ABC Nano Technology

ABC NANO TECHNOLOGY

[History, Applications & Fabrication]

Collected By
Dr. Eng. Abdullah Mohamdy A.

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Table of Contents

Page
INTRODUCTION 6
CHAPTER 1
1. HISTORY OF NANO TECHNOLOGY. ………………… 7
1.1. What is Nanotechnology? ………………………………… 7
1.1.1. Definition of nanotechnology. ……………………………… 7
1.1.2. Concept of nanotechnology. …………………………… 8
1.1.3. What is a nanoparticle? ………………………………… 8
1.1.4. What is a nano-composite? 10
1.2. History of Nano Technology. 12
1.2.1. General. 12
1.2.2. PRE 18th century Lycurgus cup - Roman Period (30BC-640AD). 12
1.2.3. Stained Glass – Medieval Period (500-1450). 13
1.2.4. Deruta Ceramicists – Renaissance Period (1450-1600AD) 13
1.2.5. In 1827 - Photography 14
1.2.6. In 1857 - Discovery of Gold Colloids 15
1.2.7. In 1908 - Mie Theory 16
1.2.8. In 1931 - First Electron Microscope 16
1.2.9. In 1947 - The Transistor 17
1.2.10. In 1951 - Erwin Mueller’s field-ion electron microscope 18
1.2.11. In 1953 - Discovery of DNA 19
1.2.12. In 1958 - Tunneling Phenomenon 19
1.2.13. In 1960 - Ferrofluids 21
1.2.14. In 1960 - Zeolite Catalysts 22
1.2.15. In 1965 - Moore’s Law 22
1.2.16. In 1970 - Sir John Pople’s software 23
1.2.17. In 1974 - Term “Nanotechnology” First Used 24

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1.2.18. In 1974 - Molecular Electronics 24

1.2.19. In 1977 - Surface Enhanced Raman Spectroscopy (SERS) 24
1.2.20. In 1980 - Self – Assembled Monolayers (SAMS) 25
1.2.21. In 1981 - Scanning Tunneling Microscope 26
1.2.22. In 1985 - The “Buckyball” 27
1.2.23. In 1986 - Atomic Force Microscope 27
1.2.24. In 1987 - Single – Electron Tunneling Transistor 28
1.2.25. In 1988 - Discovery of Quantum Dots 29
1.2.26. In 1990 - Manipulation of Atoms 30
1.2.27. In 1991- Carbon Nanotubes 30
In 1996 - Using DNA and Gold Colloids to Assemble Inorganic
1.2.28. 31
Materials
1.2.29. In 1999 - Development of Dip-Pen Nanolithography 32
1.2.30. In year 2000 - Feedback – Controlled Lithography (FCL) 32
1.2.31. In year 2000- Establishment of National Nanotech Initiative 33
1.2.32. In 2001 - : U.S. Army to establish new center 34
1.2.33. History of Nano Ferrites 37
CHAPTER 2
2. APPLICATIONS OF NANO TECHNOLOGY 40
2.1. Factors Influencing Use of Nano-Products 40
2.1.1. Price competition …………………… 41
2.1.2. Technical performance 41
2.1.3. Awareness within the sector. 42
2.2. Nano-Materials for Building Design & Construction …… 43
2.2.1. Cement, concrete and wet mortar …… 44
2.3. Applications of Nanotechnology. ……… 45
2.3.1. Nano coatings and paints applications. …… 45
2.3.1.1. Anti-reflective Nano coatings 46
2.3.1.2. Solar protection Nano coatings 46
2.3.1.3. Self-cleaning Nano coatings (Lotus effect) 47
2.3.1.4. Self-healing (self-repairing) Nano coatings 48

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2.3.1.5. Scratch proof and abrasion resistant Nano coatings 49

2.3.1.6. Temperature regulation Nano coatings 50
2.3.1.7. Antimicrobial coatings 51
2.3.1.8. End of the line for subway-riding germs 51
2.3.1.9. Plumbing fixtures 52
2.3.1.10. Anti-corrosion coatings 52
2.3.1.11. Moisture resistance 54
2.3.1.12. Nano coatings for Wood Surfaces 55
2.3.1.13. Nanotechnology and Fire Protection 56
2.3.2. Adhesives 56
2.3.2.1. Self-assembling Nano scale chains form Nano-superglue 57
2.3.3. Plastics and polymers 58
2.3.4. Roofing ………………………………… 58
The nanotechnology potentials hierarchy for more green building
2.3.5. 59
performance
2.3.5.1. Nanotechnology adaptability to existing buildings 59
Integration of nanotechnology materials for green building
2.3.5.2. 60
impacting both architecture design and building construction:
2.3.5.3. Environmental and human health concerns 63
2.3.5.4. Safety risks of dealing with nano-products on the construction site 65
Towards further co-operation between nano scientists, nano
2.3.5.5. 66
products
CHAPTER 3
3. FABRICATION OF NANO MATERIALS 67
3.1. Fabrication of Nano materials ………… 67
Specificity and Requirements in the Fabrication Methods of
3.1.1. 68
Nanoparticles
3.1.2. Oxides …………………………………………… 69
3.1.3. From molecular species to nanoparticles …………………… 70
Hydroxylation of metal cations in aqueous solution and
3.1.3.1. 70
condensation

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3.1.3.2. Control of particle size, crystalline structure and morphology 78

3.1.3.3. Hydrolysis of metallo-organic compounds 86
3.1.3.4. Nonhydrolytic routes to oxide Nanoparticles 92
3.1.4. From minerals to materials ……………………………………. 98
3.2. Structural Behavior of Nano Material 103
3.2.1. Introduction 103
Effect of adding nano materials on the compressive strength of the
3.2.2. 104
concrete.
3.2.3. Effect of high temperature on the concrete. 108
4. REFRENCES 115

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Introduction

Every now and then, there comes along a material seems to fill a gapping void
in the endless needs of common man. Revolutionary developments conjure up visions
of dwindling housework, maintenance, free finishes, great cost savings and long term
strength. Nano materials are a modern historical material and have vast range of
applications that may be of great potential of the construction of the structures in the
21st century.

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CHAPTER 1

HISTORY OF NANO TECHNOLOGY.

1.1. What is Nanotechnology?

1.1.1. Definition of Nanotechnology.

Nanotechnology is science, engineering, and technology conducted at the Nano

scale, which is about 1 to 100 Nanometers. Nano science and Nanotechnology are the
study and application of extremely small things and can be used across all the other
science fields, such as chemistry, biology, physics, materials science, and engineering
[1].

1.1.2. Concept of Nanotechnology.

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Nanotechnology simply means the ability to observe, monitor and influence

materials (and their behavior) down to the Nanometer (nm) detail (e.g. a size range
about 10.000 x smaller than the thickness of a human hair). This involves advanced
imaging techniques to study and improve material behavior, but also the design and
production of very fine powders, liquids or solids containing particles of a size
between 1 and 100nm, so called Nanoparticles [2].

Nanotechnology is the use of very small pieces of material by themselves or their

manipulation to create new large scale materials.

Another important aspect is that, as particles become Nano-sized, the proportion

of atoms on the surface increases relative to those inside and this leads to novel
properties. It is these “Nano-effects”, however, that ultimately determine all the
properties that we are familiar with at our macro-scale” and this is where the power of
Nanotechnology comes in – if we can manipulate elements at the Nano scale we can
affect the macroproperties and produce significantly new materials and processes [3].

Nanotechnology, the understanding and control of matter at dimensions of

roughly one to one hundred billionths of a meter, is bringing dramatic changes to the
materials and processes of science and industry worldwide. By working at the
molecular level, Nanotechnology opens up new possibilities in material design. In the
Nano scale world where quantum physics rules, objects can change color, shape, and
phase much more easily than at the micro scale. Fundamental properties like strength,
surface to- mass ratio, conductivity, and elasticity can be designed in to create
dramatically different materials [4].

1.1.3. What is a Nanoparticle?

A Nanoparticle is a microscopic particle whose size is measured in Nanometres
(nm). It is defined as a particle with at least one dimension less than 200nm.
Nanoparticles made of semiconducting material (material that is between a conductor
and insulator e.g. silicon) may also be labeled quantum dots if they are small enough
(typically sub 10nm) such that jumps in energy levels occur. The importance of this is

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that the same material of different sizes can emit different colours when energized
with, for instance, UV light. Carbon Nanotubes are a sub set of Nanoparticles.
Engineered Nanoparticals have a large rang of diversity as shown in Figure (1.1) [5].

Until scientists were able to view matter at the Nano scale it was impossible to
effectively manipulate materials at that level, view the results of experiments, and
measure their properties. Optical tools, along with tools for working with matter at the
Nano scale such as electron-beam lithography, were only really developed during the
1980s and 1990s.

Carbon Nano tubes (CNT), possibly the first application of Nano materials، look
like a fine black powder to the human eye. Viewed through a microscope it's apparent
that the tubes are hollow fibers that can be over a million times as long as they are
thick. Their structure gives them a massive strength-to weight ratio, which when
blended with polymers can add strength to anything from car tires to golf clubs. They
are also good conductors, and are used at a much finer level in electronics [6].

Nanoparticles have unique mechanical, electrical, optical and reactive properties

distinct from larger particles. Their study (Nanoscience) and manipulation
(Nanotechnology) also open up the convergence of synthetic and biological materials
as we explore biological systems which are configured to the Nano scale. Crossing the
traditional boundaries between living and non-living systems allows for the design of
new materials with the advantages of both.

The market for Nano-based products and processes for sustainability is expected
to grow from $12 billion in 2006 to $37 billion by 2015. New materials and processes
brought about by Nanotechnology, for example، offer tremendous potential for
fighting global climate change [4].

Globally, Nanotechnologies are expected to reduce carbon emissions in three

main areas: Transportation, Improved insulation in buildings, and Generation of
renewable photovoltaic energy.

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Figure (1.1): Various features contributing to the diversity of engineered

Nanoparticles, the same chemical can generate a wide variety of Nanoparticles [5].

Nano-enabled advances for energy conservation in architecture include new

materials like carbon Nanotubes and insulating Nanocoatings, as well as new
processes including photocatalysis. Nanomaterials can improve the strength,
durability, and versatility of structural and non-structural materials, reduce material
toxicity, and improve building insulation [5].

1.1.4. What is a Nano-Composite?

A Nano-composite is produced by adding Nanoparticles to a bulk material in

order to improve the bulk material’s properties [3].

