CH AP T E R 1

An Overview of Membrane Science

and Technology

MEMBRANE DEFINITION CONTENTS

A membrane is defined as a thin sheet, film, or layer, which works as a selective
barrier between two phases that can be liquid, gas, or vapor. In other words, Membrane Definition.....1
a membrane is an interface between two adjacent phases acting as a selec- Historical and Key
tive barrier, regulating the transport of species between the two compartments Developments of
(Ulbricht 2006). Membrane
Technology.....................3
The membrane itself can be a solid, a liquid, or a gel. The membrane is con- Membrane Research
sidered as a molecular sieve constructed in the form of a film from more than Contributions before 1900.......3
Membrane Research
one layered material with fine mesh or small pores to enable the separation Contributions after 1900..........3
of tiny particles and molecules. It acts as a selective barrier, allowing specific
substances to pass through while retaining others. The ability of membranes to Membrane Science........7
differentiate among species is called selectivity. Membranes are used for the Membrane
separation of solute–solvent, solute–solute, particle–solute, and particles– Technology.....................8
solvents. Membrane Separation
Processes.......................9
According to the European Membrane Society, a membrane is an intervening
phase separating two phases and acting as an active or a passive barrier to the Membrane Materials...11
transport of matter between the phases adjacent to it. Inorganic Membrane
Materials................................12
Membranes can be porous or nonporous. In the porous membrane, the separa- Organic Membrane
tion process of a mixture of components is achieved by passing one or more Materials: Polymers..............13
Membrane Evaluation............14
components through the membrane (permeate fractions) and rejecting the
Membrane Evaluation
other components of the membrane (retentate fractions). Retentate is called Characteristics......................14
concentrate, as it is a concentrated media of rejected substances. For example, a Filtration Flux........................15
mixture of A, B, C, and D components can be separated by a porous membrane
Nanomaterials.............15
by rejecting C and D as retentate fractions and passing the A and B component An Overview of
permeate fractions through the pores of the membrane as shown in Fig. 1.1. Nanomaterials.......................15
The word membrane is used to indicate an interface or region of discontinuity Historical and Key Developments
between two phases. The membrane controls the zone at which compounds of Nanotechnology....................16
permeate through it. Thus the membrane can be also defined as a barrier, the General Properties of
Nanomaterials.......................16
purpose of which is to prevent the permeation of all compounds. The mem-
brane is able to control the rate at which compounds permeate (Mulder 1996).
1
Nanomaterial and Polymer Membranes. http://dx.doi.org/10.1016/B978-0-12-804703-3.00001-2
Copyright © 2016 Elsevier Inc. All rights reserved.
2 CHAPTER 1:   An Overview of Membrane Science and Technology

Conclusion...................18
Acknowledgement.......19
References...................19

FIGURE 1.1 Ideal principle of porous membrane process.

Thus the membrane can also be considered as a permeable medium. A specific

amount of energy is required to accomplish the separation of substances or
components. The minimum amount of energy, Wmin, required to accomplish
the separation is larger than the free enthalpy of mixing as shown by Wmin ≥
∆Gm = ∆Hm − T∆Sm.
Membrane processes are operations where the feed stream is divided into
two streams: a permeate and a retentate. A membrane, as applied to water
treatment, is a material that allows some physical or chemical components
to pass more readily through it than others. It is thus perm-selective, because
it is more permeable to those components passing through it—the perme-
ate—than those that are rejected by it—the retentate (Judd 2011). The reten-
tate, also called concentrate, is usually enriched with substances retained by the
membrane, whereas the permeate or filtrate is a stream passing through the
membrane, devoid of substances retained by the membrane. The membrane’s
role is to change the composition of a solution based on relative permeation
rates and to physically or chemically modify the permeating to regulate the rate
of permeation. From the other side, it is to conduct electric current, to prevent
permeation—to retentate. Depending on the membrane’s ability to alter the
chemical nature of the permeating species, membranes can be either passive
or reactive. Therefore, based on their ionic nature, membranes can be classified
into neutral or charged membranes.
 Historical and Key Developments of Membrane Technology 3

HISTORICAL AND KEY DEVELOPMENTS

OF MEMBRANE TECHNOLOGY
The history of the membrane started with the development of several materi-
als as natural or synthetic membranes for the separation of gases and vapors.

