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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

PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO
Elsevier
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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
 CH AP T E R 2

Membrane Fouling and Strategies

for Cleaning and Fouling Control

MEMBRANE FOULING CONTENTS

Traditional membrane technology is affected by fouling, which is the primary Membrane Fouling.......25
impediment to the wide use of various membrane-based processes, such as Definition of Membrane
reverse osmosis and ultrafiltration in water treatment (Khulbe, Feng & Mat- Fouling...................................25
suura 2008). Any material that causes fouling is called a foulant. Fouling results Foulants.................................25
in loss of productivity and a reduction in quality. Fouling
Classification................26
Colloidal (Particulate)
Definition of Membrane Fouling
Fouling...................................27
The term membrane fouling is used to describe the accumulation of materials Organic Fouling......................28
(foulants) at the surface or in the membrane’s pores, which give rise to decreas- Inorganic Fouling...................29
ing the permeate flux of the membrane (Speth, Summers & Gusses 1998). The Biofouling...............................30
loss in throughput capacity of the membrane is primarily caused by the forma- Factors Influencing
tion of a boundary layer on the membrane surface during the process of filtra- Fouling.........................31
tion. It causes a reduction of the membrane flux below the calculated theoretical Flux Decline...........................34
capacity of the membrane for the given driving force using a specific module. Concentration Polarization
and Osmotic Pressure...........35
Generally, fouling can be divided into two different types: external and inter- Osmotic Pressure..................36
nal. External membrane fouling is the result of the accumulation of rejected Fouling
particles or foulants on the external surface of the membrane. Internal mem- Mechanisms.................36
brane fouling is the result of the deposition or adsorption of tiny particles
Reversible and
or macromolecules within the internal pore structure of the membrane. By
Irreversible
such fouling, the membrane’s performance is degraded even under dynamic Membrane Fouling.......38
conditions. An example is the deposition of protein aggregates on or in the
Strategies of
membranes, which is considered a major cause for the initiation of such a
Membrane
fouling (Belfort, Davis & Zydney 1994; Bowen & Gan 1991; Guell, Czekaj & Cleaning.......................40
Davis 1999). It is considered to be a major obstacle to the widespread use of Categories of
membrane technology because fouling can cause severe flux decline and at the Cleaning Methods..................40
same time, affect the quality of the water produced. Cleaning Temperature
and Time................................46

Foulants Fouling Reduction

by Modification
Sources of fouling (foulants) include colloidal particles, sparingly soluble
and Coating..................46
salts, dissolved organic solvents, microorganisms, protein molecules, and 25
(Continued)
Nanomaterial and Polymer Membranes. http://dx.doi.org/10.1016/B978-0-12-804703-3.00002-4
Copyright © 2016 Elsevier Inc. All rights reserved.
26 CHAPTER 2: Membrane Fouling and Strategies for Cleaning and Fouling Control

Membrane Modification
by Nanomaterials...................47
Conclusion...................48
Acknowledgment.........49
References...................49

FIGURE 2.1 Types of foulants with examples of each type.

other ­particulates. The types of foulants and examples of each are illustrated
in Fig. 2.1. Colloidal particles are considered a source of external fouling be-
cause colloidal particles accumulate on the membrane surface and increase the
resistance to water flow through the membrane. Colloidal particles could be
clay minerals, colloidal silica, oxyhydroxide, aluminium, iron and manganese
oxides, organic colloids, large organic macromolecules, organic colloids, sus-
pended matter, and precipitated calcium carbonate (Chandavarkar 1990; Kelly
& Zydney 1997; Tracey & Davis 1994).

FOULING CLASSIFICATION
Based on the matter that is deposited on the surface of the membrane, fouling
might be grouped into four types: colloidal, organic, inorganic, and biofoul-
ing (Meng et al. 2009; Mohanty & Purkait 2012; Zhang et al. 2012). Colloidal
­fouling is described as the accumulation of colloidal particles on the mem-
brane’s surface forming a cake layer. Organic fouling includes adsorption of
organic species or the membrane. Inorganic fouling (scaling) occurs as a result
of deposition or precipitation of inorganic colloidal particles and particulates
Another random document with
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regularity:—varying their phases from full to new and from new to
full, and frequently eclipsing the sun and each other, at least to the
equatorial parts of Jupiter; and almost in every revolution suffering
eclipses themselves by falling into Jupiter’s shadow; excepting that
the outermost will seem, like a traveller fond of the sun-beams,
cautiously to avoid the shadow for whole years together. Since we
are advanced so far, if not tired of the journey, let us proceed a step
further; it is but 400 millions of miles to the globe of Saturn. Here
again all will be lost, but Jupiter itself. The Sun will put on something
of a starlike appearance, but with excessive brightness. The five[A33]
satellites of Saturn will exhibit appearances similar to those of
Jupiter, but they will very rarely eclipse the Sun, or suffer eclipses
themselves. The particular phænomena of Saturn’s ring, we cannot
explain, unless we knew the time and plane of Saturn’s revolution on
his axis. But this we know, that it must sometimes appear, by night,
like a prodigious luminous arch, almost equal to one quarter of the
heavens; and at other times, dark, so as to afford no light itself, but
to intercept the light of every star beyond it, by night, and of the sun
itself by day. And to conclude, if borne on the wings of a comet we
should travel with it to the remotest part of its orbit; our whole
planetary system would disappear, and the sun become a star, only
more refulgent than Sirius perhaps, because less distant.