Nano fibrils would lead to a new paradigm in sustainable construction as both the
production and use would be part of a renewable cycle. Some developers have
speculated that building functionality onto lignocellulosic surfaces at the Nano scale
could open new opportunities for such things as self-sterilizing surfaces, internal self-
repair, and electronic lignocellulosic devices. These non-obtrusive active or passive

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Nano scale sensors would provide feedback on product performance and

environmental conditions during service by monitoring structural loads, temperatures,
moisture content, decay fungi, heat losses or gains, and loss of conditioned air.
Currently, however, research in these areas appears limited.

Due to its natural origins, wood is leading the way in cross-disciplinary research
and modeling techniques which have already borne fruit in at least two areas. Firstly,
BASF have developed a highly water repellent coating based on the actions of the
lotus leaf as a result of the incorporation of silica and alumina Nanoparticles and
hydrophobic polymers. And، secondly, mechanical studies of bones have been
adapted to model wood، for instance in the drying process.

In the broader sense, Nanotechnology represents a major opportunity for the

wood industry to develop new products, substantially reduce processing costs, and
open new markets for bio based materials [3].

1.2. History of Nano Technology.

1.2.1. General

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Date of Nano-materials due to pre-Christmas. But they were not yet known. The
first applications that contain Nano-particles were at fifteenth century in ceramic
industry and in nineteenth century in gold industry. The first to label the word Nano
was in the twentieth century.

1.2.2. PRE 18th century Lycurgus cup - Roman Period (30BC-640AD):

Archeological remains give clues to the use of Nanotechnology materials in ancient
times. A famous artifact from this period called the Lycurgus cup resides in the British
Museum in London. The base of the Lycurgus cup is made from glass and dates from
the fourth century AD (the gilded bronze base and rim were added later). What makes
this cup unique is that its color changes from green (when illuminated from within).
What causes the color change? Transmission electron microscopy reveals that the
glass contains Nanoparticles of gold and silver. At the Nano scale, materials exhibit
properties that are different from their macro scale counterparts. Most likely the
unique properties of this ancient roman piece from this era that appear to be failed
attempts to recreate this effect.
(BC: before Christ, AD: Anno Domini)

Figure (1.2): Lycurgus cup.

1.2.3. Stained Glass – Medieval Period (500-1450): Although unaware of the

reasons, stained glass is due to gold Nanoparticles trapped in the glass matrix, while
the deep yellow color is due to silver Nanoparticles. The size of the metal
Nanoparticles produced these color variations. This example of the dramatic change in

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material properties (in this case, color) at the Nano scale is a key component of
Nanotechnology.

Figure (1.3): Stained Glass

1.2.4. Deruta Ceramicists – Renaissance Period (1450-1600AD): Artisans

coloring pottery in fifteenth- and sixteenth century Deruta. Umbia were practicing an
early form of Nanotechnology. Deruta ceramicists produced dramatic iridescent or
metallic glazes, which during the fifteenth and sixteenth centuries were in demand
throughout Europe. To achieve the red and gold luster effects, particles of copper and
silver metal between 5 and 100 billionths of a meter were used. Instead of scattering
light, the particles cause light to bounce off their surface at different wavelengths,
giving metallic or iridescent effects.

Figure (1.4): Deruta Ceramicists

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1.2.5. In 1827 - Photography –: Photography is an early example of

Nanotechnology, this depends on the production of silver Nanoparticles sensitive to
light. Photographic film is a thin layer of gelatin containing silver halides and a base
of transparent cellulose acetate. The light decomposes the silver halides, producing
Nanoparticles of silver, which are the pixels of the photographic image. In the late
eighteenth century, the British scientists Thomas Wdgewood and Sir Humphry Davy
were able to produce images using silver nitrate and chloride, but their images were
not permanent. The first successful photograph was produced in 1827, by Joseph
Niepce using material that hardened on exposure to light. This picture required an
exposure of eight hours. Niepce went into partnership with Louis Daguerre. Although
Niepce died from a stroke only four years later, Daguerre continued to experiment and
in 1839 discovered a way of developing photographic plates, a process which greatly
reduced the exposure time from eight hours to half an hour. He also discovered that an
image could be made permanent by immersing it in salt.

Figure (1.5): First Photography

1.2.6. In 1857 - Discovery of Gold Colloids –: Although the term “Nano” was
not in use at the time, early researcher Michael Faraday (berthed Sept. 22, 1791 – died
Aug.25, 1867) discovered and prepared the first metallic colloids in 1856. Colloids are
fine particles that suspend in a solution (in between particles that dissolve in solution
and those that settle). Faraday’s gold colloids had special electronic and optical
properties, and are now known as one of the many interesting metallic Nanoparticles.

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Figure (1.6): Gold Colloids

Considered by many to be one of the greatest experimentalists who ever lived,

the English chemist and physicist Faraday received little more than a primary
education, and at the age of 14 was apprenticed to a bookbinder. There he became
interested in the physical and chemical works of the time. After hearing a lecture by
the famous chemist Humphrey Davy, he sent Davy the notes he had made of his
lectures. As a result Faraday was appointed assistant to Davy in the laboratory of the
Royal institution in London at the age of 21. The entire set of specimens (over 600)
used by Faraday in his 1856 research are still housed at the Royal Institution of Great
Britain.
1.2.7. In 1908 - Mie Theory –: German physicist, Gustav Mie played a hand in
Nanotechnology with his theory of light scattering by particles. His theory shows that
light scatters from particles more efficiently at short wavelengths than at long
wavelengths. For example, we see the sky as being blue because the molecules in air
(which are extremely small particles) scatter light from the sun more efficiently for
blue light than for yellow or red, as blue light has the shorter wavelength.
When the sun sets, the sunlight travels through the atmosphere over a longer
distance than when it is overhead. The most important scattering in this case arises
from dust particles. These particles still scatter light more effectively for blue colors,
so the light that is not scattered is a mixture of red and yellow. This produces the
characteristic red color of the setting sun.

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Mie theory helped scientists to realize that the size of particles determines the
colors that we see. Mie went on to develop a way to calculate the size of particles by
determining the light they scatter. For Nanoparticles and larger particles, this theory
requires a huge number of calculations, so it was rarely used until about 20 years ago
when supercomputers became available. Now, Mie theory (as well as others
developed more recently) helps researchers predict and determine the size of
nonoparticles.
1.2.8. In 1931 - First Electron Microscope –: Although light microscopes had
been around since the Renaissance, they were unable to recognize objects that were
smaller than the wavelength of visible light (0.4-0.7 micrometers). To see particles
smaller than this, scientists had to bypass light altogether and use a different sort of
“illumination”, one with a shorter wavelength.
In 1931, German scientists Max Knott and Ernst Ruska developed an entirely
new type of microscope that would eventually open up a new “small” world. With the
electron microscope, electrons are accelerated in a vacuum until their wavelength is
extremely short, only one hundred-thousandth that of white light. Beams of these fast-
moving electrons are focused on a sample. Parts of the sample soak up the electrons,
other parts scatter them. An electron-sensitive photographic plate “records” this action
and creates an image. In 1933 the electron microscope was able to exceed the detail
and clarity of the traditional light microscope. This was an important first step in the
development of techniques and instrumentation that would eventually enable research
at the Nano scale.

Figure (1.7): Electron Microscope

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1.2.9. In 1947 - The Transistor –: Until the mid1940’s, vacuum tubes were the
state of-the-art in electronics. Capable of converting alternating current to direct
current (AC to DC) and amplifying an electronic signal, vacuum tubes were used in
everything from switching telephone calls to building the first high speed computer,
ENIAC. But the limitations were clear. The tubes were bulky and to make more
powerful computers more tubes were needed (17000 tubes were used in ENIAC). The
tubes were also fragile and overheated easily. In 1945, Bell Labs established a
research group to look into finding a solution. The group was led by William
Shockley and included Walter Brattain and John Bardeen.
After two years, Bardeen and Brattain created an amplifying circuit that seemed
to work, using the element germanium. They called it the point-contact transistor. The
discovery did not gain attention until 1951, when Shockley improved upon the
original idea with a junction transistor. The transistor was a solid (giving rise to the
term “solid-state technology”), but had the electrical properties of a vacuum tube.
Furthermore, it was inexpensive, sturdy, used little power, worked instantly, and best
of all, was tiny. The three men shared the 1956 Nobel Prize in physics “for their
researches on semiconductors and their discovery of the transistor effect”. The
invention of the transistor and the integrated circuit marked the beginning of
microelectronics, a field that relies on tools for miniaturization. The semiconductor
industry is one of the largest technology drivers in the field of Nanotechnology.
Researchers today are looking to enable the creation of chips holding billions or even
trillions of Nano scale transistors. [7]

Figure (1.8): Transistors

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1.2.10. In 1951 - Erwin Mueller’s field-ion electron microscope –: The

development of Nanotechnology was, and is, dependent upon advances in scientific
instrumentation. Erwin Mueller, a professor at Penn State University’s department of
physics, made an important contribution when he invented the field-ion electron
microscope in 1951. For the first time in history, individual atoms and their
arrangement on a surface could be seen. For this accomplishment, Professor Mueller
is known as the first person to “see” atoms. The device was a landmark advance in
scientific instrumentation that allowed a magnification of more than 2 million times.
Born in Berlin in 1911, Erwin was the only child of a family of modest means.
His father was a construction worker who specialized in plastering ceilings in houses.
He obtained his doctorate in engineering from the Technische Hochschule Berlin-
Charlottenburg in 1936. After practicing for many years in Germany, Erwin was
recruited by Penn State. He and his family moved there in 1952 and he became a U.S.
citizen in 1962. His achievements were recognized by numerous awards, including
election to the prestigious National Academy of Sciences. [8]
1.2.11. In 1953 - Discovery of DNA –: One of the landmark achievements in the
20th century was the discovery of DNA. By the 1950s, scientists already knew that
DNA –deoxyribonucleic acid – carried genetic information, but they didn’t know what
it looked like or how it worked.
In 1953, Dr. James Watson and Professor Francis Crick published an article in
Nature describing the double helix structure of DNA. They showed that when cells
divide, the tow strands that make up the DNA helix separate and a new “other half” is
built on each strand, a copy of the one before. This means that DNA can reproduce
itself without changing its structure, except for occasional errors or “mutations”.
James Watson, Francis Crick, Maurice Wilkins and Rosalind Franklin all played
critical roles in this discovery of the DNA structure. In 1962 Wilkins shared the Nobel
Prize with Watson and Crick. Tragically, Rosalind Franklin had died a few years
earlier at the age of 37, and since Nobel Prize are not awarded posthumously, she was
not included in the honor.