Membrane Research Contributions before 1900

Thomas Graham reported on the use of flat rubber membranes to study the
diffusion of gases and vapor species (Graham 1829; 1833). He reported the
solution-diffusion mechanism, which he observed using rubber as a liquid in
which the gas dissolves and diffuses to a concentration gradient. Before that in
1748, French cleric, Abbé Jean-Antoine Nollet discovered the phenomena of
water transport (Nollet 1748; 1779). Nollet placed spirit of wine in a vessel.
The mouth of the vessel was closed with an animal bladder, and then he im-
mersed the vessel in the water. Because it was more permeable to water than to
wine, the bladder swelled and sometimes even burst, demonstrating semiper-
meability for the first time. Eighty years after that, the term osmosis was coined
by the French physiologist Henri du Trochet (du Trochet 1828).
Mitchell reported on gas permeation through natural rubbers (Mitchell 1831).
Schoenbein reported on the synthesis of cellulose nitrate, the first synthetic (or
semisynthetic) polymer (Schoenbein 1846). The frog battery is an example of
a class of biobatteries, which can be made from any number of animals. The
general term for an example of this class is the muscular pile. The first well-
known frog battery was created by Carlo Matteucci in 1845, but there had been
others before him. Matteucci also created batteries out of other animals, and
Giovanni Aldini created a battery from ox heads.
Fick made a synthetic membrane of cellulose nitrate coated onto a ceramic thim-
ble in his classic study “Ueber Diffusion” to dialyze biological fluids (Fick 1855).
Fick worked on the dialysis of solutions through artificial membranes formed
from collodion. Based on his experiments, he published his law of diffusion,
which is still in use. Graham worked with isolated bacteria and “colloids from
crystalloids.” Graham is credited with the use of the term dialysis as he reported
the dialysis experiments with synthetic membranes. He also demonstrated that
rubber films exhibited different permeabilities to different gases. A device con-
sisting of flat membranes with a vacuum on one side was reported for perme-
ability rate measuring (Graham 1866). Graham postulated mechanisms for the
permeation process (Graham 1861; 1866). Table 1.1 summarizes the achieve-
ments in the field of membrane technology made before 1900.

Membrane Research Contributions after 1900

John William Strutt (1900) determined the relative permeability of oxygen,
nitrogen, and argon in rubber (John William Strutt 1900). Later on, polymer
4 CHAPTER 1:   An Overview of Membrane Science and Technology

Table 1.1  Membrane Research Contributions before 1900

Development Contributor Year
Discovery of osmosis phenomenon in natural Nollet 1748
membranes
Research on anisotropy of natural membranes Matteucci 1845
Laws of diffusion Fick 1855
Dialysis, gas permeation Graham 1861
Synthetic membrane from nitrocellulosis Fick 1865
Solution-diffusion transport mechanism Graham 1866
Research on gas separation on rubber membranes Graham 1866
Research on osmosis on synthetic membranes Traube 1867
Research on osmosis on ceramic membranes Pfeffer 1877
Research on osmosis phenomena Gibbs; van’t Hoff 1897;1888
Theory of osmosis phenomena Gibbs; van’t Hoff 1897;1888
Osmotic pressure Pfeffer; Traube; 1860–1887
van’t Hoff

membranes were used for the separation of gases, and so forth (Glater 1998;
Matthes 1944). Traube and Pfeffer prepared artificial membranes, and they
developed the van’t Hoff osmotic pressure relationship as a result of their
work with osmotic phenomena. Bechold coined the term ultrafiltration in 1906
(Bechold 1907, Bechold & Schlesinger 1931). Michaels (1968) further de-
veloped ultrafiltration. Zigmondy developed asymmetric microporous filters
made with a fine porous skin on the feed side and open structure on the per-
meate side (Zsigmondy 1922). The tightest of the ultrafiltration membranes
were made from cellophane or cellulose.
Reverse osmosis was initiated and studied in the 1920s. It was rediscovered by
Reid and his coworkers in the 1950s. The practical phenomenon of hemodialy-
sis was developed by Kolff (Kolff & Berk 1944). Reverse osmosis, also called hy-
perfiltration, for desalinating seawater was initiated by the Office of Saline Water
to meet future water demands. Because of their large pore size, microporous
membranes were not suitable for desalination (Sing, Hoffman & Judd 2006).
Reid and Berton discovered polymeric membranes that could show high salt
rejections. Their challenge was that the membranes were too thick and required
casting a thin film without imperfections. Because the thickness was about
6.0 mm, which is not enough to provide high flux, the water flux was nonprac-
tical. This problem was relatively solved when Loeb and Sourirajan, during
1958 to 1962, discovered how to make asymmetric membranes of small thick-
ness and with controlled pore sizes (Loeb 1981; Loeb & Sourirajan 1963). The
membrane was made of very thin cellulose acetate film, supported by a fine cel-
lulose acetate porous substrate, using the phase-inversion method, and it was
called L-S membrane (Loeb & Sourirajan 1963). This development was a great
breakthrough in membrane technique, and especially in the pressure-driven
 Historical and Key Developments of Membrane Technology 5