The opinion of the earth’s rotation on its axis was once violently
opposed, from a notion of its dangerous tendency with respect to the
interests of religion:[A34] But, as truth is always consistent with itself,
so many new proofs were furnished from time to time by new
discoveries, that a mistaken interpretation of some passages in the
bible was compelled to give way to the force of astronomical
evidence. The doctrine of a plurality of worlds, is inseparable from
the principles of Astronomy; but this doctrine is still thought, by some
pious persons, and by many more I fear, who do not deserve that
title, to militate against the truths asserted by the Christian religion. If
I may be allowed to give my opinion on a matter of such importance,
I must confess that I think upon a proper examination the apparent
inconsistency will vanish. Our religion teaches us what philosophy
could not have taught; and we ought to admire with reverence the
great things it has pleased divine Providence to perform, beyond the
ordinary course of Nature, for man, who is undoubtedly the most
noble inhabitant of this globe. But neither religion nor philosophy
forbids us to believe that infinite wisdom and power, prompted by
infinite goodness, may throughout the vast extent of creation and
duration, have frequently interposed in a manner quite
incomprehensible to us, when it became necessary to the happiness
of created beings of some other rank or degree.

How far indeed the inhabitants of the other planets may resemble
man, we cannot pretend to say. If like him they were created liable to
fall, yet some, if not all of them, may still retain their original
rectitude. We will hope they do: the thought is comfortable.—Cease,
Galileo, to improve thy optic tube: and thou, great Newton, forbear
thy ardent search into the distant mysteries of nature: lest ye make
unwelcome discoveries. Deprive us not of the pleasure of believing
that yonder radiant orbs, traversing in silent majesty the etherial
regions, are the peaceful seats of innocence and bliss: where neither
natural nor moral evil has ever yet intruded; where to enjoy with
gratitude and adoration the creator’s bounty, is the business of
existence. If their inhabitants resemble man in their faculties and
affections, let us suppose that they are wise enough to govern
themselves according to the dictates of that reason their creator has
given them, in such manner as to consult their own and each other’s
true happiness, on all occasions. But if, on the contrary, they have
found it necessary to erect artificial fabrics of government, let us not
suppose that they have done it with so little skill, and at such an
enormous expence, as must render them a misfortune instead of a
blessing. We will hope that their statesmen are patriots, and that
their kings, if that order of beings has found admittance there, have
the feelings of humanity.—Happy people! and perhaps more happy
still, that all communication with us is denied. We have neither
corrupted you with our vices, nor injured you by violence. None of
your sons and daughters, degraded from their native dignity, have
been doomed to endless slavery by us in America, merely because
their bodies may be disposed to reflect or absorb the rays of light, in
a way different from ours. Even you, inhabitants of the moon,
situated in our very neighbourhood, are effectually secured, alike
from the rapacious hand of the haughty Spaniard, and of the
unfeeling British nabob. Even British thunder impelled by British
thirst of gain, cannot reach you: And the utmost efforts of the mighty
Frederick, that tyrant of the north and scourge of mankind, if aimed
to disturb your peace, becomes inconceivably ridiculous and
impotent.

Pardon these reflections; they rise not from the gloomy spirit of
misanthropy. That being, before whose piercing eye all the intricate
foldings and dark recesses of the human heart become expanded
and illuminated, is my witness with what sincerity, with what ardor, I
wish for the happiness of the whole race of mankind: how much I
admire that disposition of lands and seas, which affords a
communication between distant regions, and a mutual exchange of
benefits:[A35] how sincerely I approve of those social refinements
which really add to our happiness, and induce us with gratitude to
acknowledge our great Creator’s goodness:—how I delight in a
participation of the discoveries made from time to time in nature’s
works, by our Philosophic brethren in Europe.