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Figure (1.9): DNA

Decades later, DNA’s ability to self-assemble into tiny structures would inspire
researchers to use the same principles to develop Nano scale structures with specific
dimensions and chemical properties.

1.2.12. In 1958 - Tunneling Phenomenon –: In 1958, Leo Esaki, a Japanese

physicist working at Sony Corporation, discovered that electrons could sometimes
“tunnel” through a potential barrier formed at the junctions of certain semiconductors
even though classical theory predicted that this was not possible. What Dr. Esaki
observed was an example of how materials at the Nano scale are controlled by
different laws of behavior, i.e., they are controlled by quantum mechanics as opposed
to classical physics. The discovery lead to the creation of the tunneling diode
(sometimes called the Esaki diode), an important component of solid-state physics,
and the first time that tunneling (an important Nano-electronics phenomenon) was
used in a real device. Dr. Esaki was awarded the 1973 Nobel Prize in physics for this
discovery along with physicists Ivar Giaever of Norway and Brian D. Josephson of
Great Britain. [9]
In 1959 - Richard Feynman –: Richard P. Feynman is often credited with
predicting the possibilities and potentials of Nano-sized materials. Feynman, who
would go on to win the Nobel Prize in physics, gave a talk on December 29, 1959
entitled, “there’s Plenty of Room at the Bottom.” In his speech he stated.

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Figure (1.10): Richard Feynman

“What I want to talk about is the problem of manipulating and controlling things
on a small scale.
As soon as I mention this, people tell me about miniaturization, and how far it
has progressed today. They tell me about electric motors that are the size of the nail on
your small finger. And there is a device on the market, they tell me, by which you can
write the Lord’s Prayer on the head of a pin. But that’s nothing; that’s the most
primitive, halting step in the direction I intend to discuss. It is a staggeringly small
world that is below. In the year 2000, when they look back at this age, they will
wonder why it was not until the year 1960 that anybody began seriously to move in
this direction.” [10]

1.2.13. In 1960 - Ferrofluids –: In the 19610’s, NASA researchers were trying

to find ways to control liquids in space. They discovered that Nano-size magnetic
particles of iron that were given a chemical coating, or surfactant, that prevented them
from clumping together could be dispersed in oil or water. They could then control the
location of the fluid (called a ferrofluid) with a magnet.

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Figure (1.11): Ferro fluids

On Earth, Ferro fluids are used inside loudspeakers, where they help keep the
inner parts cool. They are also used on computer hard drives and in semiconductor
manufacturing, as seals to keep out dust and other contaminants.
Nanotechnologists want to harness Ferro fluids for other important uses such as
developing tiny sensors, or inside the body as biomedical devices, to deliver drugs,
absorb toxins, or treat hypothermia. It is even possible that Ferro fluids could be used
to help clean up hazardous waste spills.

1.2.14. In 1960 - Zeolite Catalysts –: A zeolite is an inorganic porous material

which works as a kind of molecular sieve – allowing some molecules to pass through
while excluding or breaking down others. Zeolites can be natural or synthetic, and
new zeolites are still being discovered and invented.
In 1960, Charles Plank and Edward Rosinski developed a process to use zeolites
to speed up chemical reactions. Plank and Rosinski’s process focused on using
zeolites to break down petroleum into gasoline more quickly and efficiently.

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Figure (1.12): Zeolite Catalysts

Researchers are currently working to design zeolite catalysts at the Nano scale.
By adjusting the size of the zeolite pores on the Nano scale, they can control the size
and shape of molecules that can enter. In the case of gasoline production, this
technique could mean that we would get more and cleaner gasoline from every barrel
of oil. It is hoped that Nanotechnology will help reduce the cost and pollution
associated with producing gasoline and other petroleum products. [11]

1.2.15. In 1965 - Moore’s Law –: Writing for Electronics magazine in 1965,

Gordon E. Moore the founder of Intel Corporation, noted that the number of
transistors per integrated circuit had double every two years. He predicted that this
trend would continue for another 10 years and his prediction were quickly dubbed
“Moore’s Law” by the press. Moore’s prediction turned out to be prophetic. In fact,
the complexity of a chip continued to double yearly, long after 1975. The rate of
doubling has only recently slowed to about every 18 months. Many researchers
believe that devices which use electronic Nanotechnology and molecular electronics
will keep Moore’s Law accurate into the future. [12]

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Figure (1.13): Moore’s Law

1.2.16. In 1970 - Sir John Pople’s software –: Mathematics is a foundation for

science. It provides mathematical descriptions of complex real-world phenomena or
“models”. Modeling develops hand-in-hand- with the science it describes. Developing
new mathematical formulas is an essential part of science, and as science becomes
more complicated, new, faster formulas are needed. Although computers had become
dramatically more powerful by this time, new software must be developed in order for
that power to be useful. Up until this time, it was very difficult to solve the complex
mathematical equations needed to determine the properties of molecules. In 1970,
John Pople and his research group developed Gaussian, a software program that
would perform these calculations. This pioneer in the use of computers to predict the
behavior of atoms and molecules also developed many of the algorithms that made
computer-based modeling at the Nano scale possible. For this work, Dr. Pople, a
Northwestern University Board of Trustees professor and British citizen, shared the
1998 Nobel Prize for chemistry and was knighted by Queen Elizabeth in 2003. [13]

1.2.17. In 1974 - Term “Nanotechnology” First Used –: The term

“Nanotechnology” was first used by Norio Taniguchi of the Tokyo Science

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University. He used the word to refer to “production technology to get the extra high
accuracy and ultra-fine dimensions, i.e. the preciseness and fineness on the order of 1
Nanometer.” [14]
1.2.18. In 1974 - Molecular Electronics –: In 1974, Northwestern University
Charles and Emma Morrison Professor of Chemistry. Mark A. Ratner and A. Aviram
IBM, proposed that individual molecules might exhibit the behavior of basic
electronic devices, thus allowing computers to be built from the bottom up by turning
individual molecules into circuit components. This hypothetical application of
Nanotechnology, formulated long before the means existed to test it, was so radical
that it wasn’t pursued or even widely understood for another 15 years. For this
groundbreaking work, Ratner is widely credited as the “father of molecular-scale
electronics” and his contributions were recognized in 2001 with the Feynman Prize in
field of Nanotechnology. [15]
1.2.19. In 1977 - Surface Enhanced Raman Spectroscopy (SERS) –: Some of
the tools needed in the field of Nanotechnology were many years in the making. For
example, spectroscopy is a set of techniques that use the interaction of light with
matter to obtain information about its identity and structure of molecules. Sir
Chandrasekhara Venkata Raman (Calcutta University) won the 1930 Nobel Prize in
physics for his 1928 discovery that the scattering of light by molecules could be used
to provide information about a sample’s chemical composition and molecular
structure. Although a ground-breaking technique, Raman Spectroscopy was not
capable of detecting at the Nano scale. The technique was greatly improved in the
1960s by the invention of the laser, but it wasn’t until 1977, when Richard P. Van
Duyne (Northwestern University) discovered Surface Enhanced Raman Spectroscopy
(SERS), that Nano scale studies became possible. Van Duyne deduced that when
molecules were attached to a surface which had hills and valleys that were
approximately 50-100 Nanometers in size, the Raman intensity was amplified
1,000,000 times. The discovery of SERS completely transformed Raman
Spectroscopy from one of the least sensitive to one of the most sensitive techniques in
all of molecular spectroscopy. Today, SERS is used to study the chemical reactions of

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molecules in electrochemistry, catalysis, materials synthesis, and biochemistry. The

sensitivity of SERS is now so high that even single molecules can be studied. [16]

Figure (1.14): Surface Enhanced Raman Spectroscopy (SERS)

1.2.20. In 1980 - Self – Assembled Monolayers (SAMS) –: In 1980, Jacob

Sagiv at the Weitzman Institute in (Occupied Palestine) discovered that molecules
containing a chemical called Octadecyl Trichloro Silane or OTS would spontaneously
react with a glass surface to assemble by themselves onto individual layers. In 1983, a
Bell Labs research team lead by David Allara discovered that molecule with Thiol
groups (groups containing surfur) on a gold surface would also self-assembled
monolayers are typically a few Nanometers thick (determined by the choice of
molecule) and allow researchers to tailor the properties of a surface. For the first time,
scientists could envision building three dimensional Nano scale structures layer-by-
layer, like laying rows of bricks to build a wall. These structures are being used to
build molecule-based electronic devices, biosensors, and new types of optical
materials. [17], [18]

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Figure (1.15): Self – Assembled Monolayers (SAMS)

Figure (1.16): Scanning Tunneling Microscope

1.2.21. In 1981 - Scanning Tunneling Microscope –: In 1981, the scanning

tunneling microscope (STM) was invented by Gerd Binnig and Heinrich Rohrer at
IBM’s Research Laboratory in Zurich, Switzerland. This invention allowed scientists
not only to observe Nano scale particles, atoms, and small molecules, but to control
them. The STM scans the tip of a needle, or “probe,” just a few atoms above the
surface of the sample. A voltage is applied between the tip of the probe and the
surface. As the electric current begins to flow, the STM can determine minute
variations in the distance electrons travel. In this way, the STM maps the surface of
the sample. The information is saved in data file and a “picture” of the surface is
created by computer. In this way, the STM can “see” atomic scale objects. The STM
helps researchers determine the size and form of molecules, observe defects and
abnormalities, and discover how chemicals interact with the sample. The STM quickly

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became standard equipment in laboratories throughout the world. Binning and Rohrer
were awarded the Nobel Prize in Physics in 1986 along with German scientist Ernst
Ruska, who designed the first electron microscope. [19]
1.2.22. In 1985 - The “Buckyball” –: Anther Nanotechnology breakthrough
occurred in 1985, when Richard Smalley, Robert Curl and graduate student James
Heath at Rice University, and Sir Harry kroto at the University of Sussex discovered
\c60, a carbon Nanoparticle shaped like a soccor ball. The unique molecule was
named Buckminister fullerene after the visionary American architect and engineer
Buckminster Fuller who designed the geodesic dome. More commonly called a “buck
ball”, the molecule is extremely rugged, capable of surviving collisions with metals
and other materials at speeds higher than 20,000 miles per hour.

