61 percent
 Fresh water lakes: 0.009 percent
 Inland seas: 0.008 percent
 Soil Moisture: 0.005 percent
 Atmosphere: 0.001 percent
 Rivers: 0.0001 percent.

Fig. (1.1) Global water distribution

Despite the availability of fresh water not in comparable quantity as marine water but it is
present in sufficient amount to fulfill the demands of the world. However, the humans are
not preserving this gift of God for their successors because they are contaminating the fresh
water with pollutants or wastes which are excreted during different activities. Here are listed
some facts about the world where fresh water is depleting gradually:

 Globally, 70 percent of industrial waste is dumped directly into water.

 Even greater than the dumping of toxic industrial chemicals is the contribution of
domestic garbage and sewage, accounting for 80 percent of water pollution globally.

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  Asia has the highest number of polluted rivers in the world, mostly due to its
dumping of raw sewage and the resulting bacteria.
 The sacred Ganges River takes the prize for the world’s most polluted river, carrying
sewage, trash, animal carcasses and wasted food.
 Globally, 1.1 billion people do not have access to clean water and 2.4 billion people
do not have proper sanitation.
 Fourteen billion pounds of garbage mostly plastic, is dumped into the ocean every
year.
 Over 30 billion tons of urban sewage discharged into lakes, rivers and oceans each
year.
 Around 70% of industrial waste is dumped to water. 80% of the water pollution is
caused due to domestic sewage. More than 6 billion pounds of garbage, mainly plastic
end up in the oceans every year.
 According to recent FAO study, to feed the world in 2050, around 20% more fresh
water will be required to meet the demand.

The surface water assets of Pakistan chiefly comprise streams of the Indus River and its
feeders. The Indus River alone gives 65% of the
absolute waterway streams, while the portion of
Jhelum and Chenab is 17% and 19%
individually. Ground water supplies 90% of
domestic water in rural areas of Pakistan, 70%
of domestic water nationally, and over 50% of
agricultural water.

Fig. (1.2)Major causes of Water Pollution.

Unfortunately, Pakistan ranks at number 80 among 122 nations regarding drinking water
quality. Drinking water sources in Pakistan, both surface and groundwater are contaminated
with coliforms, toxic metals and pesticides throughout the country.

 98% of the richest people and only 79.2% of the poorest people in Pakistan have clean
water.

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 Pakistan is among the top 10 countries with the lowest access to clean water near to
home. only 20% of the country's population has access to clean drinking water.
 The remaining 80% populations depends on polluted water primarily contaminated by
sewerage (fecal, total coliforms, E. coli colonies), and secondarily by fertilizer, pesticides,
and industrial effluent.
 Pakistan is among the top 10 countries with the lowest access to clean water near to
home.
 Over 99.8% of death caused by poor quality of drinking water in the developing countries
according to World Health Organization (WHO) which make an increased need for safe
and adequate large amount of water which is free from physical, chemical, and biological
contaminations.
 Most of industries discharge discharges rich in organic and inorganic micropollutants
without prior treatment. The textile industry generates a huge volume of wastewater
which contains a variety of toxic agents like synthetic dyes, wetting agents, surfactants,
etc. Among the dyes synthesized, there are azo dyes. These are dyes widely used in the
manufacture of textiles and other consumer industries. They are dangerous for health
(carcinogenic to humans) and the environment for people at low concentrations. These
dyes have been used in the textile industry for the dyeing of textile products.

Literature Survey
Various approaches, with their inherent advantages and disadvantages, have been studied
to not only to remove microorganisms related to waterborne diseases but also for the
desalination of marine water. Traditional techniques are used for that purposes such as
boiling and using UV lamps (heat and UV based systems), flocculation, precipitation, and
adsorption (chemical treatment-based systems), settling and filtration (physical removal
processes).i

1.1 Traditional Techniques For Water Treatment

Physical Methods

These methods for treating water and wastewater do not depend on making chemical
or biological changes but on relying physical ones. The most popular physical methods to
control pollution of water are Sedimentation, Degasification and Filtration.ii

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Chemical Methods

An additional method for reducing discharge of pollutants and wastewater into water
bodies is the chemical method.

 Flocculation,
 Coagulation,
 Ozonation,
 Chemical precipitation,
 Adsorption and Ion exchange are different chemical methods used for safe disposal
of contaminants.iii

One of the wastewater treatment technologies that have seen a major boost over this
period is membrane technology. Membrane technology has grown significantly in the last
couple of decades due to the benefits it offers in water and wastewater treatment. With
significant reduction in the size of equipment, energy requirement and low capital cost,
membrane technology offers many prospects in wastewater treatment.iv

1.2 Historical Background

Membranes emerged as a viable means of water purification in the 1960s with the
development of high-performance synthetic membranes. Implementation of membranes for
water treatment has progressed using more advanced membranes made from new materials
and employed in various configurations. An increasing scarcity in fresh water sources fuelled
a push towards alternative resources such as ocean water. In the 1970s, exploration began
into using membranes for water desalination. Proving successful at producing purified water
from salt water, membranes became a viable alternative to evaporation-based technologies in
the water treatment market. Over the years, purified water standards have become more
stringent, and a plethora of new applications have appeared. However, membranes have risen
to the challenge and continue to perform efficiently and effectively.v

Definition of Membrane:

Basically, a membrane is a barrier which separates two phases from each other by
restricting movement of components through it in a selective style.vi

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 1.3 Types of Membranes

Water treatment processes employ several types of membranes. They include

 Microfiltration (MF),
 Ultrafiltration (UF),
 Reverse Osmosis (RO),
 And Nanofiltration (NF) Membranes.

MF membranes have the largest pore size and typically reject large particles and various
microorganisms. UF membranes have smaller pores than MF membranes and, therefore, in
addition to large particles and microorganisms, they can reject bacteria and soluble
macromolecules such as proteins. RO membranes are effectively non-porous and, therefore,
exclude particles and even many low molar mass species such as salt ions, organics, etc. NF
membranes are relatively new and are sometimes called “loose” RO membranes. They are
porous membranes, but since the pores are on the order of ten angstroms or less, they exhibit
performance between that of RO and UF membranes.vii

Figure (1.3) Range of nominal membrane pore sizes

1.4 Classification of Membranes

Characteristically, membranes can be classified as isotropic or anisotropic.viii

Isotropic Membranes:

Isotropic membranes are uniform in composition and physical structure. They can be
microporous; in which case their permeation fluxes are relatively high compared to when

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they are nonporous (dense) where their application is highly limited due to low permeation
fluxes. Isotropic microporous membranes are widely applied in microfiltration membranes.

Anisotropic Membranes:

Anisotropic membranes on the other hand are non-uniform over the membrane area
and are made up of different layers with different structures and composition. These
membranes have a thin selective layer supported by a thicker and highly permeable layer.
They are particularly applied in reverse osmosis (RO) processes.