But when I consider, that luxury and her constant follower tyranny,
who have long since laid in the dust, never to rise again, the glories
of Asia, are now advancing like a torrent irresistible, whose weight
no human force can stem, and have nearly completed their conquest
of Europe; luxury and tyranny, who by a vile affectation of virtues
they know not, pretend at first to be the patrons of science and
philosophy, but at length fail not effectually to destroy them; agitated
I say by these reflections, I am ready to wish—vain wish! that nature
would raise her everlasting bars between the new and old world; and
make a voyage to Europe as impracticable as one to the moon. I
confess indeed, that by our connections with Europe we have made
most surprising, I had almost said unnatural, advances towards the
meridian of glory; but by those connections too, in all probability, our
fall will be premature. May the God of knowledge inspire us with
wisdom to prevent it: let our harbours, our doors, our hearts, be shut
against luxury. But I return to my subject, and will no longer indulge
these melancholy thoughts.

Some have observed, that the wonderful discoveries of the

microscope ought to go hand in hand with those of the telescope;
lest whilst we contemplate the many instances of the wisdom and
power of divine Providence, displayed in the great works of creation,
we should be tempted to conclude that man, and other less
important beings of this lower world, did not claim its attention. But I
will venture to affirm, without at all derogating from the merits of
those who have so greatly obliged the world with the success of their
microscopical enquiries, that no such danger is to be apprehended.
Nothing can better demonstrate the immediate presence of the Deity
in every part of space, whether vacant or occupied by matter, than
astronomy does. It was from an astronomer St. Paul quoted that
exalted expression, so often since repeated; “In God we live, and
move, and have our being.” His divine energy supports that universal
substratum on which all corporal substances subsist, that the laws of
motion are derived from, and that wings light with angelic swiftness.

If the time would permit, how agreeable the task to dwell on the
praises of Astronomy: to consider its happy effects as a science, on
the human mind. Let the sceptical writers forbear to lavish
encomiums on their cobweb Philosophy, liable to be broken by the
smallest incident in nature. They tell us it is of great service to
mankind, in banishing bigotry and superstition from amongst us. Is
not this effectually done by Astronomy? The direct tendency of this
science is to dilate the heart with universal benevolence, and to
enlarge its views. But then it does this without propagating a single
point of doctrine contrary to common sense, or the most cultivated
reason. It flatters no fashionable princely vice, or national depravity.
It encourages not the libertine by relaxing any of the precepts of
morality; nor does it attempt to undermine the foundations of religion.
It denies none of those attributes, which the wisest and best of
mankind, have in all ages ascribed to the Deity: Nor does it degrade
the human mind from that dignity, which is ever necessary to make it
contemplate itself with complacency. None of these things does
Astronomy pretend to; and if these things merit the aim of
Philosophy, and the encouragement of a people, then let scepticism
flourish, and Astronomy lie neglected; then let the names of
Berkeley, and Hume, become immortal, and that of Newton be lost in
oblivion.

I shall conclude this part of my discourse with the words of Dr.

Barrow—It is to Astronomy we owe “that we comprehend the huge
fabric of the universe, admire and contemplate the wonderful beauty
of the divine workmanship, and so learn the invincible force and
sagacity of our own minds, as to acknowledge the blessings of
heaven with a pious affection.”

I now come, in the last place, to point out some of the defects of
Astronomy at this day. Which I am induced to undertake by the
hopes I entertain that some of those defects may be removed under
the auspices of this society, and of you my fellow citizens, who have
so zealously promoted its institution. “The advantages arising from
Astronomy, the pleasure attending the study of it, the care with which
it was cultivated by many great men among the ancients, and the
extraordinary attention paid to it in Europe by the present age,” all
contribute to recommend it to your protection, under which we have
the best reason to expect that it will flourish.

The mildness of our climate and the serenity of our atmosphere,

perhaps not inferior to that of Italy, and likewise our distant situation
from the principal observatories in the world (whence many curious
phænomena must be visible here that are not likely to be observed
any where else) are so many circumstances greatly in our favour.

And I trust there will not be wanting men of genius, to arise in this
new world, whose talents may be particularly adapted to
astronomical enquiries. Indeed I am persuaded that nature is by no
means so nigardly in producing them, as we are apt to imagine.
Some are never tempted forth from obscurity, some are untimely
snatched away by death, a striking instance whereof we have in
Horrox; and many are accidentally led to other pursuits.
 The Astronomy of comets is still in its infancy; not that the
attention of the learned and ingenious has at all been wanting for
more than a century past; but because it will necessarily require
many ages to bring it to perfection. I wish we were in a condition to
promote it in some degree, by carefully observing such comets as
may appear. As yet we scarce dare affirm that any one has or will
return a second time. It has never, that I know of, been certainly
proved by observation, that a comet has descended within a
parabolic orbit, and until that is done we have only a coincidence of
periods and orbits (none of which have been very precise) to depend
on for their return. Far less are astronomers able to determine the
changes that may, and probably do, happen in their orbits[A36] and
velocities in every period, so as to predict their nearer or more
remote approach to the earth or any planet. Whether their business
be to repair or destroy, whether they are worlds yet in formation or
once habitable worlds in ruins; whether they are at present habitable
and regular attendants of our Sun only, or whether they are the vast
links that connect the distant parts of creation by surrounding more
suns than one, we know not.