Figure (1.17): The “Buckyball”

Because of this ruggedness, bucky balls show promise in the development of fuel
cells that might power the automobiles of the future. Researchers are also
investigating the possibility of using bucky balls as tiny 1996 Nobel Prize in
Chemistry “for their discovery of fullerene.” [20]
1.2.23. In 1986 - Atomic Force Microscope –: Invented by Gerg Binnig and his
colleague Christoph Gerber at IBM, San Jose, and Calvin Quate at Stanford
University, the atomic force microscope or AFM uses a cantilever to “read” a surface
directly, the way a record player’s needle reads a record. Atomic force microscopy

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works by passing the cantilever – so sharp that its tip is composed of a single atom –
within a few Nanometers of a surface. The atomic forces exerting an topographical
map atom-by-atom. The AFM makes 3-D images of an object’s surface topography
with extremely high magnifications (up to 1,000,000 times). [21]
1.2.24. In 1987 - Single – Electron Tunneling Transistor –: In 1985 Dmitri
Averin and Konstantin Likharev, then at the University of Moscow, proposed the idea
of a new device called a single-electron tunneling (SET) transistor. Two years later
Theodore Fulton and Gerald Dolan at Bell Labs in the US built such a device. In this
structure the controlled movement of individual electrons through a Nano scale device
was first achieved.

Figure (1.18): Single – Electron Tunneling Transistor.

Single-electron devices are based on what is called the tunnel effect. When two
metallic electrodes are separated by an insulating barrier about 1 Nanometer thick
(approximately 3 atoms in a row), the electrons are able to “tunnel” through the
insulator, even though classical theory suggests that this is impossible. Researchers
have long considered whether SET transistors could be used for digital electronics, but
the random variations in voltage from device to device caused serious problems.
Working at the Nano scale, today’s researchers are considering how to overcome this
problem by combining all of the components of the SET transistor into a single
molecule. It is possible that conventional circuits will one day be replaced by

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electronics based upon individual molecules and form the basis for a new class of
Nano electronics. [22]
1.2.25. In 1988 - Discovery of Quantum Dots –: In the early 1980s, Dr. Louis
Brus and his team of researchers at Bell Laboratories made a significant contribution
to the field of Nanotechnology when they discovered that Nano-sized crystal
semiconductor materials made from the same substance exhibited strikingly different
colors. These Nanocrystal semiconductors were called quantum dots and this work
eventually contributed to the understanding of the Quantum Confinement Effect,

Figure (1.19): Quantum Dots

which explains the relationship between size and color for these Nanocrystals.

Due to their extraordinarily small size, the electrons inside the quantum dots
exhibit unique behavior. Specifically, the electrons are confined far fewer energy
levels than allowed in bulk semiconductors materials. This results in the quantum dots
emitting very intense light of specific color when the electrons make transitions
between these discrete energy levels. Small differences in the size of the quantum dot
change the allowed electron energies and therefore alter the color of light which they

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emit. Scientists have learned how to control the size of quantum dots making it
possible to obtain a broad range of colors (see Medieval Period and stained glass).
Quantum dots have the potential to revolutionize the way solar energy is
collected, improve medical diagnostics by providing efficient biological markers, and
advance the development of optical devices such as light emitting diodes (LEDs). [23]
1.2.26. In 1990 - Manipulation of Atoms –: Using a Scanning Tunneling
Microscope (STM), IBM researchers Donald Eigler and Erhard Schweizer were able
to arranged individual Xe atoms on a surface. Although the process was painstakingly
slow, the remarkable image allowed researchers to place individual xenon atoms with
Nano scale precision and to visualize the results. This now famous image of the
atomic world “hangs” in IBM’s STM Image Gallery, and demonstrates early attempts
to create structures one atom at a time. [24]

Figure (1.20): Manipulation of Atoms.

1.2.27. In 1991- Carbon Nanotubes –: In 1991, Smio Lijima at NEC in Japan

discovered a new form of carbon called Nanotubes, which consisted of several tubes
nested inside each other. Two years later Lijima, Donald Bethune at IBM in US and
others observed single-walled Nanotubes just 1-2 Nanometers in diameter.

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Figure (1.21): Carbon Nanotubes.

Nanotubes behave like metals or semiconductors, but can conduct electricity

better than copper, can transmit heat better than diamond, and are among the strongest
materials known. Nanotubes could play a pivotal role in the practical applications of
Nanotechnology if their remarkable electrical and mechanical properties can be
exploited. [25]
1.2.28. In 1996 - Using DNA and Gold Colloids to Assemble Inorganic
Materials –: Since Faraday’s discovery of the unique electronic and optical properties
of gold colloids in 1857, researchers have sought to harness these capabilities. In
1996, Northwestern University researchers, Chad Mirkin and Robert Letsinger,
discovered a way to do this. They attached strands of synthetic DNA onto gold
Nanopaticles. Since complementary strands of DNA can recognize and bind to each
other, the DNA served as a blueprint, a construction worker, and a sorter to create new
inorganic materials. By manipulating the DNA, they were able to make materials with
the same unusual properties as the Nano scale building blocks that they are made
from. This advance generated an explosion of interest in making designer bio-
inorganic architectures at the Nano scale. [26]

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Figure (1.22): Assemble Inorganic Materials

1.2.29. In 1999 - Development of Dip-Pen Nanolithography –: A pivotal

development in the constellation of Nanotechnology tools was Dip-Pen
Nanolithography or DPN. Invented in 1999 by Chad A, Mirkin (rathmann Professor of
Chemistry and Director of the Institute for Nanotechnology at Northwestern
University), the concept is based upon a classic quill pen – a 4,000 year old
technology. Using an atomic microscope tip, DPN allows researchers to precisely lay
down or “write” chemicals, metals, biological macromolecules, and other molecular
“inks” with Nanometer dimensions and precision on a surface. DPN has progressed to
include 1,000,000 tip serial and parallel processing – opening the door to credible
Nano-manufacturing techniques for smaller, lighter weight, faster, and more reliably
produced electronic circuits and devices, high-density storage materials, and
biological and chemical sensors. [27]
1.2.30. In year 2000 - Feedback – Controlled Lithography (FCL) –:
Feedback- controlled lithography (FCL) a technique that allow researchers to use the
Scanning Tunneling Microscope (STM) to precisely and selectively build structures at
the Nano scale.

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Figure (1.23): Dip-Pen Nanolithography

Developed by Mark Hersam (Northwestern University) and Joseph Lyding
(University of Illinois at Urbana-Champaign), FCL is conducted by first coating a
silicon sample with hydrogen (otherwise known as hydrogen passivated silicon).
Using the STM, researchers can then image (or see) the surface of the silicon sample.
When an electric voltage is applied to the STM tip from an outside source, the silicon-
hydrogen bonds are broken. By controlling the position of the STM tip, hydrogen
atoms are thus removed with atomic precision.

Figure (1.24): Controlled Lithography

This technique allows fundamental studies of chemistry at the single molecule

level and has opened the door for building prototype electronic devices and other
structures at the Nano scale. [28]
1.2.31. In year 2000- Establishment of National Nanotech Initiative –:
Attempts to coordinate work on the Nano scale began in November 1996 when staff

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members from several federal agencies decided to meet regularly to discuss their plans
and programs in Nano scale science and technology. By 1998, this group (now called
the Interagency Working Group on Nanotechnology or IWGN) was focused on
defining the art of Nano scale science and technology and forecasting possible future
developments. In August 1999, IGWN completed its first draft of a plan for an
initiative in Nano scale science and technology. The plan went through an approval
process involving the President’s Council of Advisors on Science and Technology
(PCAST) and the Office of Science and Technology Policy. As a result of this work,
the Clinton administration raised Nano scale science and technology to the level of a
federal initiative by including major funding as part of its 2000 budget submission to
Congress, and officially referred to it as the National Nanotechnology Initiative
(NNI). [29]
1.2.32. In 2001 - : U.S. Army to establish new center for "Soldier
Nanotechnologies" The U.S. Army began taking a detailed look at short-term
applications for Nanotechnology during a "Workshop on Nano science for the
Soldier", which was held by the Army Research Office at the North Carolina
Biotechnology Center in Durham, NC, in early February 2001.
The workshop marked the start of a program by the U.S. Army to establish the
Institute for Soldier Nanotechnologies (ISN) and a University Affiliated Research
Center (UARC), with academic and industry partners, to develop Nanometer-scale
science and technology solutions that could be incorporated into a soldier's gear.
Information about the intended goals of the ISN can be found in the formal
solicitation for the center released in October 2001 (available online as an Adobe
Acrobat PDF file). Funding for the ISN will be about $US 10 million per year, for at
least five years. According to the solicitation:
"The individual soldier . . . will require systems revolutionary in their
capabilities. Recent advances in the field of Nano science suggest that may be possible
to provide the soldier with radically new capabilities in full-spectrum threat protection
without incurring significant weight or volume penalties. Such soldier systems will
only be realized by directing additional resources to the Army's Science and
Technology Program in the emerging field of Nano science. . . .

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"The purpose of this research center of excellence is to develop unclassified

Nanometer-scale science and technology solutions for the soldier. A single university
will host this center, which will emphasize revolutionary materials research toward
advanced soldier protection and survivability capabilities."
Applications could include a uniform that monitors a soldier's vital signs, or
sends out an alert in the presence of toxins and decontaminates the soldier before any
damage occurs. Or it could be a material that changes color to camouflage the soldier
or protect him or her against ballistics.
An article on the Small Times website ("Army scouts out research university to
help equip tomorrow's Nano soldier", by Candice Stuart, 13 June 2001), provided
additional coverage of the Army's announcement.
According to the article, researchers expect the program will benefit the Army
but also commercial users. "They will take these enabling materials and apply them to
make solutions," said Sanford Asher, a chemistry professor at the University of
Pittsburgh who participated in the Nanotech workshops sponsored by the Army.
Although the Army is involved, he anticipates any knowledge gained through the
collaboration would remain in the public domain. "The things that are classified are
not enabling technologies," he said. "You can't keep enabling technology a secret. I
don't think that will be an issue. The issue will be once you take the enabling
technology and make something for the Army. It will be classified on the industry
side."
The new program was the subject of Congressional hearings. This included the
testimony of Delores Etter, Deputy Undersecretary of Defense for Science and
Technology, along with chief scientists from other military departments, before the
House Armed Services Strategic Subcommittee on the state of military research and
development, on 26 June 2001.
An article from United Press International ("Congressional panel hears plans for
Nanotechnology in the military", by K. Hearn, 27 June 2001) included some of the
comments:
"Nanotechnology is something that will give us revolutionary, new capabilities,
though a lot of research has to be done," said Etter. While major breakthroughs and

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benefits are still decades away, she said Nanotechnology will help systems become
smaller, "whether we look to get smaller power sources, things needing lower power
or materials built from the atomic level."
"Technology developments in Nano science and advanced materials are needed
to provide revolutionary opportunities for the war fighter to develop totally new
operational concepts and capabilities, based on such developments," Etter and another
witness, Edward "Pete" Aldridge, Undersecretary of Defense Acquisition, Technology
and Logistics, said in written testimony.
Competition between universities in the U.S. to become the host for the
University Affiliated Research Center (UARC) has been keen.
Responses to the solicitation from universities competing to host the UARC were
due by 15 November 2001. An announcement of where the facility will be hosted is
expected to be made sometime early in 2002. [30]

Winners of the 2001 Feynman Prizes in Nanotechnology

Mark A. Ratner T Charles M. Lieber

Announced during the Ninth Foresight Conference on Molecular

Nanotechnology:

Theory: Mark A. Ratner, Professor of Chemistry, Northwestern University

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Professor Ratner was cited as a theorist whose work has made major
contributions to the development and success of nanometer-scale electronic devices.
He was a visionary co-inventor of the concept and scientific study of molecular-scale
electronics. Ratner has continued to refine his early concepts with a series of
theoretical innovations and articles. His work has been instrumental in establishing
scientific understanding, worldwide, about the mechanisms and magnitudes of
conduction in molecular junctions, and in particular, the nature of charge transport in
single molecule nano structures.