Classification In Terms Of Membrane Material Make Up:

In terms of membrane material make up, membranes are classified as either organic or
inorganic.

Organic Membranes:

Organic membranes are made from synthetic organic polymers. Mostly, membranes
for pressure driven separation processes (microfiltration, ultrafiltration, Nano filtration and
reverse osmosis) are made from synthetic organic polymers. These include polyethylene
(PE), polytetrafluorethylene (PTFE), polypropylene, and cellulose acetate among others.

Inorganic Membranes:

Inorganic membranes are made from such materials as ceramics, metals, zeolites, or
silica. They are chemically and thermally stable and used widely in industrial applications
like. separation, ultrafiltration, and microfiltration

Figure (1.4) Classification of membranes for water purification in terms of pore size and retained species.

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 According to particle size of retained species, water purification systems such as
reverse osmosis (RO), nanofiltration (NF), ultrafiltration (UF) and microfiltration (MF) have
been also introducedix. A description of membrane types with corresponding pore diameter
and retained species is shown in Figure (1.4).

Significant progress has been made in research on RO and NF membranes made from
different materials for desalination applications. Extensive study on the types of RO and NF
membranes are visualized in the figure.

Figure (1.5) Representative reverse osmosis (RO) and nanofiltration (NF) membranes for water treatment.

This paper also reviews the growth and achievement in organic and inorganic
membrane studies for RO and NF procedures. The review will start by introducing the
synthesis method and structural properties of recent RO and NF membranes, followed by
discussing and comparing water purification performance of representative RO and NF
membranes made from organic and inorganic materials.x

1.5 Reverse Osmosis and Nanofiltration Membranes

Polymeric Membranes

Polymeric/organic RO and NF membranes have dominated the global market since

1980 due to their excellent performance and low cost. It can be seen that current market is
dominated by thin-film composite (TFC) membranes due to their outstanding performance.
Important polymers that are being used for making RO and NF membranes are polyamides,
cellulose acetate, cellulose diacetate, cellulose triacetate, piperazine, etc. Polyamide is a

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macromolecule containing recurring amide (-CO-NH-) groups, and can be found both
naturally and artificially. Examples of natural polyamide are wool, silk, and angora. In this
section, two classes of organic membranes made from different polymeric materials are
reviewed.xi

Thin-Film Composite Membranes

TFC membranes were invented by Cadotte in the 1970s, but were not widely used
until the second half of the 1980s. Polyamide (PA) membranes were developed by Hoehn and
Richter and had good water purification performance. The main drawback of PA membranes
was susceptibility to free chlorine attack. After development of TFC membranes, it was
found the PA TFC membranes had outstanding separation performance as well as better
chlorine resistance. The structure of a PA TFC membrane consists of a thin selective barrier
layer on a porous support. The support has a microporous structure (UF membrane),
providing mechanical strength and high-water flux, and the barrier layer has a function of ion
separation. Compared with CA membranes, which can only be made from linear, soluble
polymers, TFC membranes have more desirable characteristics. Many materials (linear and
crosslinked polymers) and approaches can be used to synthesize or modify the porous support
and barrier layer individually to optimize the thermal and chemical stabilities, permeability,
salt rejections, etc.

Figure (1.6) Thin-film composite membrane structure.

The porous support plays an important role in providing mechanical strength to

withstand high pressure during RO and NF processes. Meanwhile to form a defect-free

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barrier layer, the surface of the support needs to be uniform and smooth. Polysulfone is one
of the most significant microporous supports for TFC membranes. The surface pore size of
polysulfone support ranges from 1.9 nm to 15 nm, with a surface porosity up to 16%. The
selectivity generally increases with decreasing pore size. Since polysulfone shows good
structural stability in a wide pH range, barrier layers made from highly acidic or alkaline
precursors can be coated on polysulfone substrates. The disadvantages of polysulfone include
poor weatherability, low chlorine resistance, and prone to stress cracks. Adding nanoparticles
and applying new preparation methods are two main approaches to improve polysulfone
supports. A chlorine-resistant TFC membrane can be made by metalation sulfochlorination of
polysulfone. Plasma treatment on polysulfone support results in the exhibition of
hydrophobicity, which optimizes chlorine resistance and water permeability. xii

Metal Oxide Membranes

Compared to polymeric membranes, inorganic membranes offer higher chemical

stability and stronger mechanical properties. Metal oxides such as alumina, zirconia, and
titania form an important class of ceramic membranes. Conventionally, a RO metal oxide
membrane has an asymmetric structure consisting of a thick microporous (>50 nm) support,
an intermediate mesoporous (2–5 nm) layer, and a thin selective (<1 nm) top layer. A NF
metal oxide membrane has similar structure as RO metal oxide membrane but contains no
selective top layer. The most widely used approach for preparing metal oxide ceramic
membranes is sol-gel method, which converts precursor solutions into solid membranes in
four steps: precipitation reaction first happens between hydrolyzed precursors, followed by a
peptization reaction in which precipitation transforms into a colloid sol. The stable soil then
coated on a porous support and gelates during drying. Finally, high temperature sintering is
applied to the membrane to optimize mechanical properties and pore structure. In order to
make homogeneous membranes with fewer defects, colloidal particles are dispersed
uniformly in the solvent by stabilizers such as nitric acid, ethanolamine (MEA) and
triethylenetetramine (TETA). Since complex fabrication process of multi-layered membranes
as well as expensive precursor materials indicating high manufacturing cost, simplified
synthesis method and use of cheap materials will reduce the production cost and accelerate
the development and commercialization of ceramic membranes.

One of the most widely studied inorganic membranes is alumina membrane, which
has an average pore size of 2–5 nm (MWCO of 3000–1000 Da) and is commonly used in NF

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systems or as an intermediate layer in RO membranes. Alumina membranes with pore size
smaller than 1 nm has been made, but showed low permeability (5 LMH/bar) and cannot be
used for industrial purposes. Wang el al. has prepared a supported γ-Al2O3 hollow fiber
membrane with a mean pore size of 1.61 nm that demonstrates a high-water permeability of
17.4 LMH/bar. This membrane exhibits good selectivity for multivalent ions such as Ca2+
(84.1%), Mg2+ (85%), Al3+ (90.9%) and Fe3+ (97.1%), but very low retention of monovalent
ions such as NH4 + (27.3%) and Na+ (30.7%). Recent studies focus on surface modification
of alumina membrane to further improve its purification performance. For instance, a mixed
matrix carbon molecular sieve (CMS) and α-Al2O3 membrane fabricated by vacuum-assisted
impregnation method has a water flux up to 25 kg m−2 h −1 and a salt rejection between 93%
and 99% when tested using 3.5 wt% NaCl (seawater) at 75 ◦C.