If we descend to the Planetary System, there are still many things

wanting to compleat Astronomy.

The orbits of the primary planets have at one time been supposed
moveable with various irregularities, at other times fixed and
permanent. It seems now generally granted, that according to the
theory of gravity they must change their situations; yet not long
since, some great astronomers warmly contended that this change
was altogether insensible.

According to the best tables we now have, the planes of the orbits
of Jupiter, the Earth and Mercury are immoveable, though the orbits
themselves have a progressive motion in their planes. On the
contrary, the poles of the orbits of Saturn, Mars and Venus are
supposed to revolve about the poles of the earth’s orbit, with such
velocities as at present nearly reconcile calculation to appearances.
But there is good reason to apprehend that such a supposition is not
true in fact, and a mistake in this matter will have some important
consequences. More probable is it, that the poles of the orbits of all
the planets, the earth not excepted, revolve about some common
centre. The several quantities of these motions, I am confident, are
to be had from observation, and not from theory alone. If such a
motion of the earth’s orbit be admitted, it will account for the
diminution[A37] of the obliquity of the ecliptic; which seems now
incontestible; and that in whatever manner we divide the forces
producing such motion, amongst the two superior planets and
Venus, or even amongst all of them. And I should suspect the further
diminution of obliquity, from this cause, will amount to about one
degree and an half.

But as Astronomy now stands, it seems doubtful whether this

change is owing to a deviation in the diurnal or annual motion of the
earth; which introduces a very disagreeable uncertainty in
conclusions drawn from some nice and useful observations.

The Lunar Astronomy has been brought so much nearer to

perfection, by the celebrated Mayer,[A38] than could have been
expected, that I shall mention no deficiency in it, but this. We do not
certainly know whether that apparent acceleration of the moon’s
motion, which Mayer with other great astronomers has admitted,
ought to be attributed to a real increase of velocity in the moon, or to
a diminution of the earth’s diurnal motion. If to the former, the
destruction of this beautiful and stupendous fabric, may from thence
be predicted with more certainty than from any other appearance in
Nature: But if to the latter, it may be prettily accounted for, by Dr.
Halley’s ingenious hypotheses concerning the change of variation in
the magnetical needle. The Doctor supposes the external crust or
shell of the earth to contain a nucleus detatched from it, and that the
impulse which first caused the diurnal motion, was given to the
external parts, and from thence in time communicated to the internal
nucleus, by means of an intervening fluid; but not so as perfectly to
equal the velocity of the superficial parts of the globe. Whence it will
follow, that the external shell of the earth is still communicating
motion to the internal parts, and losing motion itself proportionably.
The diurnal motion must therefore become slower and slower, yet
can never be retarded, by this cause, beyond certain limits; nor can
we conceive that any inconvenience will follow.

There is another physical question relating to the moon, which to

me appears extremely curious; it is this—Whence is it that the moon
always turns the same side to us? or, which is the same thing, How
comes the moon’s rotation on her axis, and her monthly revolution
about the earth, to be performed in the same time? None I believe
will suppose it to be accidental, nor will the astronomer be easily
satisfied with a final cause. Was it not originally brought about by a
natural cause which still subsists? Can the attraction of any foreign
body change a rotatory motion into a libratory one, and a libratory
motion into rest, in spaces so very free from all resistance as those
wherein the planets move? There are other defects in Astronomy
that are purely optical. Removing of those, depends on the further
improvement of telescopes, or rather on the more judicious use of
them, at times and places the most favourable.

In speaking of telescopic discoveries I purposely reserved those

made on Venus for this place, because they are still uncertain.
Burratini in Poland first discovered spots in Venus, then Cassini in
Italy; and afterwards Bianchini got a sight of them. But from all their
observations it is uncertain, whether Venus revolves on its axis once
in 23 hours, or once in 24 days. Perhaps it does neither. Nor is their
determination of the axis’ situation much more satisfactory. These
spots on Venus are not to be seen but through an excellent
telescope and a pure atmosphere.

In the year 1672 and 1676 Cassini saw a small star near Venus,
which he thought might be a satellite attending on her. It appeared to
have the same phase with Venus. In 1740 Mr. Short with a telescope
of 16 inches saw a small star at the distance of ten minutes from
Venus, which from its apparent shape he likewise thought might be a
satellite. And in 1761 Mr. Montaigne, in France, saw what he took to
be the satellite of Venus, on the 3d, 4th, 7th and 11th of May.[A39] But
whether Venus has a satellite or not, must still be left amongst the
doubtful things of Astronomy.