FIGURE 1.2 A representation of an asymmetric, skinned membrane.

separation process used for the purification of water. When characterized un-
der an electron microscope by Riley in 1964, the membranes were found to
be skinned with a thickness of about 0.1 mm (Lonsdale 1982). The skinned
(asymmetric) membrane has a top layer that is skinlike and a bottom side that
has large pores over a nonwoven support fabric, which provides mechanical
strength to the membrane, as illustrated in Fig. 1.2. They were capable of pro-
ducing a flux of 5 to 11 gallons per square foot per day of 0.05% NaC1 water,
under a pressure of 100 to 135 bar(g).
Westmoreland and later Bray invented the spiral-wound module, which was
more efficient than the tube-in-shell module. The spiral-wound membrane
can be viewed as a plate-and-frame arrangement that has been rolled up. The
original module had a single leaf of membrane, whereas modern spiral-wound
modules contain multileaf membranes.
After that, cellulose triacetate hollow-fiber membranes and the means to mod-
ularize these fibers were developed by Mahon, McLain and others (Mahon
1966; McLain 1969; McLain and Mahon 1969). However, a quite competitive
development with the L-S type membrane, the hollow-fiber aromatic polyam-
ide membranes, was prepared by Henry Hoehn and George Milford at DuPont
in the late 1960s. These membranes were prepared with a solution which was
spun into hollow fibers with a 42 mm inside diameter and an 85 mm outside
diameter with a skinned structure on the shell side. Although the water flux was
well below that exhibited by cellulose acetate membranes, the salt rejection
was higher. Therefore, to enhance the flux, several hundred thousand of the fi-
bers are required to be incorporated into modules containing several thousand
square feet of membrane area. This development was key to the development
of hollow-fiber ultrafiltration and microfiltration. Tables 1.2 and 1.3 summa-
rize the achievement in the field of membrane technology after 1900 (Fer-
ry 1936; Kołtuniewicz 2006; Koros 2004; Loeb & Sourirajan 1963; Loeb 1981;
Lonsdale 1982; 1987; Michaels 1968; Petersen 1993; Strathmann 2001).
6 CHAPTER 1:   An Overview of Membrane Science and Technology

Table 1.2  Membrane Research Contributions during 1900–1950

Development Contributor Year
Affinity effects in ultrafiltration Bechold 1907
Distribution of ions law Donnan 1911
(Distribution law)
Pervaporation Kober 1916
Microporous membrane Zigmondy 1907–1918
Research on dialysis Abel 1926
Research on reverse osmosis Manegold; McBain; Michaels 1926–1931
Description of hemodialysis procedure Abel; Haas 1913
Research on electrodialysis Elder I in 1934
Membrane potential Meyer; Teorell; Sievers 1930s
Hemodialysis Kolff 1944

Table 1.3  Membrane Research Contributions after 1950

Development Contributor Year
Gas separation on silicone rubber Kammermeyer 1957
Pervaporation of azeotropic mixtures Kammermeyer 1957
Skinned membrane Loeb & Sourirajan 1959
Research on composite membranes Lonsdale 1960
Synthesis of asymmetric membranes and Loeb & Sourirajan 1962
controlling pore size in membranes
Capillary membranes Mahon 1963
Concentration polarization Merten 1963
Hollow-fiber membranes Mahon 1966
Membrane transport models Katachalsky; Kedem; Loeb 1960–1970
& Sourirajan; Lonsdale;
Merten; Pusch
Spiral-wound membrane element Bray; Westmoreland 1965–1970
Hollow-fiber RO membranes Hoehn; Mahon; Milford 1965–1970
Thin-film composite membrane Cadotte & Rozelle 1977
Classification of pressure-driven Porter 1975
processes
Models of facilitated transport Goddard 1977
Membranes with immobilized carriers LeBlanc 1980
Description of facilitated transport in LeBlanc 1980
membranes
Membranes with active centers Yoshikawa 1986
Chain model of facilitated transport Aris; Brown; Cussler 1989
Membrane hybrid processes Rautenbach 1990

In the 1970s, Cadotte and Rozelle developed thin-film composite membranes

for reverse osmosis applications. These membranes were made of polyamide
polymer deposited on a support of polysulphone membrane by interfacial po-
lymerization reaction (Schafer, Fane & Waite 2004). In 1984, Petersen devel-
oped another application using such membranes, which he called nanofiltration
 Membrane Science 7

