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 Nanomaterial and
Polymer Membranes
Synthesis, Characterization,
and Applications

Tawfik Abdo Saleh

Department of Chemistry, King Fahd University of Petroleum &
Minerals, Dhahran, Saudi Arabia

Vinod Kumar Gupta

Department of Chemistry, Indian Institute of Technology
Roorkee, Roorkee, India; Department of Applied Chemistry,
University of Johannesburg, Johannesburg, South Africa

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

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Dedicated to the memories of my late father, Abdo Saleh, Yemen.

I am thankful to my institution and department for permitting me to write

this book. It would have been a difficult task without the cooperation of my
mother and other family members. I would like to express my gratitude to
many people whom I happened to meet through this book, to all those who
provided support. I thank King Fahd University of Petroleum & Minerals.

—Tawfik Abdo Saleh

Dedicated to the memories of my late father, Shri Jeevan Lal Gupta s/o late
Shri Sita Ram ji, V&PO Lakhnauti, Distt. Saharanpur (UP), India.

I am thankful to my institution and department for permitting me to write this

book. It would have been a difficult task without the cooperation of my mother,
Smt. Kiran Devi; wife, Prerna; son and daughter-in-law, Rajat and Shilpi;
daughter and son-in-law, Vartika and Abhinav; and my dearest grand daughters,
Shiriya, Sharanya, and Navika. I thank Professor T. Marwala, DVC Research,
University of Johannesburg, South Africa and NRF South Africa for granting a
SARChI Chair (Tier-1) to work at the University of Johannesburg, South Africa.

—Vinod Kumar Gupta

Preface

Because of significant advances made by the materials science community,

nanomaterials and polymers for membrane technology have been developed.
In the excitement surrounding these materials and technologies, however, their
potential has been frequently overhyped. This book explores these kinds of
materials and their potential future applications.
Making extensive use of illustrations, the book is organized in the follow-
ing way: Chapter 1 introduces the reader to membrane science and technol-
ogy and presents the exciting developments in this field. Chapter 2 identifies
membrane fouling and strategies for cleaning and fouling control. Membrane
classification and membrane operations are discussed in Chapter 3. The syn-
thesis routes of nanomaterials, including both bottom-up and top-down, are
discussed in Chapter 4. Chapters 5 and 6 describe the synthesis and prepa-
ration of nanomaterial-polymer membranes using polymerization and other
methods. Chapter 7 describes the structural characterization of nanomaterial-
polymer membranes. Chapter 8 delineates the morphology and surface char-
acterization of nanomaterial and polymer membranes, detailing the various
tools used to characterize materials at the nanoscale. The applications of nano-
materials, ranging from water and wastewater purification to oil and gas sepa-
ration, are highlighted in Chapters 9 and 10. These chapters contain qualitative
technical descriptions and should be generally accessible to interested readers.
The authors wish to acknowledge the support of King Fahd University of
Petroleum and Minerals in Saudia Arabia during many stages of the preparation
of this book. And we welcome suggestions (via email: tawfikas@hotmail.com;
vinodfcy@gmail.com) from our readers toward improvements that can be
incorporated in future editions of Nanomaterial and Polymer Membranes.
We hope that you enjoy the book!