The spots on the sun, and those on the surfaces of several

planets, have been many years observed without our approaching
any nearer towards discovering their nature and cause. Dr. Wilson of
Glasgow, has lately succeeded in advancing one step at least, with
respect to those of the sun. He has proved from observation that
those spots are vast cavities, whose bottoms lie far below the
general surface of the sun, and whose sloping sides form the border
which we generally see surrounding them. If I should venture to add
one conjecture of my own, to those of this ingenious gentleman, I
would suppose that those prodigious cavities in the surface of the
sun, some of them capable of containing half our earth, are not
repeatedly formed by unaccountable explosions of a semifluid
substance, but permanent and solid, like the cavities within the
moon. And that it is the dark matter sometimes lodging in them, that
distinguishes them, and is only accidental.

The diurnal rotations of Saturn and Mercury are yet unknown; but
when further improvements shall be made in the art of using
telescopes, this circumstance will hardly escape the vigilance of
astronomers.

These are a few of the many things that are still left to the industry
of the ingenious in this science.

But if all higher and more sublime discoveries are not reserved for
us in a future and more perfect state; if Astronomy shall again break
those limits that now seem to confine it, and expatiate freely in the
superior celestial fields; what amazing discoveries may yet be made
amongst the fixed stars! That grand phænomenon the Milky-Way
seems to be the clue that will one day guide us. Millions of small
stars compose it, and many more bright ones lie in and near it, than
in other parts of heaven. Is not this a strong indication that this
astonishing system of worlds beyond worlds innumerable, is not
alike extended every way, but confined between two parallel planes,
of immeasureable, though not infinite extent? Or rather, is not the
Milky-Way a vein of a closer texture, running through this part of the
material creation? Great things are sometimes best explained by
small and small by great. Material substances, such as we daily
handle, have been thought composed of impenetrable particles in
actual contact: then again it has seemed necessary to suppose them
at a distance from each other, and kept in their relative situations by
attraction and repulsion. Many appearances require that those
distances should be very great in proportion to the size of the
particles. Hence some, with no small reason, have concluded that
matter consists of indivisible points endued with certain powers. Let
us compare these smaller portions of it with that great aggregate of
matter which is the object of Astronomy; Light will then appear to
have as free passage through a piece of glass, as the comets have
in the planetary regions; and several other new considerations will
arise.

If instead of descending we ascend the scale. If we consider that

infinite variety which obtains in those parts of nature with which we
are most intimate: how one order of most curiously organized
bodies, infinitely diversified in other respects, all agree in being fixed
to the earth, and receiving nourishment from thence: how another
order have spontaneous motion, and seek their food on different
parts of the earth, whilst by gravity they are confined to its surface,
but in other respects diversified like the former. How a third float in,
and below the surface of, a dense fluid, of equal weight with their
bodies, which would soon prove fatal to both the others: And a fourth
consisting of a vast variety too, have this property in common, that
by a peculiar mechanism of their bodies, they can soar to great
heights above the earth, and quickly transport themselves to distant
regions in a fluid so rare as to be scarcely sensible to us. But not to
pursue this boundless subject any further, I say, when we consider
this great variety so obvious on our globe, and ever connected by
some degree of uniformity, we shall find sufficient reason to
conclude, that the visible creation, consisting of revolving worlds and
central suns, even including all those that are beyond the reach of
human eye and telescope, is but an inconsiderable part of the whole.
Many other and very various orders of things unknown to, and
inconceivable by us, may, and probably do exist, in the unlimited
regions of space. And all yonder stars innumerable, with their
dependencies, may perhaps compose but the leaf of a flower in the
Creator’s garden, or a single pillar in the immense building of the
Divine Architect.

Here is ample provision made for the all-grasping mind of man!

If it shall please that Almighty Power who hath placed us in a

world, wherein we are only permitted “to look about us and to die;”
should it please him to indulge us with existence throughout that half
of eternity which still remains unspent; and to conduct us through the
several stages of his works; here is ample provision made for
employing every faculty of the human mind, even allowing its powers
to be constantly enlarged through an endless repetition of ages. Let
us not complain of the vanity of this world, that there is nothing in it
capable of satisfying us: happy in those wants, happy in those
restless desires, forever in succession to be gratified; happy in a
continual approach to the Deity.

I must confess that I am not one of those sanguine spirits who

seem to think, that when the withered hand of death hath drawn up
the curtain of eternity, almost all distance between the creature and
creator, between finite and infinite, will be annihilated. Every
enlargement of our faculties, every new happiness conferred upon
us, every step we advance towards the perfection of the divinity, will
very probably render us more and more sensible of his inexhaustible
stores of communicable bliss, and of his inaccessible perfections.