Table 1.4  Some Membrane Modules and Their Applications in the Market
Membrane or Module Applications
Cellulose acetate spiral-wound membranes Industrial and municipal water treatment
Thin-film composite spiral-wound reverse Water desalination and high-purity water
osmosis membranes production
Hollow-fiber reverse osmosis membranes Seawater desalination
Hollow-fiber ultrafiltration and microfiltration Industrial applications
membranes

(Petersen 1993). Stimulating from this technology, Henis and Tripodi made

industrial gas separation economical by drawing on the experience of de-
velopments in revers osmosis membranes and modules. This also led to the
development of several membrane modules and their applications in the mar-
ketplace, such as spiral-wound modules with cellulose acetate and thin-film
composite polyamide membranes, polyamide hollow-fiber membranes, and ul-
trafiltration polysulphone hallow fiber membranes (Lonsdale 1987; Table 1.4).
Understanding the mechanism of water transport through the membranes was
a key point for the development in reverse osmosis. In the 1960s, Sourirajan
developed a preferential sorption-capillary flow model based on the assump-
tion that the membrane surface has pores. Another mechanism is a model
called the solution-diffusion flow model, which is based on the assumption of a
pore-free membrane surface. It was first used by Ferry in 1936, to explain the
permeation of gases, vapors, and organic liquids through dense, nonporous,
homogeneous, and defect-free membranes (Ferry 1936). It is based on the as-
sumption that species is sorbed by the membrane at one interface, transported
by diffusion across the membrane through the voids between the polymeric
chains, and desorbed at the other interface. It involves molecular scale inter-
actions of the permeating solutes with the membrane surface (Ferry 1936;
Matsuura 1994).

MEMBRANE SCIENCE
Membrane science is a field that deals with materials development for mem-
brane design and its process performance. Therefore, membrane science can
be simply categorized into material selection, material characterization and
evaluation, membrane preparation, membrane characterization and evalua-
tion, membrane transport phenomena, membrane module design, and pro-
cess performance (Meares 1976; Turbak 1981; Starzak 1984). Each one of these
categories deals to some extent with the study of permeation and permeable
media, which is the membrane (Lloyd 1985). The basic categories of material
science are illustrated in Fig. 1.3.
8 CHAPTER 1:   An Overview of Membrane Science and Technology

FIGURE 1.3 Basic categories of material science.

MEMBRANE TECHNOLOGY
Membrane technology encompasses the related scientific and engineering
approaches for the transport or rejection of components, species, or substanc-
es through or by the membranes. Membrane technology is used to explain
the mechanical separation processes for separating gas or liquid streams
(Baker 2004; Nunes & Peinemann 2001). Some major steps in the development
of membrane technology are listed in Fig. 1.4.
Because of its multidisciplinary character, membrane technology is used in
several industries, including water treatment for domestic and industrial water
supply, chemical, pharmaceutical, biotechnological, beverages, food, metal-
lurgy, and other separation processes. A schematic representation of the ap-
plications of membrane processes is depicted in Fig. 1.5.
The wider industrial and environmental applications are because of the ad-
vantages of membrane separation as a clean technology; saving energy; and
its ability to replace conventional processes, such as filtration, distillation, ion
exchange, and chemical treatment systems. Other advantages are its ability to
produce high-quality products and flexibility in system design. The main ad-
vantages of membrane technology are listed in Fig. 1.6.
Using membrane technology, the separation can be carried out continuously
under mild conditions with relatively low energy consumption and without
 Membrane Separation Processes 9

FIGURE 1.4 Some major steps in development of membrane technology.

the need for additives. Moreover, the technology can be combined with other
separation processes, forming hybrid processes. However, this technology has
some obstacles, such as concentration polarization and membrane fouling,
low membrane lifetime, and low selectivity and flux. Fig. 1.6. illustrates the
benefits and drawbacks of membrane technology. Although membrane foul-
ing and concentration polarization are disadvantages, they are part of the sepa-
ration process.

MEMBRANE SEPARATION PROCESSES

Membrane separation process is a process where a membrane is used to sepa-
rate the components in a solution by rejecting unwanted substances and allow-
ing the others to pass through the membrane. The role of the membrane is also
to change the composition of a solution on the basis of relative permeation
rates. Membrane performance can be measured by the ability of the membrane
to prevent, regulate, or enhance the permeation. Several factors control the rate
of permeation and the transport mechanism. These include the magnitude of
the driving force and the size of the permeating molecule relative to the size
10 CHAPTER 1:   An Overview of Membrane Science and Technology

FIGURE 1.5 A schematic representation of the applications of membrane processes.