Zirconia and titania are other popular materials for ceramic membranes. In sol-gel
method, zirconium alkoxides are often used as precursors to prepare zirconia sols. However,
some zirconium alkoxides such as zirconium prop oxide is water-reactive, which could
produce agglomerates rather than stable nanoparticles. Therefore, at the beginning few
laboratories had successfully synthesized zirconia membranes. In 1998, Garem et al.
discovered that adding 13 mol% magnesium would enhance the chemical and thermal
stabilities of zirconia sols. Since then many stabilizers have been investigated for preparing
zirconia membranes. Glycerol has been introduced into the sol-gel process to make ZrO2 NF
membranes for treating high-salinity wastewater. More specifically, glycerol binds to the
surface of ZrO2 nanoparticles as a capping agent and prevents phase transformation during
calcination. Compared with alumina and zirconia membranes, the surface pore size and phase
composition of titania membranes can be controlled by synthesis procedure. Anatase is the
most preferable crystal form of titania due to its exceptional stability and narrow pore size
distribution. A TiO2 membrane with a pore diameter of 4 nm has been fabricated successfully
by gentle heat treatment and remained stable in various solutions (brackish water, sea water
and brine water) for over 350 h. In addition to traditional metal oxide membranes, composite
membranes made of two or more metal oxides is a current research focus. For example, a
bilayer membrane containing a TiO2 layer on top of a ZnAl2O4 layer has been prepared and
evaluated. It has been proved that compare to single layer membrane made from 50 mol%
TiO2 and 50 mol% ZnAl2O4 with similar pore size, the bilayer membrane which has opposite
surface charges could increase the electric interactions between membrane pores and filtered
ions, and therefore produces a higher salt rejection, especially for divalent salts. Another

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example of inorganic composite membranes is CoO-SiO2 membrane synthesized by Elma et
al. for desalination applications. The effects of cobalt addition (up to 35 mol %), feed solution
concentration (0.3–7.5 wt% NaCl), and operation temperature (22–60 ◦C) on purification
performance were investigated systematically. Experimental results showed the volume
fraction of silica mesopores increases with cobalt concentration, and with over 99.7% NaCl
retention rate at all times, the highest water flux of 20 kg m−2 h −1 was achieved for 0.3 wt%
feed solution at 60 ◦C. Furthermore, a series of studies confirm that silica membranes blended
with cobalt oxide exhibit not only excellent desalination performance but also robust
structures compared to single-element SiO2 membranes. In spite of prominent outcomes of
metal oxide RO and NF membranes, certain shortcomings such as raw material cost and
membrane thickness have hindered their commercialization for water purification. These
issues can be overcome by further reducing the membrane thickness or exploring other cheap
materials that have great chemical and thermal stabilities. Membranes that have strong
surface charges in aqueous environment are also attractive.xiii

Carbon-Based Membranes

In recent years, ordered mesoporous materials (OMMs) have attracted increasingly

research interests in addressing water pollution and water shortage problems. Among all
kinds of OMMs, ordered mesoporous carbons (OMCs) such as carbon nanotubes (CNTs) and
graphene possess important properties including large specific surface area, highly uniform
structure with tunable pore size and strong atomic bonds, thus have been selected as
promising candidates for wastewater treatment applications. As one of fullerene derivatives,
CNTs are cylindrical molecules composed of rolled-up graphite sheets with diameter ranges
from 1 nm to several centimetres. Based on the layers of graphite sheets, CNTs can be further
classified into single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes
(DWCNTs) and multi-walled carbon nanotubes (MWCNTs). For water desalination and
purification applications, CNTs can be fabricated into standalone membranes or incorporated
with other materials in many formats. Pure graphene has a closely packed structure which is
impermeable to gas and liquid molecules. Nano porous graphene can be fabricated either by
electrochemical modification of pristine graphene or by growth on supports from different
chemical reactions. The most commonly applied techniques to generate nanosized pores on
graphene structure include high-temperature oxidation, ultraviolet (UV) ozone treatment and
plasma etching. Sub-nanometre-sized pores on monolayer graphene have been created
successfully for nanofiltration and desalination applications. During synthesis process, small

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defects were first introduced by ion bombardment and further enlarged by oxidative etching.
The experimental results revealed that the separation mechanisms of the porous graphene
membrane at short and long oxidation periods are electrostatic repulsion and steric size
exclusion, respectively. Graphene oxide (GO), chemically converted from graphene
nanosheets, has oxygen functional groups such as hydroxyl and epoxy which enable it to
have better water dispersibility than graphene. Nair et al. invented a GO membrane consisting
of closed-packed GO sheets that only allow water molecules to travel through and
concurrently hinder the motion of other species. Similarly, Zhao et al. designed a free-
standing GO membrane in which the GO sheets are crosslinked by Ca2+ from Congo red
dye.xiv

Mixed Matrix Membranes

Mixed matrix membranes (MMMs), a currently popular area of research, are made by
incorporating inorganic fillers into organic matrices. Although TFC membranes have
excellent salt removal performance, there is a trade-off between permeability and selectivity.
The main advantage of MMMs is to combine the low manufacturing cost, outstanding
selectivity and high packing density of polymeric materials with long-term stabilities, high
mechanical strength and regeneration capability of ceramic materials. One type of MMMs is
a polymeric membrane blended with inorganic nanoparticles, which can be prepared by
dispersion crosslinking, interfacial polymerization, or dip coating. Inorganic fillers that have
been investigated for this purpose include titania, zeolite, silica, alumina, etc., and
experimental results indicate the addition of inorganic nanoparticles alter the polymeric
structures and effect the transportation of molecules through membrane pores. Therefore, it is
not surprising that small inorganic nanoparticles would improve the water purification
performance of organic membranes. Titania is widely used in anti-fouling coating due to its
photocatalytic property. Kim et al. studied the influence of TiO2 fillers on the properties of
carboxylate groups functionalized TFC membranes and found the carboxylate groups help
the adsorption of titania on TFC membrane surface, which result in very good anti-biofouling
properties, especially under UV excitation. Such a hybrid RO membrane also has stable
surface structure since no significant loss of titania particles was observed after being tested
for 168 h. Researchers also recognized the addition of zeolite and silica nanoparticles
increases the surface roughness, contact angle, and water flux. NaA zeolite nanoparticles are
the first successfully synthesized zeolite particles with low contact angle (<5◦) and RO
ranged pores (~0.5 nm). MMMs prepared with NaA zeolite fillers by interfacial

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polymerization method have many outstanding properties, that is, more negatively charged
and hydrophilic surface with increasing zeolite content, enhanced water permeability, and
better water purification performance. Composite membrane synthesized from carbon-based
materials and organic materials is another type of MMMs.xv

There are also other types of membranes which are equally impactful in water treatment.
These are:

1. Ceramic membranes
2. Ion exchange membranes

1.6 Ceramic Membranesxvi

Nature-based ceramic membranes made from clay materials such kaolin, ball clay,
bauxite, and bentonite. Other waste materials, such as rice husk ash and aluminium dross,
have also been utilized to make ceramic membranes. Asymmetric structures are common in
ceramic membranes and used for water and wastewater treatment, with a thin selective layer,
intermediate layer(s), and permeable supporting layer.