Experimental: Charles M. Lieber, Professor of Chemistry, Harvard University

Professor Lieber, was cited for his pioneering experimental work in molecular
nanotechnology which included seminal contributions to the synthesis and
characterization of the unique physical properties of carbon nanotubes and nanowires.
He has developed numerous innovative applications of nanowires and carbon
nanotubes, including the assembly of these building blocks into complex structures for
nanodevice applications. Lieber's work led to the creation of new tools for molecular
nanotechnology and represents a significant advance towards molecular scale
computation and nanotechnology.

1.2.33. History of Nano Ferrites.

Since the discovery of ferrites, about 80 years ago, much basic and applied
research has been carried out to explore their potentials. During the 1940's and 1950's,
ferrites were systematized in the academic field, and today ferrite theory is well
organized. From the 1950's, as radio and television sets spread, ferrites established a
significant position in the industry, and now ferrites are one of the most essential
materials in the electronics industry [31].

Ferrites constitute a special branch of ferromagnetic. The term ferrite denotes a

group of iron oxides, which have the general formula MO. Fe2O3, where, M is a

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divalent metal ion such as Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Mg2+ or Cd2+.The
typical ferrite is magnetite, Fe3O4 (on FeO.Fe2O3), which has been a well known
magnetic oxide since ancient time. The ferrites were developed into commercially
important materials chiefly during the year 1933-1945 by Sonek and his associates at
the Philips Research Laboratories in Holland. In a classical paper published in 1948,
Neel provided the theoretical key to an understanding of the ferrites [32, 33].

There are many types of Nano particles or Nano-sized materials produced and
applied in the cement-based materials matrix including: silica Nano-particles (Nano-
SiO2), Nano-iron oxide (Nano-Fe2O3), Nano-alumina (Nano-Al2O3), Nano-clay, Nano
titanium oxide (Nano-TiO2), Nano-calcium carbonate (Nano CaCO3), and Nano-
cement. A Nano-particle in the structure of the cement-based materials is not used
only in terms of Nanoparticle reaction. Other considerations should be studied to
make a decision considering performance, lower prices, and better accessibility.
Accordingly, the silica Nano-particles, whether in terms of performance or of price
and accessibility, are the most appropriate Nano-particles used in the concrete
industry. Nano-particles are used to improve the mechanical properties and durability
of cement based products according to their different behaviors. Nano-particles
improve the performance of cement-based materials matrix according to possession of
one or more of the following categories [34, 35].

- To increase the production of calcium - silicate - hydrate (CSH) gel due to

pozzolanic reaction and reduce amounts of Ca(OH)2 crystals;
- To prevent the excessive growth of crystals in the matrix and control crystallization;
- Micro and Nano-filling;
- Development of hydration reaction.
The second type of Nano-materials applied in the structure of cement-based
materials is Nano-chemical additive. These materials improve the rheological
performance of concrete products and contribute major support in order to produce
specific concretes. Nano viscosity modifying agents, Nano super plasticizers, and
Nano-polymers are some examples of these materials. Finally, the third group of
Nano-materials is Nano fibers used in the matrix of concrete materials. According to

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the types of fibers in the structure of cement-based materials, carbon Nano-fibers

(CNF), carbon Nanotubes (CNT) and Nanocellulose fibers can be indicated. Nano-
fibers improve the mechanical characteristics, create higher impact capacity, and
reduce cracks in concrete specimens. These materials increase tensile and bending
strengths by creating a bridge between micro cracks in the matrix of cement-based
materials and also acting as nucleating sites for the hydration products [36-42].

However, if these Nano-particles are not being dispersed appropriately and

agglomerate in the matrix of cement-based materials, their performance in the matrix
will be reduced. As a result, high range water reducer supper plasticizers should assist
Nano-particles, and also usage of low dosage Nano-particle contents would aid the
fabrication process. Moreover, using lower amounts of these types of materials are
preferred due to reducing the costs. The other notable point is the increase in
shrinkage while the Nano-particles are added. This issue can be effective in
serviceability of the structure. Low dosage application of Nano-particles can prevent
this defect in an acceptable manner; however, mostly we have to utilize the shrinkage
reducing agents [43, 44].

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CHAPTER 2

APPLICATIONS OF NANO TECHNOLOGY.

2.1. Factors Influencing Use of Nano-Products:

In 2003, R&D specialists shared high expectations about the near future
developments of Nano-products for the construction industry. However, only little of
the products expected that time really made it to the construction site of today.
Various reasons can be appointed. The most important ones will be discussed as [2]:

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2.1.1 Price competition.

The very first reason why Nano-products may be successful in society but still do
not make it in the construction industry is the costs involved. At the moment, Nano-
materials and consequently Nano-products are still significantly more expensive than
their non-Nano alternatives because of the technology required to produce them. For
the construction sector, this implies that already at the R&D phase of a product,
initiatives are stopped when is foreseen that the Nano-product to be produced will
never reach competitive pricing.

Largely this is due to the fact that construction products almost always come in
large volumes and small price differences at the kg level add up to enormous increase
in total costs when the total volume of the construct is considered.

As a result, manufacturers of construction materials are reluctant to develop

Nano-products and those Nano-products that are developed are only applied upon
specific request. This in particular holds for the larger volume products like concrete
or mortar and for construction coatings. However, for e.g. insulation materials and
architectural and glass coatings, the current societal focus on the improvement of
energy management in the context of climate change and the reduction of greenhouse
gasses does stimulate their further market introduction.

2.1.2 Technical performance.

The technical performance of the product is a second limiting factor for large
scale Nanoproduct introduction. The technical performance should thoroughly be
proven to meet the technical standards for that material. Obviously, this does depend
on the market sector. For concrete for example this is a major issue. For self cleaning
window coatings, this issue is much less important as the safety standards for instance
are much lower.

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2.1.3 Awareness within the sector.

Awareness (or the lack thereof) is another key element hampering the
introduction of Nanoproducts in construction works. Without awareness one simply
doesn’t know there is anything new to apply or explore. Within Europe, knowledge
about Nanotechnology in construction is very limited and at this moment is still the
property of a small number of key players that develop the market. The 2009-survey
set out by the FIEC (uropean Construction Industry Federation) and EFBWW
(European Federation of Building and Wood Workers) to monitor the awareness of
construction workers and their employers resulted in Figure (2.1), showing that the
majority of respondents (~75%) was not aware if they do work with Nanoproducts[2].

Figure (2.1): 2009-survey response of employers and worker (representatives) being

aware or not aware of the presence of Nano-products at their workplace[2].
These, together with findings from in-depth interviews conducted in parallel to
the 2009-survey with a number of involved key players do suggest that
Nanotechnology did not yet penetrate the construction sector to any significant depth.

Those respondents to the 2009-survey working with Nano-products mostly

worked with cement or concrete products, coatings or insulation materials see Figure
(2.3). Other product types, including road-pavement products، flame retardant
materials or textiles, were only indicated by some. All respondents used their Nano-

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products because of performance reasons (excluding an alternative product) and

sometimes on (additional) specific request by the customer [2].

Figure (2.2): Nano-products actually indicated to be used; number of products per

product type, from the results of the 2009-survey [2].

2.2 Nano-Materials for Building Design & Construction

The total market share of Nano-products in the construction industry is relatively
small, but it is expected to grow in the near future and Nanoparticles are expected to
play an important role at the very basis of material design, development and
production for the construction industry. Already now Nanoproducts could in
principle be found in nearly every part of an average building.

Nano-products related to coatings and cement and concrete materials probably

make up for the largest market share of Nanoproducts of today’s construction
industry, followed by insulation materials. Carbon-fuoride polymers (CF-polymers)
are Teflon like molecules that are brought onto a surface to make this surface water
and oil repellent. Applications are typically found on glass.

Titanium dioxide (TiO2) absorbs UV light and is used as a protective layer against
UV degradation. Some forms of TiO2 are photo-catalytic and catalyze the degradation
of organic pollutants like algae, PAHs, formaldehyde and NOx under the influence of
UV light. Applications are found for practically every surface type that has to be UV-

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protected, made self-cleaning or should assist in the reduction of air pollution. Zinc
oxide (ZnO) knows similar photo-active characteristics to TiO2 and can be used for
similar applications. Silica fume (amorphous SiO2) compacts concrete, making it
stronger and more durable under alkaline conditions like marine environments.

It can also be added to concrete to stabilize fillers like fly-ash, to a coating

material resulting in a very strong matrix, or used as fire retardant agent. Typical
applications are UHPC (Ultra High Performance Concrete), scratch resistant coatings
and fire resistant glass. Silver (Ag) acts as a bactericide and can be added to all sorts
of materials. In construction it is mostly found in coatings. In fact, it is the silver-ion,
formed when Ag dissolves in water that is responsible for the anti-bacterial activity.
Aluminum oxide (Al2O3) is used in coatings to interact with the binder material and to
add high scratch resistance to this coating [45].

Nanocomposites, which combine new Nanomaterials with more traditional ones

such as steel, concrete, glass and plastics, can be many times stronger than standard
materials [46].