Were we even assured that we shall perish like the flowers of the
garden, how careful would a wise man be to preserve a good
conscience, during the short period of his existence; because by his
very constitution, which he cannot alter, this is his pride and glory,
and absolutely necessary to his present happiness; because this
would insure to him at the approach of death, the soothing reflection,
that he was going to restore, pure and uncorrupted, that drop of
divinity within him, to the original ocean from whence it was
separated. How much more anxiously careful ought we to be, if we
believe, as powerful arguments compel us to believe, that a conduct
in this life depending on our own choice, will stamp our characters
for ages yet to come. Who can endure the thought of darkening his
faculties by an unworthy application of them here on earth, and
degrading himself to some inferior rank of being, wherein he may
find both his power and inclination to obtain wisdom and exercise
virtue, exceedingly diminished? On the other hand, if that humble
admiration and gratitude, which sometimes rises in our minds when
we contemplate the power, wisdom and goodness of the Deity,
constitutes by far the most sublimely happy moments of our lives,
and probably will forever continue to do so, there cannot be a
stronger incitement to the exercise of virtue and a rational
employment of those talents we are entrusted with, than to consider
that by these means we shall in a few years be promoted to a more
exalted rank amongst the creatures of God, have our understandings
greatly enlarged, be enabled to follow truth in all her labyrinths with a
higher relish and more facility, and thus lay the foundation of an
eternal improvement in knowledge and happiness.

[TRANSLATED FROM THE LATIN ORIGINAL.]

To the illustrious and celebrated Society of Sciences, at Philadelphia,

Christian Mayer, Astronomer to the most serene Prince, the

Elector Palatine, wisheth prosperity.

I have concluded on due reflection, that the opportunity of writing,

afforded me by the eminent Mr. Ferdinando Farmer, ought the less to
be neglected, as by this means I might make some small return for
the honour which the illustrious Society conferred on me, when they
enrolled me in the list of their members.

I learnt with great pleasure, by a work printed in Philadelphia, and

transmitted to me about three years since, that even there
Astronomy is cultivated. That book, together with my own
astronomical papers, having been destroyed by an unfortunate fire
about two years ago, I have been induced to address something to
your illustrious Society, concerning some of my new discoveries in
the heavens.

I occupy a new Observatory at Manheim, accommodated to all

astronomical purposes: nor is it deficient in any of the most valuable
London-made instruments. Among these, the one which principally
excels, is a mural quadrant of brass, of eight feet radius, made by
that celebrated artist Bird, in the year 1776; fitted with an achromatic
telescope, and firmly affixed to a wall, in the meridian; which I use
daily, when the weather permits. I observed, nearly two years since,
that, among the fixed stars, many of them from the first to the sixth
degree of magnitude, other small attendant stars (or satellites) were
distinguishable: some of which, by reason of their steady and dim
light, resemble an order of planets, while others do not exceed the
smallness of the telescopic size. The circumstance which principally
excited my surprize, is, that I found none of those little attendant
stars, a very few only excepted, contained in any known catalogue;
although I could clearly discover that their use, for the purpose of
determining the proper motion of the fixed stars, is very obvious. For
where the difference of right ascension and declination, of a few
seconds at most, is found between the brighter fixed star and its
attendant, the lapse of time could scarcely give any other variation to
the fixed star, than to its satellite: from what cause soever that
variation may arise, whether from the precession of the equinoxes,
the variation in the obliquity of the ecliptic, the deviation of the
instrument, or from the aberration of light or the nutation, or from any
other cause whatever, which may depend on the mutable state of the
atmosphere or the latitude of places, the fact is evident, that every
change of situation, observed, between the fixed star and its
satellite, affords the most certain proof of its actual motion; whether
this be referred to the fixed star or its satellite.

I knew that Halley, the celebrated English astronomer, was the

first, who, in the year 1719, from an actual comparison of
Flamstead’s observations with those of Ptolemy, respecting some
few fixed stars, Syrius, Arcturus, and Aldebaran, discovered that
these stars moved, with a motion peculiar to themselves: But I knew
at the same time, that in Flamstead’s British Celestial History, so
long ago as the year 1690, the name of attendant (or satellite) was
assumed by Flamstead; when that great man had not even thought
of the proper motion of the fixed stars.

Other astronomers, since the time of Halley, so far as they

examined the proper motion of the fixed stars, have followed the
Halleian method, in a comparison of their own observations with
those of the ancients. This method requires long and laborious
calculations; and continues liable to many doubts, on account of its
uncertainty, as well by reason of the inaccurate nature of the
instruments, as of the observations of the ancients. But this is not the
case with my new method; from which, by means of the variation
observed between the satellite and its brighter fixed star, it
necessarily results, that the appropriate motion, either of the one star
or the other, is to be attributed to it. Hence it is, that, within two years
past, I have observed almost two hundred attendants of divers fixed
stars; moving nearly in the same parallel, immediately before or after
their respective fixed stars: and I have communicated many
observations of this kind to the celebrated English astronomer, Nevil
Maskelyne, who assures me they prove highly acceptable to him.