Categorization of Ceramic Membranes

Ceramic membranes can be categorized into two categories according to their structure:

Porous Membranes

Porous ceramic membranes are usable in high temperature operations and aggressive
environments because they have the advantages of high porosity, high temperature and
chemical resistance. Pore diameter of microporous inorganic membranes is smaller than 2
nm (0.5–2 nm) and they are under the category of porous membranes. Microporous inorganic
ceramic membranes may be amorphous or crystalline (zeolite). Many microfiltration
applications depend on using porous ceramic membranes such as: gas purification,
membrane distillation and separation of water and oil

Dense Membranes

When polycrystalline ceramics or metals are used to fabricate membranes, those

produced membranes are called dense inorganic membranes. Dense inorganic membranes
allow permeation of gases through its crystal lattice. Dense membrane (<0.5 nm) materials
are ideally selective for O2 or H2 molecules.

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Preparation of Ceramic Membranes

They're made by depositing one or more active layers of desirable materials (TiO2,
ZrO2, ZnAl2O4, zeolite, and so on) on an inorganic membrane support made of mineral clays.
Various membrane supports for microfiltration and ultrafiltration have been developed using
a variety local mineral clay with unique qualities from Morocco, Tunisia, China, and Algeria
(porosity and pores diameter). Ceramic membranes can be fabricated by different techniques
such as slip casting, tape casting, pressing, extrusion, sol-gel process, dip coating, chemical
vapor deposition, and anodic oxidation. The selected production method greatly depends on
the desired membrane structure and the specific application. The following steps describe the
preparation of ceramic membranes:

a) Formation Of The Suspension: by mixing a suitable liquid with the starting powder

b) Forming: Where the prepared suspension is packed into membrane precursor with the
required shape such as flat sheet or tube.

c) Heat Treatment: Consolidation of the prepared shaped precursor by a heat treatment

process. Firing step is noted to be the most important step in preparation of ceramic
membranes. On the other hand, sol-gel and CVD preparation methods can be used to
produce multi-layers’ membrane before being fired by coating a membrane support with the
required layers.

Advantages of Ceramic Membranes

Ceramic membranes offer many advantages to polymer and inorganic membranes such as:

a) They are environmentally friendly.

b) Ceramic membrane filtration is a mild and highly selective process without phase
transformation.

c) They are usually characterized by low running costs whether through closed production
cycles or continuous processes.

d) Owing to the very nature of ceramic materials, they are stable thermally, chemically,
mechanically and physically. They can withstand very high temperatures, extremes of pH (0
to 14), and operating pressures up to 10 bar.

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e) They are not affected by bacteria.

f) They are regenerated easily after being used.

g) The membrane support (aluminium oxide or silicon carbide) provides maximum

permeability and excellent mechanical stability.

h) They usually show excellent separation properties and long working life

Disadvantages of Ceramic Membranes

Ceramic membranes suffer however from the following drawbacks compared to

polymeric types:

a) They have small surface area per unit volume.

b) As compared to polymeric membranes, their densities are higher.

c) Also, the production costs are higher because of the use of costly raw materials and more
complex fabrication procedures.

1.7 Ion Exchange Membranes

Electro-membrane processes are membrane-based electrochemical separation process

in which ion-exchange membranes (IEMs) and electrical potential are used to separate ionic
species from aqueous solution and other uncharged components. In IEMs functional groups
are fixed to the polymer matrix of the membrane and functional groups partially or
completely exclude ions of the same charge from the membrane.xvii

Recent Developments in IEMs:

Ion exchange membranes (IEMs) are undergoing prosperous development in recent

years. More than 30,000 papers which are indexed by Science Citation Index Expanded
(SCIE) have been published on IEMs during the past twenty years (2001–2020). Especially,
more than 3000 papers are published in the year of 2020, revealing researchers’ great interest
in this area.xviii

There are three types of IEMs:

(i) cation-exchange membranes (CEMs) in which acidic groups are fixed into the
membrane matrix.

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(ii) anion-exchange membranes (AEMs) in which basic groups are fixed into the
membrane matrix.
(iii) (iii) bipolar membranes (BPMs) can be considered as a novel composite ion-
exchange membrane just like monovalent ion selective membranes with a thin
oppositely charged layer on the surface of the main membranes.

Functionalization
Typical cation-exchange groups are sulfonic acids (–SO3H), carboxylic acids
(COOH), phosphonic acids (–PO3H2) and phenolic hydroxide groups. Materials with such
groups fixed to a polymer backbone reject anions but allow the passage of cations. On the
other hand, ion exchange materials containing ammonium (–NR3 +; with R = H or organic
residue) or phosphonium (–PR3 +; with R = alkyl or aryl) groups are anion selective and
allow the selective transport of anions through the respective material. A bipolar membrane is
composed of two layers, namely the cation exchange layer (CEL) which is similar to a CEM
and anion exchange layer (AEL) which is similar to an AEM. When power is supplied, water
will dissociate into hydrogen ions and hydroxide ions at the interface of the two
layers.bipolar membrane is mainly used for electrodialysis applications.xix

(a) (b) (c)

Figure (1.7) Schematic illustration of some special types of IEMs. (a) Cross section of a Monovalent selective CEM. (b)
Monovalent selective AEM. (c) Cross section of an amphoteric IEM.

Preparation of Ion-Exchange Membranesxx

The IEMs are dense, non-porous and charged membranes. They contain
anionic/cationic fixed groups in the membrane matrix. The IEMs in sheet form are prepared

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from ion-exchange resins. However, the physicochemical properties (swelling, mechanical
and thermal stability) of IEMs are significantly different than ion-exchange resins (IERs)
because IERs are chemically weak and easily swell in electrolytic solutions. This problem
can be avoided by preparing membranes on a suitable support of the reinforcing materials or
without any support. Nowadays, various methods are being used for the preparation of IEMs.
On the basis of their microstructure, IEMs are also classified into heterogeneous and
homogeneous ion-exchange membranes.

Preparation of Heterogeneous Ion-Exchange Membranes

The fine IERs particles are commonly embedded into the binder to prepare
heterogeneous IEMs. Thermoplastic polymers (such as polyethylene (PE), phenol resins and
polyvinylchloride (PVC)) are used as a binder while, organic or inorganic ion-exchange
resins are used as the ion-exchangeable materials. Heterogeneous IEMs are prepared by (i)
mixing of an ion-exchange resins powder with an inert binder and then membranes are
reinforced with woven fabric or a net of polymers at appropriate pressure and temperature;
(ii) dispersion of an ion-exchange resin particles into a polymer solution to make a
suspension. The resultant suspension is transferred into a thin film by solution casting
method and then the solvent is evaporated at ambient temperature.