—Tawfik Abdo Saleh and Vinod Kumar Gupta

xi
 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
1 Microfiltration
2 Ultrafiltration
3 Nanofiltration
4 Dialysis
5 Pervaporation
6 Gas separation
7 Reverse osmosis
Examples of the used materials
Cellulose nitrate, cellulose acetate, polyamide,
polysulfone, poly(ether sulfone), polycarbonate,
poly(ether imide), poly(vinylidene fluoride),
polytetrafluoroethylene, polypropylene,
polyacrylonitrile, regenerated cellulose
Cellulose acetate, polyamide, polysulfone, poly(ether
sulfone), polycarbonate, poly(ether imide),
poly(vinylidene fluoride), polyacrylonitrile, poly(methyl
methacrylate), regenerated cellulose
Polyamide
Cellulose acetate, polyamide, polycarbonate,
polyacrylonitrile, poly(methyl methacrylate), regener-
ated cellulose
Polyvinyl alcohol), polydimethylsiloxane
Cellulose acetate, polysulfone, polycarbonate,
poly(2,6-dimethyl-1,4-phenylene oxide), polyimide,
polydimethylsiloxane
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
Another random document with
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form, as he was in his court, and Gabriel said to him: “This fellow
here possesses ninety and nine sheep, but I have only one, and that
I love, and cherish in my bosom. This man claims my little ewe lamb,
and will take it from me, and, if I will not give it him, he says that he
will slay me; and take my lamb from me by force.”
Then David’s anger was kindled against Michael, and he said, “Thou
who hast so many sheep, wherefore lustest thou after the poor
man’s ewe lamb? Thou hast an evil heart and an insatiable spirit.”
Then Michael exclaimed, “Thou hast given judgment against thyself;
what thou rebukest in this man, thou hast allowed thyself to do!”[653]
And David knew that God had sent His angels to rebuke him, and he
fell upon his face to the ground. But, some say, he drew his sword
and rushed upon Michael: then Gabriel held him back, and said,
“Thou didst ask to be tried; now thou hast fallen under the
temptation.”[654]
Then the angels vanished, and David fell to the ground, tore off his
purple robe, cast aside his golden crown, and wept for forty days and
forty nights. And his tears flowed in such abundance, that every now
and then he plunged a cup into them and drank it off.
At the expiration of forty days Gabriel came to him, and said, “The
Lord salutes thee!” But David felt this was an additional reproach,
and he wept still more. It is said that during the ensuing forty days
and nights David shed more tears than Adam and all his
descendants had, and will, shed from the day of the Fall to the day of
the Resurrection.
Then God sent Gabriel to him again, and Gabriel said, “The Lord
salutes thee!” But David lifted his tearful face and said, “O Gabriel,
what will Uriah say to me on the day of the general Resurrection?”
Gabriel answered, “The Lord will give him so great an inheritance in
Paradise, that he will not have the heart to reproach thee.”
Then David knew that he was pardoned, and he rejoiced greatly. But
he never forgot his sins. He wrote them on the palm of his hand, that
he might have them always before him; therefore he says, “My
shame is ever before mine eyes.”
Nevertheless David’s heart was lifted up with pride, when he
considered that he was a king, a prophet, and a great general. And
one day he said to Nathan, “I think I am perfect, I have everything.”
“Not so,” answered Nathan, “thou exercisest no handicraft.”
Then David was ashamed, and he asked God to teach him a craft;
and God made him skilful in fabricating coats of mail of rings twined
together; his trade therefore was that of an armourer, and his
disgrace was wiped away.
After his judgment between the two angels, David had no confidence
in giving sentence in cases pleaded before him; therefore God sent
him, by the hand of Gabriel, a reed of iron and a little bell, and the
angel said to him, “God is pleased with thy humility, and He has sent
thee this reed and this bell to assist thee in giving judgment. Place
this reed in thy judgment-hall, and hang up the bell in the middle,
and place the accuser on one side, and the accused on the other,
and give sentence in favour of him who makes the bell to tinkle when
he touches the reed.”
David was highly pleased with this gift, and he gave such righteous
judgment, that men feared, throughout the land, to do wrong to one
another.
One day, two men came before David, and one said, “I left a goodly
pearl in the charge of this man, and when I asked for it again, he
denied it me.”
But the other said, “I have returned it to him.”
Then David bade each lay his hand on the reed, but the bell gave