From amongst many of my observations, I transmit to your

illustrious society a few, by way of specimen; the corresponding
observations to which, I find in the Britannic Celestial History of
Flamstead; whence at the same time it is obvious, that observations
of this kind are eminently useful, for the purpose of discovering the
proper motion of such stars.

[The Table, containing the Observations here referred to, will be

found in the second volume of the Society’s Transactions, annexed
to Mr. Mayer’s communication: he then proceeds thus, referring to
that Table.]
 The first and second left-hand column of the following Table are
easily understood, from the title. The third column shews the
difference of right ascension, in mean time, between the star and its
satellite: The attendant, preceding the fixed star, is set down in the
first place, in the table; the attendant, following, is placed after its
fixed star. The fourth column notes the difference between the fixed
star and its attendant, as I have observed it at Manheim. The letter A
denotes, that the attendant is to the southward; letter B more
northward. The following columns contain the observations of the
same star, made by Flamstead.

It appears from the whole of the observations, that, of all the stars,
Arcturus is carried with the greatest celerity, by his own motion,
westward; since the same attendant, which in Flamstead’s time, on
the 14th of February, 1690, preceded Arcturus 5″ in time, now enters
the meridian 6″ after him. From the diminished difference also, of
declination between Arcturus and his attendant, it is evident, that
Arcturus progresses annually, by his own appropriate motion, nearly
2″ in a circular course, towards the south. From this it clearly results,
that the declination of the attendant, as observed by me, reduced to
the parallel of Greenwich, produces the same altitude of the
Greenwich pole, as that deduced from Flamstead’s observation; but
not so, the declination of Arcturus, observed at the present day, even
with the aberration and nutation corrected.

A similar investigation may be made, with respect to the other

fixed stars and their attendants; and, from the comparison already
begun with other fixed stars, it may be ascertained whether an
appropriate motion is to be attributed to the fixed star or its
attendant, or to both.

All my observations are made in a meridienal plane with a mural

quadrant, at Manheim, in his Serene Highness the Elector Palatine’s
new Observatory, erected for me: its longitude, East from
Greenwich, is nearly 34′ 6″, in time; its latitude, nearly 49° 27′ 50″.

It will give me very great pleasure, if I shall learn that these

observations of mine do not prove unacceptable to your illustrious
society: to whose goodness I most respectfully commend myself;
being ever the very devoted admirer and humble servant of your
illustrious and celebrated Society.

Christian Mayer,
Astronomer to his Serene Highness the Elector
Palatine and Duke of Bavaria.
Manheim, in Germany, April 24, 1778.

Letter from Mr. Rittenhouse to Professor Mayer of Manheim, in

Germany.

Philadelphia, August 20th. 1779.

Sir,

I am directed by the Philosophical Society to acknowledge your

letter of the 24th of April, 1778, and to return you their thanks for
communicating the Observations it contains, wishing you success in
further prosecuting so curious a Discovery. They likewise embrace
this occasion to replace the volume of their Transactions which
shared the fate of your more valuable papers.

This country having been the seat of war, our meetings have been
interrupted for two years past, and the publication of a second
volume thereby prevented; but as the Society is again revived, and
we have materials for the purpose, it will not be much longer
delayed.

You will please to accept, by this conveyance, a discourse

delivered some years ago before the Philosophical Society, which I
the rather present you with, because I, therein, gave my opinion that
the fixed stars afforded the most spacious field for the industry of
future Astronomers, and expressed my hopes that the noblest
mysteries would sometime be unfolded in those immensely distant
regions.[A40] Your excellent discovery has proved that passage to be
well founded, and I shall be happy in hearing farther from you on this
subject. It is unnecessary for me to suggest to you a comparison
between the many Observations you have made, in order to
determine whether the several changes observed will agree with any
imagined motion of our system. Those you have communicated
seem to favour such a supposition. I am, Sir, your most obedient and
humble servant.

David Rittenhouse, Vice-President.

Some Remarks of Mr. Rittenhouse, on the famous Problem of

Archimedes.[A41]
To the Printers of the Pennsylvania Gazette.

Philadelphia, Oct. 8th. 1767.

Gentlemen,

In your paper, No. 2017, an ingenious gentleman who signs

himself T. T. has favoured the public with remarks upon that
celebrated saying of the famous Syracusean geometrician: “Give me
a place to stand on, and I will move the Earth.” When these remarks
appeared, I was engaged in matters that would not allow me to pay
that attention to them, which they deserved. The justice, however,
due to Archimedes, and the respect I bear for that truly great man’s
memory, oblige me now (though late) to offer my sentiments upon
this interesting subject.

I readily agree with your sensible correspondent, as to the

conclusion he has drawn from the principles whereon he seems to
have founded his calculation, without being at the trouble to examine
his numbers. All that I propose is, to place this grand mechanical
problem in another light, wherein it will appear more feasible.