FIGURE 1.6 Benefits and drawbacks of membrane technology.

 Membrane Materials 11

FIGURE 1.7 Simple classification of membrane separation processes into physical and
chemical processes.

of the available permanent. The chemical nature—dispersive, polar, ionic, and

so forth—of both the permeant and the material used to make the membrane
may also effect on the separation. The membrane process conditions must be
engineered carefully, however, the performance limits are determined by the
membrane properties. Membrane separation processes are used in numerous
industrial and environmental applications. Membrane separation processes
can simply be classified into physical and chemical processes, as shown in
Fig. 1.7. A variety of membrane separation processes can be categorized ac-
cording to either driving force, membrane type and configuration, or removal
capabilities and mechanisms. Transport of selected substances through the
membrane can be achieved by applying a driving force (pressure, temperature,
concentration, electrical potential) across the membrane.

MEMBRANE MATERIALS
The selection of the materials suitable to make a membrane for a specific
application is a key factor that requires more investigation. The selection of mem-
brane material allows control over the nature and magnitude of the interactions
between permeants and membranes. It determines the packing density and the
12 CHAPTER 1:   An Overview of Membrane Science and Technology

Table 1.5  Organic Materials for Fabricating Membranes for Separation

Processes
Separation
Serial No. Process Examples of the used materials
1 Microfiltration Cellulose nitrate, cellulose acetate, polyamide,
polysulfone, poly(ether sulfone), polycarbonate,
poly(ether imide), poly(vinylidene fluoride),
polytetrafluoroethylene, polypropylene,
polyacrylonitrile, regenerated cellulose
2 Ultrafiltration Cellulose acetate, polyamide, polysulfone, poly(ether
sulfone), polycarbonate, poly(ether imide),
poly(vinylidene fluoride), polyacrylonitrile, poly(methyl
methacrylate), regenerated cellulose
3 Nanofiltration Polyamide
4 Dialysis Cellulose acetate, polyamide, polycarbonate,
polyacrylonitrile, poly(methyl methacrylate), regener-
ated cellulose
5 Pervaporation Polyvinyl alcohol), polydimethylsiloxane
6 Gas separation Cellulose acetate, polysulfone, polycarbonate,
poly(2,6-dimethyl-1,4-phenylene oxide), polyimide,
polydimethylsiloxane
7 Reverse osmosis Cellulose acetate

segment mobility of the polymer chains that comprise the solid regions of the
membrane. Although both material selection and membrane preparation proce-
dures influence the mechanism of transport, membrane stability, and membrane
performance, the latter determines the membrane morphology, which influences
the rate of permeation by physical properties, such as steric hindrance.
Membranes are fabricated from a wide variety of organic and inorganic materi-
als. Examples of inorganic materials are carbons, alumina, and zeolites. How-
ever, the majority of commercial membranes are fabricated from polymers and
liquids. Examples of organic materials are listed in Table 1.5. These materi-
als are used to fabricate membranes with high mechanical strength, thermal
stability, and chemical resistance, in addition to stable long-term separation
properties.

Inorganic Membrane Materials

Inorganic membranes are used for gas separation, microfiltration, and nano-
filtration. These membranes vary greatly in pore size, support material, and
configuration (De Vos & Verweij 1998). Examples of this type are glass, metal,
alumina, zirconia, zeolite, and carbon membranes. However, other inorgan-
ic materials such as silica, silicon carbide, silicon nitride, titania, cordierite,
tin oxide, and mica can be used to produce porous membranes. Generally,
inorganic membranes covering a wide range of materials can be classified into
 Membrane Materials 13