the same indication for both. Then David thought, “They both speak
the truth, and yet that cannot be; the gift of God must err.”
Then he bade the men try again, and the result was the same.
However, he observed that the defendant, when he went up to the
reed to lay his hand upon it, gave his walking staff to the plaintiff to
hold, and this he did each time, so that David’s suspicion was
awakened, and he took the staff, and examined it, and found that it
was hollow, and the stolen pearl was concealed in the handle. Thus
the bell had given right judgment, for when the accused touched the
reed, he had returned the pearl into the hand of the accuser; but
David by his doubt in the reed displeased Him who gave it, and the
reed and the bell were taken from him.
After that, David often gave wrong judgment, till Solomon, his son,
was of age to advise him.
One day, when Solomon was aged thirteen, there came two men
before the king. The first said, “I sold a house and cellar to this man,
and on digging in the cellar he found a treasure hidden there by my
forefathers. I sold him the house and cellar, but not the treasure. Bid
him restore to me what he has found.”
But the other said, “Not so. He sold me the house, the cellar, and all
its contents.”
Then King David said, “Let the treasure be divided, and let half go to
one, and half go to the other.”
But Solomon stood up and said to the plaintiff, “Hast thou not a
son?” He said, “I have.”
Then said Solomon to the defendant, “Hast thou not a daughter?” He
answered, “I have.”
“Then,” said Solomon, “give thy daughter to the son of this man who
sold thee the house, and let the treasure go as a marriage gift to thy
daughter and his son.” And all applauded this judgment.
On another occasion, a husbandman came before the judgment-seat
to lay complaint against a herdsman, whose sheep had broken into
his field, and had pastured on his young wheat.
Then King David said, “Let some of the sheep be given to the
husbandman.”
But Solomon stood up, and said, “Not so; let the husbandman have
the wool, and the milk of the flock, till the wheat is grown up again as
it was before the sheep destroyed it.”
And all wondered at his wisdom.
But the king’s elders and councillors were filled with envy, because
this child’s opinion was preferred before theirs; and they complained
to King David.
Then David said, “Call an assembly of the people, and prove
Solomon before them, whether he be learned in the Law, and
whether he have understanding and wit.”
So the people were assembled, and the elders took council together
how they might perplex him with hard questions. But or ever they
asked him, he answered what they had devised, and they were
greatly confounded, so that the people supposed this was a
preconcerted scene arranged by the king. Then, when the elders
were silenced, Solomon turned to their chief, and said, “I too will
prove you with questions. What you have asked me have been trials
of my learning, but what I will ask you shall put to proof the readiness
of your wits. What is all, and what is nothing? What is something,
and what is naught?”
The elder was silent; he thought, but he knew not what was the
answer. And all the people perplexed themselves to discover the
riddle, but they could not. Then said Solomon, “God is all, and the
world He made is as nothing before Him. The faithful is something,
but the hypocrite is naught.”
Thereupon he turned to a second, and he said: “What are most, and
what are fewest? What is the sweetest, and what is the bitterest?”
But when the second could find no solution to these questions,
Solomon answered, “Most men are unbelievers, the fewest have true
faith. The sweetest thing is the possession of a virtuous wife, good
children, and a competence; the bitterest thing is to have a
disreputable wife, disorderly children, and penury.”
Then Solomon turned to a third elder and asked: “What is the most
odious sight, and what is the most beautiful sight? What is the surest
thing, and what is that which is most insecure?”
And when this elder also was unable to give an answer, Solomon
interpreted his riddle once more, “The most odious sight is to see a
righteous man fall away; the most beautiful sight is to see a sinner
repent. The surest thing is death, the most insecure thing is life.”
After that Solomon said to all the people, “Ye see that the oldest and
the most learned men are not always the wisest. True wisdom
comes not with years, nor is derived from books, but is a gift of God
the All-wise.”
Solomon by his words threw the whole assembly into astonishment,
and all the heads of the people cried with one voice, “Praised be the