2.2.1 Cement, concrete and wet mortar

CO2 emissions from the global cement industry are significant and they are
increasing. Global cement production is currently around 1.6 bn tones/yr, and through
the calcination of limestone to produce calcium oxide and carbon dioxide,
approximately 0.97 tones of CO2 is produced for each tone of clinker produced.
Around 900 kg of clinker is used in each 1000kg of cement produced so the global
cement industry produces around 1.4 tonnes of CO2 each year. This represents about
6% of the total worldwide man-made CO2 production.

Fly ash not only improves concrete durability, strength and, importantly for
sustainability, reduces the requirement for cement, however, the curing process of
concrete is slowed by the addition of fly ash and early stage strength is also low in
comparison to normal concrete.

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With the addition of SiO2 Nanoparticles part of the cement is replaced but the
density and strength of the fly-ash concrete improves particularly in the early stages.
Research into haematite (Fe2O3) Nanoparticles added to concrete has shown that they
also increase strength as well as offering the benefit of monitoring stress levels
through the measurement of section electrical resistance [3].

For concrete, the combination of an already existing good performance available

at low costs implicates a high challenge for any successful application of
Nanotechnology. One of the areas where Nanotechnology does prove extremely
valuable now and in the near future is the understanding and optimization of material
properties.

Nanoparticles use in cementageous and concrete materials does concentrate on

TiO2 and silica fume. Both additives though, are used in small quantities or in a two-
layer system and only when specifically required for performance reasons because of
the costs involved.

Near future developments are expected in the field of silica fume to stabilize
concrete containing significant fractions of recycled concrete aggregates and
encapsulated additives to optimally tune the hardening process [47].

2.3 Applications of Nanotechnology.

2.3.1 Nano coatings and paints applications.

First of all, it's pretty hard to distinguish between the meaning of coatings and
paints. So, it might be better just to think of it as "Coatings" being the general term and
"Paints" coming under the umbrella of Coatings. But how do Nanocoatings work?

In the context of surface coatings, comparing the size and behavior of ordinary
particles in traditional coatings to those that are Nano-sized, a traditional coating has
particles which are actually too large to adhere to the majority of the substrate, but a
Nano particle is much smaller and collectively, the mass of Nano particles has many

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more sides to adhere to the substrate, figure (2.3). Because of this, the Nano coating
can be applied more successfully and thinner than the non-Nano coating. One can also
see that the finished result is a much tighter, thinner, stronger and smoother coating
[48].

Fig (2.3): A comparison between the traditional coating and the Nano coating
[48].

Hence, designers should be able to align with Nanotechnology and use the new
innovations of Nano materials during design process. Given that the innovations of
Nano materials coincide with the advocacy to Design Trends that are compatible with
the Environment, So the designer can utilize and harness Nanotechnology and Nano
materials, especially Nano coatings to apply the Concepts of Green and Sustainable
Design, as one of the important goals which advocated by engineers and designers for
achieving in the future building.

2.3.1.1. Anti-reflective Nano coatings: Antireflective glass can be used as a

tailored system for protecting historical facades and ancient glazing. For this
application, color neutrality is of crucial importance since the optical appearance of
the building should not be influenced. The antireflective glass can easily be adjusted
in its reflectance color by varying the coating thickness.

2.3.1.2. Solar protection Nano coatings: The Company Raven Brick has
invented and patented a thermo chromic window material that responds to changes in
temperature by automatically changing tint according to its temperature. The result
looks a little like the way transitions lenses in eyeglasses tint in bright light. When the

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material heats up, the molecular structure on the Nano scale changes its optical
properties, which makes electronically-tin table glass for building windows can be
programmed to respond to changing weather conditions without needing electricity
[49]. The idea is simple enough: when it gets hot the windows darken to block
incoming solar radiation, and when it is cold they are clear to allow the free heat in all
without electricity. The windows do not change tint on a gradient but rather change
from transparent directly to semitransparent and back again. The founder of Raven
Brick estimates that these windows can cut a building’s energy use by 30-40% each
year [50].

2.3.1.3. Self-cleaning Nano coatings (Lotus effect): The Lotus-Effect is most

well suited for surfaces that are regularly exposed to sufficient quantities of water,
such as rainwater. The Lotus - Effect drastically reduces the cleaning requirement and
surfaces that are regularly exposed to water remain clean. The advantages are cleaner
appearance and considerably reduced maintenance demands [50]. Some
Nanotechnologists have developed treatments, coatings, paints, roof tiles, fabrics and
other surfaces that can stay dry, and clean themselves in the same way as the lotus
leaf. This can usually be achieved using special fluoro chemical or Silicone treatments
on structured surfaces or with compositions containing micro-scale particulates [53].

Figure (2.4): The thermo chromic glass [51].

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Figure (2.5): Self-cleaning (Lotus Effect) is one of the best-known means of designing
surfaces with Nano materials [54].

2.3.1.4. Self-healing (self-repairing) Nano coatings: Self-repairing materials

have been the dream of engineers for centuries. Many have been inspired by human
skin and tissue which meshes itself together if it is damaged. Scientists as Dr Marek
Urban who developed an intelligent polymer at the University of Southern
Mississippi, Hattiesburg claim to have invented a "self-healing" coating that repairs
scuffs or blemishes on paint when exposed to sunlight [55]. Some materials include
networks of tunnels or tiny Nanoparticles that "bleed" when broken, filling in gaps
caused by scratches. The coating is a Poly urethane containing Chitosan, a chemical
produced in the shells of crabs, lobsters and shrimps, and organic compounds called
Oxetanes arranged in rings. When the coating is scratched, the rings of Oxetane are
broken to expose chemically reactive sites. Ultraviolet light splits open the Chitosan
molecules exposing another set of reactive sites. The oxetane and chitosan attract each
other, bond and close the scratches, Figure (2.6) [55]. The speed of the repair depends
on the sunshine. In Mediterranean weather scratches vanish three or four times
quicker than they would in typical British weather. However, the material also needs
more testing before it can be used in paints and protective coatings. Although the
material is still at the laboratory stage, it could be available on commercial products
within five years, experts say [55].

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Figure (2.6): Self-repairing action in Nano coatings [55].

2.3.1.5. Scratch proof and abrasion resistant Nano coatings: Nanotechnology

makes it possible to improve scratch-resistance in order to reduce traces of use whilst
maintain transparency. Likewise, cleanly designed surfaces maintain their appearance
better through the use of scratchproof and abrasion-resistant surfaces [52]. Liquid
Glass- a kind of scratch-resistance- is a thin layer, also known as Silicon dioxide
(SiO2) in ultra thin layering, which is only 100 Nanometer thick (1/500 the width of a
human hair), but it can protect against wear, and still allow the surface underneath to
breathe[56]., because the coating is flexible. It can protect underlying matter from
water, bacteria, dirt and even UV radiation. Liquid Glass is harmless to the
environment and could replace a variety of harsh cleaning chemicals. The coating can
be cleaned with water alone [57]. Zinc oxide, another Nanomaterial, is used for
surface coatings, paints, and outdoor furniture varnishes [58]. Scratch-resistance is a
desirable property for many materials of different kinds such as wood, metal and
ceramics.

Scratchproof paints and varnishes are desirable, for instance to protect the varnished
surfaces of parquet flooring or the surfaces of other gloss lacquered surfaces [52].
Liquid Glass cleaner is perfect for windows architectural glasses, and ceramic frits.
Figure (2.7) shows methods of using liquid glass on surfaces.

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Figure (2.7): Methods of using Liquid Glass on surfaces [57, 59].

Liquid Glass is completely harmless and even safe to use around food [59, 60]
and could revolutionize household cleaning; one application would help keep every
surface sterile for a year and only require light rinsing with warm water. So, the
kitchen counter tops can be covered in it, and it can stay clean and sterile for months
[56]. It is perfect for and granite worktops, chafing dish table tops, and dinner table
tops.

2.3.1.6. Temperature regulation Nano coatings: These climatic regulating

characteristics make these coatings real problem solvers all around the house.

Buildings and structural facilities, particularly those in southern regions, are

exposed to extreme climatic influences. These heat, UV radiations, moisture, and salty
air. Only effective coating protection for facades and roofs will avoid this high cost of
renovation and repairs while counteracting these various stresses in a regular manner,
Figure (2.8) [61].

Figure (2.8): Temperature regulation Nano coatings [61].

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2.3.1.7. Antimicrobial coatings: Many of the multifunctional coatings

already mentioned incorporate antimicrobial properties. Others are marketed
specifically for their antimicrobial properties.

Antimicrobial products are marketed in sprays, liquids, concentrated powders,

and gases. The U.S. Environmental Protection Agency (EPA) says that approx. $1
billion each year is spent on antimicrobial products. Conventional antimicrobial
products can contain any of about 275 different active ingredients, including
biocides, which may release into the environment. Some biocidal ingredients in
antimicrobial products pose both environmental hazards and indoor air quality
concerns.

Antimicrobial Nanocoatings reportedly offer the benefits of conventional

antimicrobial products without these environmental and health concerns. One of
these products has a combination of antimicrobial and heat deflective properties.
And its low thermal conductivity and the ability to reflect up to 90 % of the sun’s
rays reduce heat absorption in coated walls, thereby reducing air conditioning and
energy consumption.

Researchers in Bremen, Germany have developed a process for binding

antibacterial silver Nanoparticles permanently to paint. The coating is certified as
emission-free, and can destroy antibiotic-resistant bacteria and has been used in
more than 20 hospital projects in Europe and the Gulf region, including the 40,000
square meter Discovery Gardens project in Dubai. Many antimicrobial
Nanocoating manufacturers can “cross-link” a variety of Nanoparticles to add
additional functionality such as UV protection and improved wear resistance to
their coating [62].

2.3.1.8. End of the line for subway-riding germs: Many surfaces that people
touch every day in a subway carry thousands of bacteria and germs. With news of
powerful flu strains like avian flu and hand-transmissible diseases like colds,
public transportation operators like these pioneers are considering using new

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Nano-enhanced disinfectants in their subways. Hong Kong is among the first cities
to apply silver-titanium dioxide Nanocoating to subway car interiors, and this
coating can kill most of the airborne bacteria and viruses they come into contact
with [68]. Preliminary tests show the disinfectant reduced the presence of bacteria
by 60%.