Preparation of Homogeneous Ion-Exchange Membranes

The homogeneous IEMs are made up of only ion-exchanging materials, and they are
prepared by various methods: (i) polymerization of monomers in which one of them contains
cationic/anionic functional groups; (ii) chemical modification of thin film to introduce
acidic/basic functional groups and (iii) functionalization of different thermoplastic polymers
(poly (ether sulphone) (PES), poly(ethere ketone) (PEEK) and polyimide)) and then
functionalized polymers are dissolved in a suitable solvents to make the membranes.

Applications of IEMs

IEMs are extensively applied in various applications, which can be generalized into
two big categories, where the water-based category mainly includes electrodialysis, diffusion
dialysis and membrane capacitive deionization, while the energy-based category mainly
includes reverse electrodialysis, fuel cells, redox flow battery and electrolysis.

20 | P a g e
Limitations

Different resins are used to synthesize IEMs, are chances of membrane fouling every
time. Calcium sulphate fouling, Iron fouling, Adsorption of organic matter, organic
contamination from the resin, Bacterial contamination & Chlorine contamination are the real
major limitations in IEMs made up of resins.

Another polymer-based membrane technology called cellulose-based membranes are

the most Important in terms of their diversity, efficiency and most noticeably their synthetic
ease. As, it is our main topic of the research, detailed introduction, methodology, limitations
and novelties to diminish these limitations are emphasized.

1.8 Cellulose-Based Membranesxxi

The initial leader in the RO membrane market was the Loeb-Sourirajan Cellulose
acetate (CA) membrane. These CA membranes were asymmetric. CA membranes are made
from acetylated cellulose. Cellulose is a naturally occurring polymer found in plants such as
cotton. It is a linear, rod-like material that is relatively inflexible, which renders CA
membranes mechanically robust. Acetylation of the cellulose occurs via the following
reaction:

The degree of acetylation describes how many of the pendant OH groups on the
cellulose are replaced with acetyl groups, CH3COO. The degree of acetylation can range
from 0 to 3 where 0 represents unreacted cellulose and 3 corresponds to completely
substituted cellulose, also called cellulose triacetate (CTA). The degree of acetylation has a
large effect on the resulting membrane properties. The filtration performance of CA
membranes depends on the degree of acetylation. For instance, CA membrane with 40 wt%
acetate and a 2.7 degree of acetylation had a salt rejection between 98% and 99%. Higher
acetylation will result in higher selectivity but lower water permeability. A high degree of
acetylation gives high salt selection but low permeability. Lower degrees of acetylation yield
membranes with lower rejection but higher 8 flux. Commercial CA membranes used for

21 | P a g e
reverse osmosis have a degree of acetylation of about 2.7. This composition provides a good
balance between salt rejections and permeate flux. CA membranes are stable in pH range 4–
6. Some membranes also use blends of CA and CTA. Blending CA with CTA increases the
mechanical stability and resistance to hydrolysis but decreases the permeability.

Synthetic Means
There are different ways to synthesize CA membranes using different chemicals and
different approaches. The general synthesis process of CA membrane is called phase
inversion method. Cellulose acetate is first dissolved in an organic solvent or solvent mixture
to form a casting solution. Then the solution is coated on a flat or tubular support. Finally,
the support is immersed in a non-solvent bath, where polymer coagulation occurs and a CA
membrane forms.

Pore Forming Concept in CA Membranes

A procedure for the production of mesoporous microfiltration membranes by

removing a nanoparticle pore template was developed by Kellenberger et al. In their method,
calcium carbonate nanoparticles were used as pore templates to fabricate polymeric
membranes with tunable pore sizes. This technique was upscaled to an industrial level and
resulted in the development of the commercially available DrinkPure water filter. The key
part of this water filter is a microfiltration membrane that is produced via pore templation
using calcium carbonate nanoparticles. The industrial production of this membrane is easy
and cheap, but it relies heavily on sophisticated machinery for processes such as ball-milling,
dispersion coating, and solvent evaporation.

Advantages

CA membranes offer several advantages over other RO membranes on the market

today. They are relatively easy to make and they have excellent mechanical properties. They
are also relatively resistant to attack by chlorine. CA membranes can tolerate up to 5 ppm of
free chlorine, which is much higher than the tolerance shown by other membranes such as
those based on aromatic polyamides.

Limitations

CA membranes also possess shortcomings which new membranes have tried to address.
Followings are limitations which can be monitored:

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  Fouling

A major problem posed by CA and is fouling. In general, fouling occurs either on the
surface of a membrane or within its pores, and it causes a decrease in flux. There are four
major types of fouling: biofouling, scaling, organic, and colloidal.xxii

A. Biofouling:

Biofouling results from microbial contamination of feed water and produces a biofilm on
the surface of the membrane, which increases the resistance to water permeation through the
membrane.

B. Scaling:

Scaling arises from the precipitation and deposition of salts on the membrane surface.

C. Organic fouling:

Organic fouling comes from substances such as hydrocarbons which coat the surface
and/or plug pores in the porous support layer.

D. Colloidal fouling:

Colloidal fouling mainly stems from particles, such as clay or silica, accumulating on the
surface of the membrane.

 CA membranes tend to hydrolyse over time, which decreases their selectivity.

 Also, they are extremely sensitive to changes in pH and are stable only in pH ranges
of 4 to 6.
 Salt rejection of CA membranes decreases as temperature increases. Therefore, feed
water temperature typically does not exceed 35°C’.

Novelties to Diminish Limitations

 Various types of nanoparticles has been used for modification of organic membranes,
such as SiO2, Al2O3, Fe3O4 and TiO2 which aims to improve the performance and
antifouling properties of the membranes. Among all, TiO2 exhibited outstanding
antifouling and antibacterial properties and it can be potentially used for membrane
performance enhancement.
 It is investigated that antibacterial properties of membrane can be entrapped with
TiO2. The TiO2 modified nanocomposite membrane exhibit improved antibacterial

23 | P a g e
 properties with the aid of UV light due to photocatalytic property of TiO2. However,
the presence of TiO2 could change the membrane surface from hydrophobic to
hydrophilic due to the presence of hydroxyl group.xxiii
 Coating phospholipid polymer on CA membrane during phase conversion resulted in
a fouling-resistant membrane with high water flux.
 Dispersing silver nanoparticles on CA membrane surface can increase its biological
stability while maintain the permeability and salt rejection.
 A small percentage of mineral fillers such as aluminium oxide improved the
compaction resistance of CA membranes remarkably.

Finally, in this paper research has been made on the synthesis of cellulose acetate
membrane. We have tried to synthesize at cheap cost and more efficient cellulose acetate
membranes with readily available chemicals and instrumentation. Cellulose acetate can
be used as polymeric substance to develop the main framework of the membrane. To
make pores of desired size in the membrane, calcium carbonate is used. Calcium
carbonate particles imbedded in the matrix of the membrane can be removed by the action
of hydrochloric acid. Acetone is used as organic solvent for dissolving cellulose acetate.
Glycerol is used as plasticizer to give stability and definite shape to membrane. Cellulose
acetate was prepared by using cellulosic material and action of the anhydrous acetic acid,
acetic acid and catalyst such as sulphuric acid.