dense (nonporous) or porous (symmetric and asymmetric). Each of these in-

organic materials has advantages for a specific use in membrane technology.
Dense membranes can be made of palladium and its alloys, silver, nickel, and
stabilized zirconia. They are used for the purpose of gas separation. For ex-
ample, ceramic dense membranes are used in the separation of oxygen from
the air or the separation of hydrogen gas from a mixture. The limitation in their
industrial applications is caused by their low permeability.
Conversely, porous membranes are used in industrial applications because of
their molecular sieving properties, such as high permeabilities and selectivities.
They have high chemical stability, which makes them usable in separations
where aggressive media, such as acids and strong solvents, are present. They
also have high thermal tolerance, which makes them usable in high-temper-
ature membrane operations. They are highly resistant to corrosive chemicals.
Special attention is given to the porous membranes, such as silica, zeolites, and
carbons, which appear to be promising in separation of gases in real applica-
tions (Chen & Yang 1994; Fuertes & Centeno 1995).
For example, silica-based membranes selectively separate hydrogen from other
gases (Hayashi et al. 1997) however; permselectivity between similar-sized
molecules, such as oxygen and nitrogen, seems insufficient and invisible for
real applications. Carbon molecular sieves produced from the pyrolysis of
thermosetting polymers, such as polyacrylonitrile, poly(vinylidene chloride),
perfluoroalkoxy polymer (PFA), cellulose, cellulose triacetate, saran copoly-
mer, and phenol formaldehyde resins, or from coals such as coconut shell, are
promising to be effective for gas separation in adsorption applications. Sev-
eral parameters influence the size and pore dimensions of carbon, and thus
the molecular sieving effect. These are (1) morphology of the organic precur-
sor, (2) the chemistry of pyrolysis, (3) mild activation, and (4) sintering steps
(­Koresh & Soffer 1981; 1983;1986;1987).

Organic Membrane Materials: Polymers

A polymer can be defined as a very long chain (molecule or macromolecule)
made up of small molecules or units called monomers. Polymers can be natural-
ly occurring or synthetic. Synthetic and natural polymers play an essential and
ubiquitous role in membrane science because of their broad range of properties
(McCrum et al. 1997; Painter & Coleman 1997; Roiter & Minko 2005). Mem-
branes fabricated from polymers are use more in industrial application be-
cause of their high performance and ease of design (Osada & Nakagawa 1992;
Pinnau & Freeman 1999). There are a number of polymers, but choosing a
membrane polymer is not an easy task because the polymer has to have appro-
priate characteristics for the intended application (Zeaman & Zydney 1996).
In addition to chemical and mechanical stability and with good separation
14 CHAPTER 1:   An Overview of Membrane Science and Technology

FIGURE 1.8 Major measurements for membrane evaluation.

properties, the polymer has to offer a low binding affinity for separated mol-
ecules and has to withstand harsh cleaning conditions. Moreover, it has to be
compatible with membrane fabrication technology (Zeaman & Zydney 1996).
The polymer has to be suitable in terms of its chain rigidity and interaction and
the polarity of its functional groups (Zeaman & Zydney 1996). It should be
obtainable at a good price. Some of the common polymers used in membranes
are listed in Table 1.5 (Madaeni 2001; Martinez et al. 2000; Palacio et al. 1998;
Templin et al. 2006; Zydney & Ho 2003).

Membrane Evaluation
It is important to evaluate the performance of the membrane, using essential
parameters, before employing it in real applications. There are some measures
used to evaluate the membrane performance. These include measurements of
flux, rejection factor, separation factor, capacity, membrane activity, membrane
fouling, membrane compaction, release rates, and barrier property (listed in
Fig. 1.8). These measures are directly related to materials selection and mem-
brane preparation methods.

Membrane Evaluation Characteristics

The membrane can be used in industrial and environmental separation pro-
cess if it exhibits the required characteristics. These include high flux, high
 Nanomaterials 15

selectivity with required rejection, mechanical stability, tolerance to feed stream

components, fouling resistance, tolerance to temperature variations, manufac-
turing reproducibility, cost- effectiveness, and the ability to be packaged into
high-surface-area modules (Baker et al. 1991; Kesting 1971; Koros et al. 1988).
The selectivity determines the extent of separation toward a specific applica-
tion because a higher product purity can be achieved if the membrane is of
higher selectivity.

Filtration Flux
The rate of membrane surface fouling is a function of the permeate flux rate,
measured as gallons per square foot of membrane area per day (GFD). The
lower the flux rate, the lower the rate of fouling. With higher filtration flux,
solutes are dragged more in the direction of the pores, and result in pore
blocking and a cake layer on top of the membrane surface. The optimum
flux is a flux that is low enough to make sure that no deposition takes place
on top of the membrane. Selection is made using the critical flux hypothesis,
which is that on start-up there exists a flux below which a decline of flux with
time does not occur; above it, fouling is observed (Field et al. 1995). This
flux is the critical flux and its value depends on the hydrodynamics and prob-
ably other variables. The level of the critical flux depends, among others, on
cross-flow velocity, membrane type, type of solute, and bulk concentration of
the solute.