One of these products is a Nanotech-water-based antimicrobial with no

poisons, as a preventative product for use in homes and businesses in hurricane
paths. Antimicrobial Nanocoatings can also be incorporated into ceramic surfaces.
A German plumbing-fixture manufacturer, for example is developing a new
coating which is fired over traditional ceramic glazing to create a surface so
smooth that dirt, germs, and fungus cannot stick to it. In addition, water beads up
and run off the hydrophobic surface without lime and soaps being able to build up.

Many paints contain Nanoparticles (commonly TiO2) to prevent mildew, are

specially produced for interior spaces, bathrooms and kitchens [64].

2.3.1.9. Plumbing fixtures: An antimicrobial polymeric, a plastic resistant to

germs, molds, yeast, and mildew is used in more than 450 products ranging from
cleaning supplies, paints and caulking to medical products, plumbing fixtures, and
other kitchen and bath products. According to the manufacturer, it does not wash
or wear off of its material substrate [75].

Several plumbing fixture manufacturers are starting to paint anti-microbial

coatings on sinks and toilets, which means less maintenance and lower costs [46].

2.3.1.10. Anti-corrosion coatings: The cost of corrosion in the U.S. is

estimated at $276 billion per year. In Germany, 4% of the GNP is lost every year
as a result of corrosion damage. Corrosion takes a toll not only on steel structures,
but on concrete ones, which require steel reinforcing. In fact, 15% of all concrete
bridges are structurally deficient because of corroded steel reinforcement.

For protecting metal surfaces from corrosion, chrome plating is becoming an

increasing concern because of the negative health and environmental effects of

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chromium. But corrosion can be reduced by coating materials with chemically

resistant Nanofilms of oxides. Some related technologies consist of homogeneous
thin films using alkoxides with chemically attached ceramic Nanoparticles [66].

Another technology is using organic metals that are free from heavy metals.
This makes it possible to replace not only lead compounds, chromate treatments
and chromate, but also the zinc-rich coatings that will in the future be classified as
containing heavy metals.

Measurements have shown that the Nanoceramic coating delivers markedly

better corrosion protection and paint adhesion than iron phosphate, in addition, it
do not require bath heating, and can be applied at room temperature, thus saving
energy.

An organic-metal solder able surface finish technology could be applied to

architectural metals and this new process consumes less than 10% of the energy
compared to other metallic finishes, and promises to save more than 90% of raw
materials [67].

Another range of Nano-structured metal coatings have properties that meet or

exceed those of hard chrome, including wear resistance, corrosion resistance,
coefficient of friction, and also allow for the complete elimination of chromium.
Another Nano-product is an oil-free, Nanotechnology-enhanced surface treatment,
which easily removes all staining and soiling and leaves behind a clean surface
that is water and dirt repellent. It protects stainless steel against contamination for
up to two years, even if fully exposed to weathering or harsh environments.

During the lifetime of the coating, the producer said, maintenance is reduced
to wiping the surface with a wet cloth. It is VOC- and acid -free.

Scientists in India have devised a method to protect copper from corrosion by

coating it with conducting polymers (poly O-anisidine coatings) reduce corrosion
by a factor of 100 [68].

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2.3.1.11. Moisture resistance: Resistance to moisture penetration is critical to

the durability of construction materials. Moisture causes rot in susceptible
materials and feeds harmful mold and bacteria. Unfortunately, many conventional
waterproofing materials, such as polyurethane, give off harmful VOCs as they
cure. Nanocoatings, in contrast, provide moisture resistance without these harmful
side effects. One of these Nano-products is a breathable antimicrobial sealant that
protects wood, sheet rock and other porous materials from moisture as it
encapsulates any mold spores that might have settled on building materials and
prevents future mold growth. Made up of cross-linking polymers, it bonds itself to
the cellulose in wood and paper, eliminating mold's nutrient sources.

Water is a principal source of damage to concrete as well, and even dense,

high-quality concrete does not eliminate absorption of water and soluble
contaminates through capillary action and surface permeability. This can cause
efflorescence and corrosion of the reinforcement. Some water based micro
emulsions can help in reducing water absorption in concrete, and can be applied to
the surface or blended into the concrete mix. The result, says the manufacturers, is
a low water absorptive concrete that is salt and frost resistant and cannot be
affected by efflorescence, moss or algae. Its penetration properties are similar to or
better than solvent-based solutions and these products are VOC- and odor -free
[69].

Another Nano-product is of an integral waterproofing system that eliminates

the need for external membranes, coatings and sheeting treatments for concrete
construction. With this product, concrete is batched with the liquid admixture to
achieve hydrophobic performance with less than 1 % absorption.

Another range of coatings was invented to coat reinforcing steel surface with a
monomolecular film while providing waterproofing properties to the concrete. It
reacts with metals in the water, concrete, and reinforcement to form a precipitate
that fills the capillaries of the concrete, repelling water and shutting down capillary
absorption. The product is so environmentally safe it is the first material certified

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by Cradle-to-Cradle, a new program that evaluates and certifies the quality of

products by measuring their positive effects on the environment, human health,
and social equity [70].

Another Nano-product is a water-based solution with a very high penetration

depth for concrete materials. The hydrophobic treatment is long lasting and can
only be removed by damaging the surface. Another exterior coating possesses a
highly water-repellent surface similar to that of the lotus leaf. Its microstructure
has been modeled on the lotus plant to minimize the contact area for water and
dirt.

Self-cleaning awning fabrics are extremely dirt, grease, oil and water repellent
by highly dirt repellent finish offering UV protection and ensure long lasting
radiant colors [72].

Ohio State Univ. engineers, for example, are designing super-slick, water
repellent surfaces that mimic the texture of lotus leaves for application in self-
cleaning glass. Hong Kong Univ. of Science and Technology has available, “Novel
TiO2 Material and the Coating Methods Thereof.”[72].

One of new products on that field, cleans, protects, preserves and enhances the
appearances of leather or vinyl surfaces used for covering items in the home or in
vehicles. It dries quickly and leaves no oily residue behind. It is a combination of
natural camauba wax Nanoparticles and zinc oxide Nanoparticles with a
quaternary siloxane compound [73].

2.3.1.12. Nano coatings for Wood Surfaces: Nano coatings for wood
products are developed for walls and facades (exterior), but also for parquet
flooring systems and furniture (interior) and do focus on water (and to a lesser
extent oil) repulsion, scratch resistance and UV protection. Though there are
several products on the market, there is skepticism regarding the durability of
especially the water and UV protective coatings because of the quality of some of
the first generation products.

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New generation UV-protective coatings can be based on organic UV absorbers

or the metal oxides ZnO and CeO2. TiO2 is less used because of transparency and
photo-catalytic activity reasons.

Example of high scratch resistant wood lacquers containing Nano-SiO2 or

Nano-sized Al2O3 particles. In contrast to external wear factors like UV or
scratching, part of the properties of wood is the bleeding of complex chemicals
like tannins that, in time, decolorize the wood surface. By treating the wood
surface with a Nano-clay containing coating (i.e. Hydrotalcite
Mg4Al2(OH)12CO3.H2O).

Nano coatings that protect wood against water or oil are based on CF
polymers)[74].

2.3.1.13. Nanotechnology and Fire Protection: Fire resistance of steel

structures is often provided by a coating produced by a spray-on cementations’
process. Current Portland cement based coatings are not popular because they need
to be thick, tend to be brittle and polymer additions are needed to improve
adhesion. However, research into Nano-cement (made of Nano-sized particles) has
the potential to create a new paradigm in this area of application because the
resulting material can be used as a tough, durable, high temperature coating. This
is achieved by the mixing of carbon Nanotubes (CNT’s) with the cementinous
material to fabricate fibre composites that can inherit some of the outstanding
properties of the Nanotubes such as strength. Polypropylene fibers also are being
considered as a method of increasing fire resistance and this is a cheaper option
than conventional insulation [3].

2.3.2. Adhesives:

While not the most glamorous technology, adhesives have revolutionized the
construction industry. Construction adhesives were, in fact, voted the most
significant technological advance of the last half of the 20th century in one survey
of industry professionals. But many contain environmentally harmful substances

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like formaldehyde. Much of the inspiration for Nano enabled adhesives comes
from nature. Adopting nature’s tricks is sometimes referred to as biomimicry.
Examples of how Nano scientists mimic nature can be found in the water-repellent
properties of Nano coatings, which take their lessons from the hydrophobic lotus
leaf, and in a new generation of Nano-adhesives now under investigation, which
are based on the remarkable feet of the gecko, which enable it to climb walls and
even ceilings [2].

Rensselaer Polytechnic Institute and the Univ. of Akron have created synthetic
gecko Nanotube tape with four times the gecko’s sticking power that can stick and
un-stick repeatedly [2].

2.3.2.1. Self-assembling Nano scale chains form Nano-superglue:

Researchers have developed a new method using self-assembling Nano materials
to bond materials that don’t normally stick together.

New bio-mimetically inspired Nanostructures have been developed, which can

stick to wet, dry, rough or smooth surfaces, and can be peeled off and reused.
These materials are also self-cleaning, leave no residue, and are bio-compatible.
Max Planck Institute for Metals Research in Stuttgart, Germany, has developed
materials whose surface structure allows them to stick to smooth walls without any
adhesives. The extremely strong adhesive force of these materials is the result of
very small, specially shaped hairs based on the soles of beetles' feet. Their artificial
adhesive system lasts for hundreds of applications, does not leave any visible
marks, and can be thoroughly cleaned with soap and water [75].

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Figure (2.9): Scientists have developed materials whose surface structure allows them
to stick to smooth walls without any adhesives. (Max Plank institute for Metal
Research) [75].

2.3.3. Plastics and polymers

Vinyl (PVC), which is used in a wide range of building materials, has come
under fire recently as detrimental to human health. Phthalates, used to make PVC
flexible, have been cited as bronchial irritants and potential asthma triggers. In
addition, PVC production is the world’s largest consumer of chlorine gas, using about
16 million tons of chlorine per year worldwide.

New alternatives for many conventional plastics are resulting from Nano
composite research. For example, glass microspheres, or micro balloons, created using
a spray pyrolysis process, can be cast in a polymer matrix to create syntactic foam
with extremely high compressive strength and low density. Naturally occurring Nano
scale aggregates can also be used in making Nano composites. The crystalline
structure of these ceramic materials allows them to be easily separated into flakes or
fibers [76].

2.3.4. Roofing

Nanotechnology is beginning to make an impact on roofing. For example, a self-

cleaning clay roof which tile’s burned-in surface finish destroys dirt particles, grease

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deposits, soot, moss and algae with the aid of sunlight, another product is solar roofing
tiles embedded with Nano rods.