24 | P a g e
Chapter 02
Experimental work
2.1 Material Used

The experiment utilizes infrastructure and materials available in an undergraduate level

chemistry laboratory as well as some additions, which can easily be obtained:

 Two 250 ml Schott flasks

 Kitchen blender with at least 800 W power (e.g. Philips HR 2195/04)
 50 small beakers
 Mirror or glass plate (148 x 210 mm or larger area)
 Scotch tape
 Ruler with stainless steel cutting edge or aluminium profile
 Two plastic basins for diluted hydrochloric acid and water bath
 Spatula
 Pair of scissors
 Filter flask
 Rubber ring
 Büchner funnel
 Büchner funnel filter
 Permanent marker
 Magnet stirrer
 Magnet stir bar
 Water and ethanol safety wash bottles
 Safety goggles
 Nitrile safety gloves (all the glassware’s were made up of Pyrex).

2.3 Chemicals Used:

 20 g Cellulose acetate (prepared in the lab).

 41g Calcium carbonate (Sigma-Aldrich No. 21069)
 17.6 g Glycerol (Sigma Aldrich Germany)
 5 litres 0.24 M HCl (prepared by Instructor from concentrated HCl solution)
 200 g Acetone (Sigma Aldrich Germany).
 Ethanol (Sigma Aldrich Germany).

25 | P a g e
  10 L water (demineralized)
 Watercolour
 Watercolour Pan Set
 Food colouring (e.g. Brilliant Blue FCF E133)

2.3 Synthesis of Cellulose Acetatexxiv

As cellulose acetate was not available in the store, it was prepared in the lab readily by a
recognized formulated synthesis process. Details of the synthetic process of cellulose acetate
are given below:

Cellulose is the most natural polymer and abundant renewable carbon source on Earth,
and is widely considered a long-term renewable fossil fuel alternative. The cellulose
conversion into high value cellulose esters and ethers has gained significant attention in the
fields of green and sustainable chemistry, and has proportioned the development of friendly
environmental technologies. Cellulose acetate (CA) is one of the most important esters of
cellulose due to its renewable source, biodegradability, nontoxicity, low cost, and very poor
flammability property.

Industrially, CA is produced by the reaction of cellulose with acetic acid and an excess of
acetic anhydride in the presence of sulfuric acid as the catalyst. The reaction is performed in
two-step process of acetylation, followed by a hydrolysis reaction in order to produce a CA
with the desirable degree of substitution (DS), about 2.45–2.5. This DS range confers high
solubility (in several types of solvent systems) and good melt properties.

Experimental

Materials

Chemicals used in this work were analytical grade. These were obtained from university
lab (Sigma Aldrich Germany), from university lab, and used without any further purification.

Raw material

Sugarcane straw was courtesy of the sugar and ethanol plant. Fresh sugarcane straw was
obtained from the manual harvesting. The material was dried at room temperature until the
dry matter content was above 10% of moisture content and placed in plastic bags until used.

26 | P a g e
Cellulose Extraction

Acid Pre-Treatment:

Acid pre-treatment was conducted in 4 L glass beaker flask with 10% (v/v) H2SO4
and 1/10 (w/v) solid/liquid ratio of dry SCS loading under stirring at 100 ◦C for 1 h. After the
reaction was stopped, the solid fraction was separated from liquid fraction by vacuum
filtration, and washed with distilled water until the yellow colour of the effluent was totally
removed and the pH was neutral.

Alkaline Pre-Treatment:

Alkaline treatment was conducted in 4 L polypropylene beaker flask with 5% (w/v)

NaOH and 1/10 (w/v) solid/liquid ratio of dry acid pre-treated material loading under stirring
at 100 ◦C for 1 h. After the reaction was stopped, the solid fraction was separated from liquid
fraction by vacuum filtration, and washed with distilled water until the dark alkali liquor was
totally removed and the pH was neutral. The material was dried at room temperature and
stored for subsequent chemical analysis.

Chelating:

The chelating process was carried out using 0.5% EDTA for 30 min at 70 ◦C in a
polypropylene bag with a final concentration medium of 10% (w/v). After de reaction, the
material was filtrated and washed with distilled water at 70 ◦C.

Bleaching:

Bleaching stage was performed with 5% (v/v) H2O2, 0.1% MgSO4 in polypropylene
bags for 1 h, at 70 ◦C under concentration of 5% (w/v). At the end of the process, the material
was washed with distilled water at 70 ◦C until pH 7.

Cellulose Acetate Synthesis

For the synthesis of CA, 24 mL of glacial acetic acid was added to 10 g of sugarcane
straw cellulose, and this mix was stirred at 37.8 ◦C for 1 h. Subsequently, it was aggregated
40 mL of glacial acetic acid and 0.08 mL of H2SO4 to the mixture, which was stirred for 45
min. After that, the mixture was cooled to 18.3 ◦C and 28 mL of acetic anhydride and 0.6 mL
of H2SO4 were added. Then, the temperature was elevated to 35 ◦C and the mixture was
stirred for 1.5 h. Then, a solution of 10.0 mL of water and 20 mL of glacial acetic acid was

27 | P a g e
added in small portions for 1 h under stirring. Finally, the material obtained was washed with
distilled water until pH 7.0.

Determination of the Degree Of Substitution (DS) Of CA:

0.1 g of cellulose acetate was added to 5 mL of 0.25 M NaOH and 5 mL of ethanol.

This mixture was left to stand for 24 h. After that, 10 mL of 0.25 M HCl was added to the
mixture and the system was left to stand for 30 min. Subsequently, the mixture was titrated
by a standard 0.25 M NaOH solution, using phenolphthalein as indicator. This procedure was
carried out in triplicate. The percentage of acetyl groups (%AG) was calculated by the
following equation

%GA = {[(Vbi + Vbt) ∗ b − (Va ∗ a)] ∗ M ∗ 100}/mac

where:

Vbi: volume of NaOH added to the system (L);

Vbt: volume of NaOH spent in titration (L);

µb: NaOH concentration (M);

Va: volume of HCl added to the system (L);

µa: HCl concentration (M)

M: molar weight of acetyl group (43 g mol−1)

mac: weight of cellulose acetate sample (g).

28 | P a g e
 2.4 Characterization of Synthesized Cellulose Acetatexxv

Infrared Spectroscopy

Figure (2.1) FTIR of sugarcane straw and extracted cellulose.