NANOMATERIALS
An Overview of Nanomaterials
Nanomaterial is defined as a substance or a set of substances where the external
dimensions or at least one dimension is in the range of 1 to 100 nanometers.
The word nano is derived from the Greek “nanos” meaning “dwarf. (Boholm
and Boholm 2012)” Nanoscience is the study of phenomena and manipula-
tion of material at the nanoscale, where properties differ significantly from
those at bulk. The nanomaterials that have the same composition as known
materials in bulk form may have different physical, mechanical, and chemi-
cal properties than the same materials in bulk form. Nanomaterials can be in
the form of particles, tubes, rods, or fibers. Nanomaterials are an increasingly
important product of nanotechnologies.
Nanotechnology is the science and technology of small things. It is the study
and application of extremely small things and can be used across all the other
scientific fields, such as chemistry, physics, materials science, and engineer-
ing. It is a science, engineering, and technology conducted at the nanoscale;
it is a multidisciplinary field, meaning that it involves ideas integrated from
many traditional disciplines, such as solid-state physics, chemistry, electrical
16 CHAPTER 1:   An Overview of Membrane Science and Technology

and chemical engineering, biochemistry and biophysics, and materials science.

Nanotechnology includes materials with at least the following three properties:
1. They are of small size, measured in hundreds of nanometers or less.
2. They have unique properties because of their small size.
3. The properties are controlled by regulating the structure and
composition on the nanometer scale.

Historical and Key Developments of Nanotechnology

The physicist Richard Feynman at an American Physical Society meeting at the
California Institute of Technology in December 1959, delivered a talk titled
“There’s Plenty of Room at the Bottom” and described a process in which sci-
entists would be able to manipulate and control individual atoms and mole-
cules. However, the first one to use the term nanotechnology was Professor Norio
Taniguchi (Taniguchi 1974). With the development of the scanning tunneling
microscope in 1984, and the great microelectronics revolution, the techniques
of micro- and nanolithography and etching, nanotechnology-based research
has been significantly developed.
Although some nanomaterials occur naturally, engineered nanomaterials are
of particular interest and can be designed for many commercial products and
processes. Nanomaterials have a much greater surface-area-to-volume ratio
than their conventional forms, which can lead to greater chemical reactivity
and affect their strength. Also at the nanoscale, quantum effects can become
much more important in determining the material’s properties and characteris-
tics, leading to novel optical, electrical, and magnetic behaviors. Table 1.6 illus-
trates the milestones in nanotechnology developments achieved before 1990
(Klein et al. 2011; U.S. National Nanotechnology Initiative, n.d.). Table 1.7 and
Table 1.8 illustrate the milestones in nanotechnology developments achieved
during 1990 to 2000 and after 2000, respectively.

General Properties of Nanomaterials

Nanomaterials combine distinctive physical, chemical, and biological proper-
ties compared to their bulk, which endow them with their beneficial character-
istics. These properties are mainly caused by their structure and higher surface-
area-to-volume ratio. These unique properties of nanomaterials are promising
for applications in water and wastewater treatments. Carbon structures, such
as carbon nanotubes and graphene, can be used as adsorbents because of their
properties, such as high specific surface area and assessable adsorption sites,
selective and more adsorption sites, short intraparticle diffusion distance, and
tunable surface chemistry. Titania and zinc oxides are used in photocatalysis
degradation of organic pollutants in waters because of their photocatalytic ac-
tivity in the solar spectrum, high stability and selectivity, and low cost (Amin
et al. 2014).
 Nanomaterials 17

Table 1.6  The Milestones in Nanotechnology Developments Achieved before

1990
Contributions Contributor Year
Colloidal ruby gold discovered: nanostructured Faraday 1847
gold under certain lighting conditions pro-
duces different-colored solutions
Field emission microscope invented, allowing Müller 1936
near-atomic-resolution images of materials
Semiconductor transistor invented: greatly Bardeen, Shockley & 1947
expanded scientific knowledge of semicon- Brattain
ductor interfaces, laying the foundation for
electronic devices and the Information Age
Theory and process for growing monodisperse La Mer & Dinegar 1950
colloidal materials to fabricate colloids for
industrial uses (papers, paints, thin films,
dialysis) developed
Field ion microscope developed Müller 1951
Concepts of molecular engineering introduced von Hippel 1956
as applied to dielectrics, ferroelectrics, and
piezoelectrics
Technology and engineering at the atomic scale Feynman 1960
presented: “There’s Plenty of Room at the
Bottom” at an American Physical Society
meeting at Caltech
Moore’s Law developed by Intel cofounder; Moore 1965
described the density of transistors on an
integrated chip, increasing reliance on nano-
technology as chip and transistors approach
atomic dimensions
Nanocrystals produced by inert gas evaporation Granqvist & Buhrman 1976
technique
Scanning tunneling microscope invented; Nobel Binnig & Rohrer 1981
Prize awarded in 1986
Nanocrystalline, semiconducting quantum dots Ekimov 1981
discovered in a glass matrix with electronic
and optical properties
Buckyball fullerene (C60) discovered; awarded Kroto, O’Brien, Curl & 1985
1996 Nobel Prize in Chemistry Smalley
Colloidal semiconductor nanocrystals (quantum Brus 1985
dots) discovered
Atomic force microscope invented Binnig, Quate & Gerber 1986
Manipulated individual xenon atoms to spell out Eigler & Schweizer 1989
IBM logo; ability to precisely manipulate atoms