Lord, who has given to our king a son who surpasses all in wisdom,
and who is worthy to ascend the throne of his father David.”
And David thanked God that He had given him such a wise son, and
now he desired but one thing further of God, and that was to see him
who was to be his companion in Paradise; for to every man is
allotted by God one man to be his friend and comrade in the Land of
Bliss.
So David prayed to God, and his prayer was heard, and a voice fell
from heaven and bade him confer the kingdom upon his son
Solomon, and then to go forth, and the Lord would lead him to the
place where his companion dwelt.
David therefore had his son Solomon crowned king, and then he
went forth out of Jerusalem, and he was in pilgrim’s garb, with a staff
in his hand; and he went from city to city, and from village to village,
but he found not the man whom he sought. One day, after the lapse
of many weeks, he drew near to a village upon the borders of the
Mediterranean Sea, and alongside of him walked a poorly dressed
man laden with a heavy bundle of faggots. This man was very old
and reverend of aspect, and David watched him. He saw him
dispose of his wood and then give half the money he had obtained
by the sale of it to a poor person. After that he bought a piece of
bread and retired from the town. As he went, there passed a blind
woman, and the old man broke his bread in half, and gave one
portion to the woman; and he continued his course till he reached
the mountains from which he had brought his load in the morning.
David thought, “This man well deserves to be my companion for
eternity, for he is pious, charitable, and reverend of aspect: I must
ask his name.”
He went after the old man, and he found him in a cave among the
rocks, which was lighted by a rent above. David stood without and
heard the hermit pray, and read the Tora and the Psalms, till the sun
went down. Then he lighted a lamp and began his evening prayers;
and when they were finished, he drew forth the piece of bread, and
ate the half of it.
David, who had not ventured to interrupt the devotions of the old
hermit, now entered the cave and saluted him.
The hermit asked, “Who art thou? I have seen no man here before,
save only Mata, son of Johanna, the companion destined to King
David in Paradise.”
David told his name, and asked after this Mata. But the aged man
could give him no information of his whereabouts. “But,” said he, “go
over these mountains, and observe well what thou lightest upon, and
it may be thou wilt find Mata.”
David thanked him, and continued his search. For long it was
profitless. He traversed the stony dales and the barren mountains,
and saw no trace of human foot. At last, just as hope was
abandoning him, on the summit of a rugged peak he saw a wet spot.
Then he stood still in surprise. “How comes there to be a patch of
soft and sloppy ground here?” he asked; “the topmost peak of a
stony mountain is not the place where springs bubble up.”
As he thus mused, an aged man came up the other side of the
mountain. His eyes were depressed to the earth, so that he saw not
David. And when he came to the wet patch, he stood still, and
prayed with such fervour, that rivulets of tears flowed out of his eyes,
and sank into the soil; and thus David learnt how it was that the
mountain-top was wet.
Then David thought, “Surely this man, whose eyes are such copious
fountains of tears, must be my companion in Paradise.”
Yet he ventured not to interrupt him in his prayer, till he heard him
ask, “O my God! pardon King David his sins, and save him from
further trespass! for my sake be merciful to him, for Thou hast
destined him to be my comrade for all eternity!”
Then David ran towards him, but the old man tottered and fell, and
before the king reached him he was dead.
So David dug into the ground which had been moistened by the
tears of Mata, and laid him there, and said the funeral prayer over
him, and covered him with the earth, and then returned to
Jerusalem.
And when he came into his harem, the Angel of Death stood there
and greeted him with the words, “God has heard thy supplications;
now has thy life reached its end.”
Then David said, “The Lord’s will be done!” and he fell down upon
the ground, and expired.
Gabriel descended to comfort Solomon, and to give him a heavenly
shroud in which to wrap David. And all Israel followed the bier to
Machpelah, where Solomon laid him by the side of Abraham and
Joseph.[655]
It will doubtless interest the reader to have an English version of the
Psalm supposed to have been composed by David after the slaying
of Goliath, which is not included in the Psalter, as it is supposed to
be apocryphal.