The cellulose acetate obtained presented a DS value of 2.72 ± 0.19 and a percentage
of acetyl groups of 41.05 ± 2.77%, characterizing it as a triacetate. The removal of the most
part of lignin was crucial to reach this result, as lignin competes with cellulose for the
acetylation reactants. The proceeding to extract cellulose also contributed to the almost
completed acetylation of sugarcane straw cellulose. During the process, the reactants, mainly
the NaOH, promoted the swelling of the fibers, increasing the accessibility of acetic
anhydride to the OH groups of cellulose and improving the activation of cellulose pulp for
the acetylation reaction. The cellulose activation stage has an important role. It is almost
impossible to obtain soluble CA (DS ≥ 2.0) without the activation stage. In this process, the
reactant diffuses into the inner layer of the cellulose fibre, ruptures both intra and
intermolecular hydrogen bonds, and degrades the crystalline region of fiber, raising the
accessibility to the OH groups which results in the increase of the DS value. FTIR spectrum
of CA is shown in comparison with cellulose spectrum in Fig (2.2).

Figure (2.2) FT-IR spectra of cellulose and cellulose acetate structure

29 | P a g e
Five main changes in CA spectra were observed:

1. Decrease of the band in 3400 cm−1, corresponding to the stretching of OH groups of

cellulose.

2. Rise of the band in 1750 cm−1, corresponding to the stretching of C O bond of ester
carbonyl.

3. Decrease of the band in 1650 cm−1, corresponding the absorption of water.

4. Rise of the band in 1360 cm−1, corresponding to the vibration of C H bond.

5. Rise of the band in 1220 cm−1, corresponding to the vibration of C O bond.

Table.(2.1) Results of DMA analysis of SCS membrane and membrane synthesized from commercial grade cellulose
acetate.

The decrease of the band in 3400 cm−1 is result of the OH group replacement for the
acetyl groups in cellulose structure. Hence, there was a rise in the vibration of C O and C H
bonds, present in the acetyl structure, and of C O bond, responsible for the link between
cellulose and acetyl group. The decrease of the band in 1650 cm−1 demonstrates that CA
presents a hydrophobic nature. A band in 1032 cm−1 was also observed, corresponding to
O=C-O-CH3 bonds, typical of cellulose acetate sp2 hybridization.

2.5 Procedure for Production of the Membranexxvi

Preparation of Cellulose Acetate Polymer Solution

The cellulose acetate polymer solution was prepared by mixing 20 g of cellulose

acetate with 200 g of acetone in a 250 mL Schott flask. A magnet was added to the flask, the
flask was closed (to limit solvent evaporation), and the polymer solution was stirred over a
period of 1 h using a magnetic stirrer. The mixing of the polymer solution was finished when
the solution became clear.

30 | P a g e
Preparation of Cellulose Acetate Dispersion

The whole cellulose acetate polymer solution was transferred into a kitchen blender.
Next, 41 g of calcium carbonate and 17.6 g of glycerol were added, and the suspension was
stirred for 3 min at the highest setting of the kitchen blender. The dispersion was put into a
fresh 250 mL Schott flask and closed to limit solvent evaporation. The kitchen blender was
immediately filled with water to precipitate the remaining dispersion, and the polymer waste
was disposed into the household refuse.

Production of Membrane Sheet

Two parallel edges of a mirror or glass plate were plastered with four consecutive
layers of Scotch tape, which will define the thickness of the membrane. Subsequently, the
surface was rinsed with a towel and small amount of ethanol. Approximately 10 g of the
cellulose−acetate polymer dispersion was transferred from the Schott flask to a smaller
beaker glass to facilitate the pouring process. This amount of dispersion was then poured onto
the mirror as an ∼1 in. wide stripe.

Figure (2.3) a) Cellulose acetate polymer solution b, c) Polymer-Particle dispersion in kitchen blender glass e) Scotch tape
on glass f) Transfer of dispersion onto glass surface g) Membrane sheet production with stainless steel ruler h) Drying of
membrane at ambient air i) Transfer of mirror or glass plate into diluted hydrochloric acid bath j) Removal of membrane
from glass surface k) Washing of membrane in water bath l) Drying of membrane.

31 | P a g e
 The stripe of dispersion was then distributed from the top to the bottom of the glass
plate using the edge of a stainless-steel ruler. The final membrane sheet was dried in ambient
air for 5 min.

Figure (2.4) Production of polymeric membranes using a kitchen blender. A calcium carbonate particle−polymer dispersion
is cast on a glass support and the solvent evaporated in ambient air. Acid bath incubation of the membrane dissolves the
calcium carbonate particles and yields a porous membrane.

Removal of Calcium Carbonate Particles

For the removal of the calcium carbonate particles, one plastic basin was filled with 5
L of water, and another basin was filled with 5 L of hydrochloric acid (0.24 M). The mirror
plate containing the membrane sheet was then submerged into the hydrochloric acid bath.
The membrane sheet loosened itself from the mirror plate, and gas bubbles indicated the
removal of calcium carbonate particles. After 10 min, the membrane sheet was transferred
into the basin containing only water and washed for another 5 min. Finally, the membrane
sheet was pulled out of the water bath and placed onto a kitchen towel. Another kitchen towel
was used to dry the membrane.

Functional Testing of Membrane

A standard filter for a Buchner funnel was placed onto the dried membrane sheet and
the shape of the filter copied using a permanent marker and then cut out of the membrane.
The cut-out membrane was placed cautiously onto a Buchner funnel on top of a suction flask.
A 20 mL portion of blue watercolour dispersion was prepared in a small beaker glass and
transferred onto the same membrane. The watercolour solution was filtered by applying
vacuum. Next, a 20 mL portion of an aqueous food colouring solution was prepared and also
filtered by means of the membrane. The suction flask and Buchner funnel were then washed,
and the two filtration experiments were repeated with a standard Buchner funnel filter.

32 | P a g e
Hazards

Safety goggles must be worn at all times. Nitrile safety gloves must be worn while
working with hydrochloric acid. Hydrochloric acid is corrosive. Acetone and ethanol are
flammable. Handle all chemicals employed with care and in the case of skin contact, wash
immediately with water and soap, and rinse for at least 15 min. In the case of eye contact,
rinse with water for at least 15 min.

33 | P a g e
Chapter 03
Characterization
3.1 SEM Microscopy

Characteristic for this type of membrane is its asymmetric structure. As apparent from the
cross-section image of the membrane, the size of the cavities increases from the top to the
bottom side of the membrane. On the images of the top- and bottom side one can see that the
removal of the calcium carbonate particles leaves behind small pores with a diameter of
approximately 1 – 5 µm. These pores enable the diffusion of water through the membrane,
but hamper the transport of dispersed watercolour pigments and bacteria.xxvii

Figure (1.3). Left: Cross-Section, Middle: Top side, Right: Bottom side

34 | P a g e
Figure (3.2) Scanning electron microscopy (FEI nova Nano SEM 450, 3 kV, spot size 2.5) images of cellulose acetate
membrane cross sections at various magnifications. Images on the top row show the membrane cross sections prior to
removal of the calcium carbonate pore template; images on the bottom row show the membrane cross sections after the
calcium carbonate pore template has been removed.