If a ball of earth, weighing 200 pounds, were left at liberty near the
surface of this globe, it would descend, by its own gravity, about 15
feet in one second of time, and about 20 miles in 80 seconds: And if,
as this gentleman supposes, there are about 2000 trillions of such
balls in the whole Earth,—the Earth, by their mutual attractions, in 80
seconds of time; will move toward the ball 1/1736,000,000,000,000
of an inch; and if the same force were to act continually for 105
years, it would move about one inch. Therefore, the force wherewith
a man acts, when he lifts a weight of 200 pounds, if applied without
intermission for the space of 105 years, is sufficient, without any
machinery, to move the Earth one inch in that time;[A42] and it must,
from the velocity received by that force alone, continue for ever after
to move at the rate of one inch in about 50 years.

A Mechanic.

Letter from Mr. Rittenhouse, to the Rev. Mr. Barton.

Norriton, July 20th. 1768.

Dear Brother,

In Hall and Sellers’ paper of last Thursday, we have some curious

remarks on an Essay for finding the Longitude, lately published in
the Pennsylvania Chronicle, and which I had before seen in the
London papers.

The first remark is no doubt just, and is perhaps the only one
made, which Mr. Wood’s essay gave just occasion for; how he could
commit such a mistake, is not easy to conceive. But the remarker
immediately charges him with another: for he tells us, that he (Mr.
Wood I suppose) says, that Mr. Harrison’s Machines were finished
about Christmas 1765; whereas his father (whether Wood’s father or
Harrison’s, is not clear,) made three, which the remarker saw in
motion about 18 years since. He then proceeds to assure us, (by the
spirit of prophecy I presume, at least I cannot conceive how he could
come by this piece of knowledge in a natural way,) that neither the
father or his son will ever be able to finish their machines.

A machine, says the remarker, to measure the mean motion, will

be far preferable to any other method yet proposed; and immediately
afterwards he confesses, he cannot conceive that a true meridian
can be found at sea, to several minutes. Now this “uncertain error”
must certainly affect any other machine for that purpose, as well as
Wood’s Sand-Glass, and exceed the error occasioned by turning the
glass somewhat quicker at one time than another. Besides, it would
not be easy to shew, why a machine to measure the Earth’s mean
motion on its axis, with respect to the Sun, will be preferable to one
that will measure the Earth’s true motion on its axis, with respect to
the fixed Stars.

I would not be thought to recommend Wood’s project. He himself

takes notice of two disadvantages attending it, viz. the wearing of the
orifice through which the sand passes, and the sand itself becoming
polished in time, so as to run more freely; to which if we add, that
perhaps it may be greatly affected by heat and cold, there seems to
be but little probability of its usefulness. Nor do I see how it can even
have the merit of being new: for the scheme itself, with all the
remarker’s objections that have any weight in them, must readily
occur to every person that thinks at all on the subject. I shall only
observe, that it appears doubtful to me, whether the remarker does
not equally deserve the censure he so freely bestows on Mr. Woods
—“His works are full of errors, and his writings of contradictions.”

* * * * * * * * * *

I remain your affectionate brother.

David Rittenhouse.
 Dr. Rittenhouse’s Chronometer.
The construction of this Time-piece is thus described by Mr. Henry Voight, chief
coiner in the Mint, heretofore an eminent clock and watch maker in
Philadelphia; an artist of great ingenuity, and well known for the excellence of
his workmanship. The description is given in Mr. Voight’s own words.

“The Clock which Dr. Rittenhouse made use of in his Observatory

was a construction of his own. It had but three wheels in its
movement, of high numbers. Only one pinion, without a wheel,
driven by the main wheel; whose axis goes through the front plate,
that carried the dial-work; and this wheel[A43] has a perpetual rochet.
[A44]
The seconds are eccentric, as in the common clocks.

“The pallet-wheel moves outside of the back-plate, and the pallets

are fastened to the rod of the pendulum, which has double
suspending springs fixed in a cross-bar, to which the rod is rivetted in
the middle. These springs are suspended as in common; but they
are not so long as in general, and have only one-and-an-half inch
free action, which keeps the pendulum very steady in its vibrations.

“On the rod of the pendulum there is fixed a glass tube, of the
thickness of a strong thermometer-tube, and is in the whole as long
as the rod: but it is bent, about one-third upwards; like a barometer,
but longer; and upon that end, on the top, the tube is as wide again
as it is below, for about one-and-an-half inch in length: the other two-
thirds of the length is filled with spirits of wine; and at this end, the
tube is hermetically sealed. The shorter part is filled with mercury, so
high as to fill the widest part of it, about half an inch, and is not
sealed but remains open. The bend is close together, and there is no
more space between the tubes than three-eighths of an inch.

“This tube is fastened to the pendulum-rod with common sewing-

thread, and rests upon two pins fixed in the bob of the pendulum, as
high up as possible. The bob has no slide, but is immoveable; and