Psalm CLI. (Pusillus eram).

1. I was small among my brethren; and growing up in my father’s
house I kept my father’s sheep.
2. My hands made the organ: and my fingers shaped the
psaltery.
3. And who declared unto my Lord! He, the Lord, He heard all
things.
4. He sent His angel, and He took me from my father’s sheep:
He anointed me in mercy with His unction.
5. Great and goodly are my brethren: but with them the Lord was
not well pleased.
6. I went to meet the stranger: and he cursed me by all his idols.
 7. But I smote off his head with his own drawn sword: and I
blotted out the reproach of Israel.

This simple and beautiful psalm does not exist in Hebrew, but is
found, in Greek, in some psalters of the Septuagint version, headed
“A Psalm of David when he had slain Goliath.” S. Athanasius
mentions it with praise, in his address to Marcellinus on the
Interpretation of the Psalms, and in the Synopsis of Holy Scripture. It
was versified in Greek in A.D. 360, by Apollinarius Alexandrinus.[656]
The subjoined shield of David is given in a Hebrew book on the
properties and medicaments of things. It is said to be a certain
protection against fire. A cake of bread must be made, and on it
must be impressed the seal or shield of David, having in the corner
the word ‫ ט״יר‬and in the middle ‫( אנ״לא‬Thou art mighty to everlasting,
O Jehovah); and it must be cast aside into the fire with the words of
Psalm cvi. 30, “Then stood up Phinees and prayed; and so the
plague ceased;” and also Exod. xii. 27, “It is the sacrifice of the
Lord’s pass-over, who passed over the houses of the children of
Israel in Egypt, when He smote the Egyptians, and delivered our
homes.”[657]
 XXXVIII.
SOLOMON.[658]
 1. HOW SOLOMON OBTAINED POWER.