In addition to direct contribution of nanomaterials to water purification,

nanomaterials could be used for the modification of membrane characteris-
tics to improve resistance to fouling or for specific pollutant types. For exam-
ple, nanoparticles of silver, titania, zeolites, and other metal and metal oxides
are used as fillers in membrane technology because of their strong antimi-
18 CHAPTER 1:   An Overview of Membrane Science and Technology

Table 1.7  Milestones in Nanotechnology Developments Achieved during

1990s
Contributions Contributor Year
Nanotechnology began to operate: in 1989 by Klein et al. 2011
Nanophase Technologies; in 1990 by Helix Energy
Solutions Group; in 1997 by Zyvex; in 1998 by
Nano-Tex
Carbon nanotube (CNT) discovered: Iijima shared the Iijima 1991
Kavli Prize in Nanoscience in 2008 for this advance
and other advances in the field.
Nanostructured catalytic materials MCM-41 and Kresge et al. 1992
MCM-48 discovered at Mobil Oil; now used heavily
in refining crude oil as well as for drug delivery, water
treatment, and others
Method for controlled synthesis of nanocrystals Murray et al. 1993
(quantum dots) for biology and high-efficiency
photovoltaics and lighting invented
Molecule [iron carbonyl Fe(CO)2] from constituent Lee & Ho 1999
components [iron (Fe) and carbon monoxide (CO)]
assembled with a scanning tunneling microscope to
prove chemical bonding
Dip-pen nanolithography invented, leading to writing of Ginger et al. 2004
electronic circuits and patterning of biomaterials for
cell biology research, and nanoencryption

crobial activity, hydrophilicity low toxicity, high mechanical and chemical

stability, high permeability and selectivity, and/or photocatalytic activity. The
synthesis of nanomaterials will be discussed in Chapter 4, while the synthesis
of nanomaterials/polymer membranes will be discussed in Chapters 5 and 6.
The characterization of the nanomaterials/polymer membranes will be dis-
cussed in Chapters 7 and 8 followed by discussion in other chapters for their
applications.

CONCLUSION
In this chapter, basic concepts related to the historical overview of membranes,
membrane technology, and membrane separation processes were discussed.
These include membrane definition, history, and contributions in membrane
science and technology. Membrane separation processes and methods for
membrane evaluation were also highlighted and we attempted to provide a
complete overview. Various major types of membrane materials were classi-
fied. An overview of nanomaterials and the history of their development was
also discussed. Accelerate the development of membrane materials with high
filtration flux and low membrane blocking, may further promote membrane
application in different fields including water treatment.
 References 19

Table 1.8  The Milestones in Nanotechnology Developments Achieved after

2000
Contributions Contributor Year
Gold nanoshells developed, which when tuned Halas, West, Drezek & 2003
in size to absorb near-infrared light, serve as a Pasqualin
platform for the integrated discovery, diagnosis,
and treatment of breast cancer without invasive
biopsies, surgery, or systemically destructive
radiation or chemotherapy
First college-level education program in SUNY Albany 2004
nanotechnology in the United States launched:
the College of Nanoscale Science and
Engineering
DNA-based computation and algorithmic Winfree & Rothemund 2005
self-assembly theories developed in which
computations are embedded in the process of
nanocrystal growth
Nanoscale car built of oligo(phenylene ethynylene) Tour et al. 2006
with alkynyl axles and four spherical C60 fullerene
(buckyball) wheels. In response to increases in
temperature, the nanocar moved about on a
gold surface as a result of the buckyball wheels
turning, as in a conventional car
Lithium-ion battery built with a common type Belcher et al. 2007
of virus that is nonharmful to humans at the
Massachusetts Institute of Technology (MIT).
The batteries have the same energy capacity
and power performance as state-of-the-art
rechargeable batteries being considered to
power plug-in hybrid cars.
Creating DNA-like robotic nanoscale assembly Seeman 2009–2010
devices
First carbon nanotube computer developed by 2013
Stanford University researchers

Acknowledgement
The author(s) would like to acknowledge the support provided at King Fahd University of Petro-
leum & Minerals (KFUPM) for conducting this work.

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