3.2 FT-IR Spectra

FT-IR spectra exhibit major changes, proving the functionalization of the used
membranes. Thus, after the partial hydrolysis of cellulose acetate membranes, in order to
increase the number of hydroxyl groups at the surface of the membrane, the band specific for
C=O decreases in intensity because the number of acetyl groups have been reduced during
the hydrolysis process. The 1750 cm−1 band, assigned to C=O groups, has the highest
intensity in cellulose acetate, which is highly diminished after hydrolysis with sodium
hydroxide. The band is still present in the case of other membranes, which indicates that the
hydrolysis of the membrane is not complete, leaving fewer C=O groups behind. In addition,
another decrease in intensity can be observed for the 1250 cm−1 band assigned to the etheric
groups C–O. This is also explained by the partial hydrolysis of acetyl groups in cellulose
acetate, but it can also be due to the hydrolysis of the polymer chains, as indicated by the
thermal analysis. In the case of cellulose acetate after treatment with sodium hydroxide (to
increase the number of –OH groups), band intensity increases due to the increase in hydroxyl
groups number.

35 | P a g e
Figure (3.3) Fourier transform infrared spectroscopy (FT-IR) spectra of synthesized CA, CA/APTES, CA/APTES/GA, and
CA/APTES/CAL membranes with details for the range 600–2000 cm−1 (left) and 500–4000 cm−1 (right). GA:
Glutaraldehyde.

Calmagite immobilization on the functionalized membrane surface can be observed in

the IR spectrum of the CA/APTES/GA/CAL membrane where, besides the cellulose acetate
corresponding bands, one can notice the presence of two additional bands at 1579 and 1520
cm−1 from the CAL structure. These peaks correspond to the stretching vibration of the C=O
and NH2 amide bonds and are consistent with the values reported in the literature.xxviii

3.3 Raman Spectra

Results were further supported by their respective Raman spectra. Several new peaks
attributed to the presence of new functional groups on the pristine membrane were clearly
visible. The intensities of the pristine membrane peaks were higher after functionalization,
resulting in an enhanced surface showed by resonance scattering.xxix

Figure (3.4). Raman spectra of synthesized CA, CA/APTES, CA/APTES/GA, and CA/APTES/CAL membranes .

36 | P a g e
Chapter 04

Results and Discussion

The method outlined above usually produced enough material for the production of 25
membrane sheets, each having the surface area of about 1/2 page. Removal of the calcium
carbonate particles using hydrochloric acid left behind pores with a diameter of
approximately 1−5 μm as shown in the scanning electron microscope images. Hydrochloric
acid dissolves the calcium carbonate particles, and carbon dioxide escapes as gas according to
the following chemical equation:

CaCO3(s) + 2H+ (aq) Ca+2(aq) + H2O (aq) + CO2(g)

Consequently, holes in the membrane are formed, which have the same size as the
calcium carbonate particles. For achievement of a good particle size (and resulting pore size),
the blending step is important. This step not only is required for the formation of a
homogeneous particle dispersion in the polymer solution, but also decreases the size of the
particles. The chosen blending time (3 min) ensures a good dispersion, and a significant
decrease in the particle size. Longer blending times, however, do not result in significantly
smaller particles (and pore sizes) because as the particles get smaller the shear stress acting
on the individual particles decreases as well, resulting in a minimal achievable particle size
(to achieve smaller particles more energy intensive mixing methods are required, e.g., ball-
milling).

Cross-section images of the membranes show highly inhomogeneous cavity sizes as

well as asymmetric membrane morphology: the size of the cavities increases from the top
side of the membrane (air side) to the bottom side (side facing the glass substrate). This can
be explained by the asymmetry of the drying process, where solvent evaporation only occurs
on one side (the air side) of the membrane and results in a polymer solubility gradient within
the material. On a similarly produced membrane based on poly (ether sulfone) (PES), Hess et
al. showed that glycerol and the template (in this instance, zinc oxide nanoparticles) are the
key parameters in controlling the pore size and pore gradient along the cross section of the
membrane.

The performance of the membrane was tested with a filter setup consisting out of a
suction flask and Buchner funnel. A watercolour dispersion and food colouring solution were

37 | P a g e
filtered, and both filtration results were compared. Watercolour paints are pigments (10−100
μm particle size) held together by a water-soluble binder. The pigments are insoluble,
coloured particles and are rejected by the membrane. Food colouring (e.g., Brilliant Blue FCF
E133) is completely soluble in water and therefore passes through the pores of the membrane.
The pores of standard filter paper used in school laboratories usually have a wider diameter
(>20 μm), and therefore, the pigments can pass the membrane relatively easily.xxx

There are some questions which can be raised by the learner. Questions with their
answers are given below for the reader’s ease.

What is the chemical nature of the watercolor?

As the watercolour does not pass through the membrane filter, the colour is not
dissolved in water, but consists of solid particles (pigments), which are larger than the pore
size of the membrane. This can further be confirmed by leaving the dispersion to stand for
several hours, as the pigmentary particles will sediment to the bottom of the solution.

What can be drinking water contaminants that will behave like the food colouring and
pass through the filter?

Viruses’ particles (most < 200 nm) and any dissolved chemical will pass through the
filter. This includes heavy metal ions (arsenic, chromium, selenium, lead etc.) as well as
dissolved organic chemicals such as hormones, chemical toxins (e.g. dioxins,
hexachlorobenzene, pesticides) and also bacterial toxins (enterotoxins).

What can be drinking water contaminants that will behave like the watercolour and be
removed by an advanced membrane filter with pore sizes in the 1 µm range?

Most bacteria are larger than 1 µm and can be removed by such a filter. This includes
E. coli, legionella, vibrio cholera, salmonella, shigella. Also, parasites (e.g. amoebae, giardia,
cryptosporidium) are potential water contaminants and larger than 1 µm and can be removed.

What can you say about the pore size of the commercial filter paper?

As the pigmentary watercolour travels through the commercial filter paper, the pore
size is larger than the particles in the dispersion. The pore size of the filter paper is therefore
larger than the pore size of the membranes made by the students.

38 | P a g e
 Chapter 05

Conclusion
In this paper, we present a new laboratory experiment that includes production of
porous membrane materials for water purification. In a three-step process, membranes are
produced at room temperature and tested with a solution of watercolour and food colouring.
The purpose the performed work was the development or synthesis of porous cellulose
membrane at cheap cost and by readily means. Cellulose acetate membranes that are
synthesized were characterized by different analytical tools to confirm that whether the
membranes have definite morphology and composition have or not. Pore size was also
determined. Ultimately, cellulose acetate membranes were developed with low cost, within
two labs and most importantly, all required features were also achieved in the membranes.

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39 | P a g e
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