After Solomon had executed the last offices for his father, he rested
in a dale betwixt Hebron and Jerusalem, and fell asleep. As he
returned to himself, there stood before him eight angels, each with
countless wings, diverse in kinds and colours; and the angels bowed
themselves before him three times.
“Who are ye?” asked Solomon, with eyes still closed.
“We are the angels ruling over the eight winds of heaven,” was their
reply. “God hath sent us to give thee dominion over ourselves and
over the winds subject to us. They will storm and bluster, or breathe
softly, at thy pleasure. At thy command they will swoop down on
earth, and bear thee over the highest mountains.”
The greatest of the angels gave him a jewel inscribed with “God is
Power and Greatness,” and said, “When thou hast a command for
us, then raise this stone towards heaven, and we shall appear before
thee as thy servants.”
When these angels had taken their departure, there appeared four
more, of whom each was unlike the other. One was in fashion as a
great whale, another as an eagle, the third as a lion, and the fourth
as a serpent. And they said, “We are they who rule over all the
creatures that move in the earth, and air, and water; and God hath
sent us to give thee dominion over all creatures, that they may serve
thee and thy friends with all good, and fight against thine enemies
with all their force.”
The angel who ruled over the winged fowls extended to Solomon a
precious stone, with the inscription, “Let all creatures praise the
Lord!” and said, “By virtue of this stone, raised above thy head, canst
thou call us to thy assistance, and to fulfil thy desire.”
Solomon immediately ordered the angels to bring before him a pair
of every living creature that moves in the water, flies in the air, and
walks or glides or creeps on the earth.
The angels vanished, and in an instant they were before Solomon
once more, and there were assembled in his sight pairs of every
creature, from the elephant to the smallest fly.
Solomon conversed with the angels, and was instructed by them in
the habits, virtues, and names of all living creatures; he listened to
the complaints of the beasts, birds, and fishes, and by his wisdom he
rectified many evil customs amongst them.
He entertained himself longest with the birds, both on account of
their beautiful speech, which he understood, and also because of the
wise sentences which they uttered.
This is the signification of the cry of the peacock: “With what
measure thou judgest others, thou shalt thyself be judged.”
This is the song of the nightingale: “Contentment is the greatest
happiness.”
The turtle dove calls, “Better were it for some created things that
they had never been created.”
The peewit pipes, “He that hath no mercy, will not find mercy
himself.”
The bird syrdar cries, “Turn to the Lord, ye sinners!”
The swallow screams, “Do good, and ye shall receive a reward.”
This is the pelican’s note: “Praise the Lord in heaven and earth.”
The dove chants, “The fashion of this world passeth away, but God
remaineth eternal.”
The kata says, “Silence is the best safeguard.”
The cry of the eagle is, “However long life may be, yet its inevitable
term is death.”
The croak of the raven is, “The further from man, the happier I.”
The cock crows before the dawn and in the day, “Remember thy
Creator, O thoughtless man!”
Solomon chose the cock and the peewit to be his constant
companions—the first because of its cry, and the second because it
can see through the earth as through glass, and could therefore tell
him where fountains of water were to be found.
After he had stroked the dove, he bade her dwell with her young in
the temple he was about to build to the honour of the Most High.
This pair of doves, in a few years, multiplied to such an extent, that
all who sought the temple moved through the quarter of the town it
occupied under the shadow of the wings of doves.
When Solomon was again alone, an angel appeared to him, whose
upper half was like to earth, and whose lower half was like to water.
He bowed himself before the king and said, “I am created by God to
do His will on the dry land and in the watery sea. Now, God has sent
me to serve thee, and thou canst rule over earth and water. At thy
command the highest mountains will be made plain, and the level
land will rise into steep heights. Rivers and seas will dry up, and the
desert will stream with water at thy command.” Then he gave to him
a precious stone, with the legend engraved thereon, “Heaven and
earth serve God.”
Finally, an angel presented to him another stone, whereon was cut,
“There is no God save God, and Mohammed is the messenger of
God.”
“By means of this stone,” said the angel, “thou shalt have dominion
over the whole world of spirits, which is far greater than that of men
and beasts, and occupies the space between earth and heaven. One
portion of the spirits is faithful, and praises the One only God; the
other portion is unfaithful: some adore fire, others the sun, others
worship the planets, many revere winter. The good spirits surround
the true believers among men, and protect them from all evil; the evil
spirits seek to injure them and deceive them.”
Solomon asked to see the Jinns in their natural and original shape.
The angel shot like a column of flame into heaven, and shortly
returned with the Satans and Jinns in great hosts: and Solomon,
though he had power over them, shuddered with disgust at their
loathsome appearance. He saw men’s heads attached to the necks
of horses, whose feet were those of an ass; the wings of an eagle
attached to the hump of a dromedary; the horns of a gazelle on the
head of a peacock.[659]
 2. HOW SOLOMON FEASTED ALL FLESH.

When Solomon returned home, he placed the four stones, which the
angels had given him, in a ring, so that he might at any moment
exercise his authority over the realms of spirits and beasts, the earth,
the winds, and the sea.
His first care was to subject the Jinns. He made them all appear
before him, with the exception of the mighty Sachr, who kept himself
in concealment on an unknown island in the ocean, and the great
Eblis, the master of all evil spirits, to whom God had promised
complete liberty till the day of the last Judgment.
When all the demons were assembled, Solomon pressed his seal
upon their necks, to mark them as his slaves. Then he commanded
all the male Jinns to collect every sort of material for the construction
of the temple he was about to build. He bade also the female Jinns
cook, bake, wash, weave, and carry water; and what they made he
distributed amongst the poor. The meats they cooked were placed
on tables, which covered an area of four square miles; and daily
thirty thousand portions of beef, as many portions of mutton, and
very many birds and fishes were devoured. The Jinns and devils sat
at iron tables, the poor at tables of wood, the heads of the people at
silver tables, the wise and pious at tables of gold; and these latter
were served by Solomon in person.
One day, when all spirits, men, beasts, and birds rose satisfied from
the tables, Solomon besought God to permit him to feed to the full all
created animals at once. God replied that he demanded an
impossibility. “But,” said he, “try, to-morrow, what thou canst do to
satisfy the dwellers in the sea.”
On the morrow, accordingly, Solomon bade the Jinns lade a hundred
thousand camels and the same number of mules with corn, and lead
them to the sea-shore. He then cried to the fishes and said: “Come,
ye dwellers in the water, eat and be satisfied!”
Then came all manner of fishes to the surface of the water, and
Solomon cast the corn to them, and they ate and were satisfied, and
dived out of sight. But all at once a whale lifted his head above the
surface, and it was like a mountain. Solomon bade the spirits pour
one sack of corn after another down the throat of the monster, till all
the store was exhausted, there remained not a single grain. But the
whale cried, “Feed me, Solomon! feed me! never have I suffered
from hunger as I have this day!”
Solomon asked the whale if there were any more in the deep like
him. The fish answered: “There are of my race as many as a
thousand kinds, and the smallest is so large that thou wouldst seem
in its belly to be but a sand-grain in the desert.”
Solomon cast himself upon the earth, and began to weep, and
prayed to God to pardon him for his presumption.
“My kingdom,” called to him the Most High, “is far greater than thine.
Stand up, and behold one creature over which no man has yet
obtained the mastery.”
Then the sea began to foam and toss, as though churned by the
eight winds raging against it, and out of the tumbling brine rose the
Leviathan, so great that it could easily have swallowed seven
thousand whales such as that which Solomon had attempted to feed;
and the Leviathan cried, with a voice like the roar of thunder:
“Praised be God, who by His mighty power preserves me from
perishing by hunger.”[660]
 3. THE BUILDING OF THE TEMPLE.[661]

When Solomon returned from the sea-shore to Jerusalem, he heard

the noise of the hammers, and saws, and axes of the Jinns who
were engaged in the building of the temple; and the noise was so
great that the inhabitants of Jerusalem could not hear one another
speak. Therefore he commanded the Jinns to cease from their work,
and he asked them if there was no means whereby the metals and
stones could be shaped and cut without making so much noise.
Then one of the spirits stepped forth and said: “The means is known
only to the mighty Sachr, who has hitherto escaped your authority.”
“Is it impossible to capture this Sachr?” asked Solomon.
“Sachr,” replied the Jinn, “is stronger than all the rest of us together,
and he excels us in speed as he does in strength. However, I know
that once every month he goes to drink of a fountain in the land of
Hidjr; by this, O king, thou mayest be able to bring him under thy
sceptre.”
Solomon, thereupon, commanded a Jinn to fly to Hidjr, and to empty
the well of water, and to fill it up with strong wine. He bade other
Jinns remain in ambush beside the well and watch the result.[662]
After some weeks, when Solomon was pacing his terrace before his
palace, he saw a Jinn flying, swifter than the wind, from the direction
of Hidjr, and he asked, “What news of Sachr?”
“Sachr lies drunk on the edge of the fountain,” said the Jinn; “and we
have bound him with chains as thick as the pillars of the temple;
nevertheless, he will snap them as the hair of a maiden, when he
wakes from his drunken sleep.”
Solomon instantly mounted the winged Jinn and bade him transport
him to the well at Hidjr. In less than an hour he stood beside the
intoxicated demon. He was not a moment too soon, for the fumes of
the wine were passing off, and, if Sachr had opened his eyes,
Solomon would have been unable to constrain him. But now he
pressed his signet upon the nape of his neck: Sachr uttered a cry so
that the earth rocked on its foundations.
“Fear not,” said Solomon, “mighty Jinn; I will restore thee to liberty if
thou wilt tell me how I may without noise cut and shape the hardest
metals.”
“I myself know no means,” answered the demon; “but the raven can
tell thee how to do this. Take the eggs out of the raven’s nest and
place a crystal cover upon them, and thou shalt see how the raven
will break it.”
Solomon followed the advice of Sachr. A raven came, and fluttered
some time round the cover, and seeing that she could not reach her
eggs, she vanished, and returned shortly with a stone in her beak,
named Samur or Schamir; and no sooner had she touched the
crystal therewith, than it clave asunder.
“Whence hast thou this stone?” asked Solomon of the raven.
“It comes from a mountain in the far west,” replied the bird.
Solomon commanded a Jinn to follow the raven to the mountain, and
to bring him more of these stones. Then he released Sachr as he
had promised. When the chains were taken off him, he uttered a
loud cry of joy, which, in Solomon’s ears, bore an ominous sound as
of mocking laughter.
When the Jinn returned with the stone Schamir, Solomon mounted a
Jinn and was borne back to Jerusalem, where he distributed the
stones amongst the Jinns, and they were able to cut the rocks for the
temple without noise.[663]
Solomon also made an ark of the covenant ten ells square, and he
sought to bring it into the Holy of Holies that he had made; and when
he sought to bring the ark through the door of the temple, the door
was ten ells wide. Now, that was the width of the ark, and ten ells will
not go through ten ells. Then, when Solomon saw that the ark would
not pass through the door, he was ashamed and cried, “Lift up your
heads, O ye gates, and the King of Glory shall come in!” Then the
gates tottered, and would have fallen on his head to punish what
they supposed to be a blasphemy, for the doors thought that by “the
King of Glory” he meant himself; and they cried to him in anger,
“Who is the King of Glory?” and he answered, “It is the Lord of
Hosts, He is the King of Glory.” And because the doors were so
zealous for the honour of God, the Lord promised them that they
should never fall into the hands of the enemies of Israel. Therefore,
when the temple was burnt and the treasures were carried into
Babylon, the gates sank into the earth and vanished. And to this the
prophet Jeremiah refers (Lament, ii. 9).[664]
Solomon also built him a palace, with great riches in gold, and silver,
and precious stones, like no king that was before him. Many of the
halls had crystal floors and crystal roofs. He had a fountain of liquid
brass.[665] He had also a carpet five hundred parasangs in length;
and whenever the carpet was spread, three hundred thrones of gold
and silver were placed on it, and Solomon bade the birds of the air
spread their wings over them for a shade.[666] He built a throne for
himself of sandal wood, encrusted with gold and precious stones.
 4. THE TRAVELS OF SOLOMON.

Whilst the palace was being built, Solomon made a journey to

Damascus. The Jinn, on whose back he flew, carried him directly
over the valley of ants, which is surrounded by such crags and
precipices, that no man had hitherto seen it. The king was much
astonished to see such a host of ants under him, which were as big
as wolves, and which, on account of their grey eyes and grey feet,
looked from a distance like a cloud. The queen of the ants, who, till
this moment, had not seen a man, was filled with fear when she
beheld Solomon, and she cried to her host, “Hie to your holes, fly!”
But God commanded her not to fear, and to summon all her
subjects, and to anoint Solomon king of all insects. Solomon, who
heard the words of God, and the answer of the queen from a
distance of many miles, borne to him upon the wind, descended into
the valley beside the queen. Immediately the whole valley was filled
with ants, as far as the eye could see.
Solomon asked the queen, “Why didst thou fear me, being
surrounded with such a countless and mighty host?”
“I fear God alone,” answered the queen; “if any danger were to
threaten my subjects, at a sign from me seven times as many would
instantly appear.”
“Wherefore then didst thou command the ants to fly to their holes
when I appeared?”
“Because I feared they would look with wonder and reverence on
thee, and thereby for a moment forget their Creator.”
“I am greater than thou,” added the queen of the ants.
“How so?” asked Solomon in surprise.
“Because thou hast a metal throne, but my throne is thy hand, on
which I now repose,” said the ant.