Nanogel was used with translucent aerogel in energy efficient day-lighting

roofing systems. The Nanogel day-lighting material combines high light transmission
with energy efficiency and sound insulation. It will be incorporated into polycarbonate
panels made specifically for translucent roofing applications. The combined panel
provides more than 5 times the energy efficiency of glass panels typically used in
residential sloped glazing and this technology allow penetration of natural, filtered
daylight into home living areas without the energy loss and increased heating and
cooling costs associated with traditional glass roof inserts [77].

2.3.5 The nanotechnology potentials hierarchy for more

green building performance
The potential for energy conservation and reduced waste, toxicity, nonrenewable
resource consumption, and carbon emissions through the architectural applications of
Nanotechnology is significant. These environmental performance improvements will
be led by current improvements in insulation, coatings, followed by forthcoming
advances in solar and lighting technology, and more distant (>10 years) potential in
structural components and adhesives [78].

2.3.5.1 Nanotechnology adaptability to existing buildings

The market for Nano materials in insulation for all industries is projected to reach
$590 million by 2014, and the application of insulating Nano coatings to existing
buildings will be one of the greatest contributions of Nanotechnology to the reduction
of carbon emissions worldwide in the 21st century, for example: adding thermal
insulation to existing European buildings could cut current building energy costs and
carbon emissions by 42% or 350 million metric tons. But while insulation is the single
most cost effective strategy for reducing carbon emissions, existing buildings can be
difficult to insulate with conventional materials like rigid boards and fiberglass bats
because wall cavities where the insulation needs to go are inaccessible without partial

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demolition. Insulating Nano coatings could exceed the insulating values of

conventional materials through the much simpler application of an invisible coating to
the building envelope. Aerogels could also play a major role in insulating existing
structures.

Further study is needed to determine the exact insulating value of Nano coating
products, but considering that half of the buildings that will be standing at mid-century
have already been built, the prospect of easily improving their energy conservation
capabilities is urgent [79].

Nano Insulation is one of the most commercialized Nano products: It gets

around the problem of insulating existing buildings, which is hard to do with bulky
conventional materials like fiberglass. You literally paint or spray the insulation on –
it’s invisible and non-toxic. The insulating coatings are so thin and clear that you
don’t know they’re there.

With demand for energy efficient buildings rising, insulation is the most cost
effective way to reduce carbon emissions from buildings; it lowers a building’s energy
consumptions while maintain a comfortable indoor environment [46].

2.3.5.2 Integration of nanotechnology materials for

green building impacting both architecture design and
building construction:

Nanotechnology, a science that works on the molecular scale is set to transform

the way we design and build, it will profoundly affect the industry of architecture at
all scales; and, interior design, building design and city design will all benefit.

Even more dramatic breakthroughs are now in development such as paint on

lasers that could one day allow materials to send information to each other, windows
that shift from transparent to opaque with the flip of a switch, and environmentally
friendly biocides for preserving wood. The Nanotechnology application for green

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building has an emphasis on the energy conservation capabilities of architectural Nano

materials and the role of Nano sensors in green building [79].

Nano materials offer a whole new frontier for green building materials: It is
predicted that Nanotech’s many environmental performance benefits will be led by
current improvements in solar insulation and coatings, followed by advances in water
and air infiltration, solar technology and, more distant, in lighting and structural
components.

As an example, we can point to available improvements in Nano coatings for

insulating, self-cleaning, UV protection, corrosion resistance and waterproofing. Some
available coatings are considered “healers”, in that they remove and render benign
pollutants from a building’s surrounding atmosphere.

Product costs continue to fall, making Nanotech’s promise of reduced waste and
toxicity, lower energy and raw material consumption, greater safety and security,
cleaner and healthier buildings and other human health and environmental benefits far
more accessible.

Application for Nano-materials in Sustainable Construction Industry:

Nanotechnology offers longer life to the building materials with lower maintenance
cost and efforts. Use of Nano materials can improve fluidity, strength and durability of
the concrete. Nano materials also have the potential to be used to improve the
reinforcement qualities like anti-corrosion. Nano products like architectural paints,
water sealers and deck treatments; treatments applied during fabrication, such as
scratch-resistant coatings on vinyl or wood flooring, insulation coatings etc. Nanotech
products and applications, among other benefits, may enhance the performance with
regard to UV blocking, transparency of the structures, photo reactivity, and resistance
to stain and odor. Moreover, Nanotechnology based coatings can enable creating self
cleaning surfaces. Many of these are already being embedded into window glasses and
plumbing fixtures [80].The following Table (2.1) shows some prominent issues and
how nano materials can resolve.

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Table (2.1) : Some prominent issues and how nano materials can resolve.
Prominent issues How Nano materials can resolve
Maintenance of glass Anti-fogging and self-cleaning glasses, low
structures maintenance windows
Rusting & scratch Long lasting scratch resistant floors using
Nanotechnology
Corrosion/ rusting in Super strong structural components made with
structures Nanotechnology
Low life of paints: fading Longer lasting house paint using Nanotechnology
etc
Numerous problems solved Healthy and safe indoor climates using Nanotechnology
at one stroke by integrating Self cleaning skyscrapers using Nanotechnology
Nano science! Antimicrobial steel surfaces using Nanotechnology
Better industrial building maintenance
Less energy consuming buildings using
Nanotechnology
Long lasting roads and bridges using Nanotechnology
Self-sterilizing kitchen counters using Nanotechnology
Humidity controlling materials using Nanotechnology

Nanotechnology for Smart, Sustainable Building Systems: One such next-

generation technology is Nanotechnology, and it’s utilizing new materials that defy
conventional thinking. Spray-on Solar cells, VOC-eating Nano coatings, and windows
that change color at the flip of a switch; they are here today and they promise to
change the future of Green Building.

We will need to learn to identify Nanotechnology products that meet our specific
green building needs, compare their costs and benefits, and evaluate their
environmental, health and safety impacts.

Recent advances in scanning electron microscopes and other technologies now

make it possible to see and manipulate matter at the molecular scale more

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economically than ever before. Using these tools, Nanoscientists are creating
revolutionary materials like coatings a single atom thick, carbon Nanotubes up to 50
times stronger than steel yet 10 times lighter, and quantum dots that could enable us to
change the color of almost any object instantaneously. In this quantum world, objects
can change color, shape, and phase much more easily that at the macro scale.
Fundamental properties like strength, surface-to-mass ratio, conductivity, and
elasticity can be engineered to create dramatically different materials [46].

Architectural design area that will be influenced by Nanotechnology is the

smart environment: For example, tiny embedded Nano sensors will make
architectural features responsive. Communication will occur between object and
object, between occupant and object, between object and environment and between
occupant and environment.

As new materials gain more transient properties, objects and architectural features
will impact the process of design by making ‘fields of interaction’ a major focus.

By working on ‘fields of interaction’ architecture professionals will have some

framework by which to design for dynamic environments. Since smart architecture
will be changing states and communicating heavily, architects will likely focus on
relationships as much as they focus on design forms during the design stage. It is
likely that both forms and their relationships will make up rule-based systems by
which smart architectural spaces can function.

Nanotechnology will impact environments. Nanotechnology will give architecture

superior interactive functions – allowing occupants to better ‘communicate’ with their
surroundings. Windows and walls with variable transparency and mood/context
sensitive clothing are just a few ways this will become possible [81].

2.3.5.3 Environmental and human health concerns

Nanotechnology's unique benefits come with unique hazards. The large surface
area to mass ratio that makes Nano particles more effective in chemical reactions

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could also increase the level of exposure to an organism. While this could improve the
effectiveness of medications using Nano particles, it could also increase toxicity. Also,
because they can pass through biological barriers, Nanoparticle drugs could pose a
potent threat if unwanted particles migrate through the body. Inhalation of
Nanoparticles is particularly worrisome. Several studies during the last decade have
shown that exposure to airborne Nanoparticles can result in significant deposition of
those particles in the respiratory system.

One exposure route that doesn't get a lot of attention is disposal of used or waste
products. If little is known about the safety of Nanotechnology manufacturing, even
less is known about the safety after disposal. Unpredictable hazards could occur from
burning, biodegradation and leaching in landfills, and exposure to water [6].

The uncertainty surrounding the effects of Nanoparticles on the environment and

the human body is sure to continue as a concern in the development from
experimental Nanoscience to marketplace products. Reports find, for example, that
ultra-fine particles behave differently and can be more toxic than equivalent larger-
sized particles of a given material at similar doses per gram of body weight.
Regulation of Nano-based products based solely on particle size, however, is proving
extremely difficult [4].

Self-cleaning or easy to clean surfaces can reduce the amount of cleaning

required. In the case of industrial cleaning in particular it can reduce labor costs and
extend a material's durability. Lower energy costs and less use of cleaning detergents
are expected to be the primary environmental benefits. It was in anticipation of such
outcomes that the German Federal Foundation for the Environment (DBU) awarded
Wilhelm Barthlott its respected Environment Prize in 1999 for his discovery of the
"Lotus- Effect". However, there are currently no reliable, quantitative studies of actual
potential environmental benefits.

As a rule, descriptions of products' environmental benefits do not contain an

analysis or evaluation of the amount of resources used and/or the energy consumption
involved in their manufacture. Future evaluation should also include information on

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the fate and behavior of the materials once they reach the end of their life cycle (waste
stage).

Current risk assessments conclude that there is very little probability of a harmful
impact on the environment or human health from coatings in which Nanoparticles are
firmly embedded in a coating matrix, as in the case of "Easy-to-Clean" coatings.
There have so far also been no indications of environmental or health risks from
surfaces coated with the "Lotus-Effect". A recent investigation into the abrasion
resistance of test structures which had been coated with zinc oxide Nanoparticle layers
showed no significant release from the coating material. It does appear possible
however, that Nanoparticles are released as a result of the effects of weathering on the
coating matrix, for example where they consist of biodegradable materials. An
investigation by Kaegi et al. has shown that house paints release very small amounts
of synthetic TiO2 particles, between 20 and 300 nm in size, as a consequence of
weathering, and that these can enter the soil via rainwater drains.

The photocatalytic activities of TiO2 produce free oxygen radicals that are toxic
for aquatic organisms if such Nanoparticles enter the waters they inhabit. To date,
threshold levels remain unknown. The release of particles into the environment can
however be reduced or prevented if Nanocoatings and Nanomaterials are designed
accordingly.

Although surface coatings which have Nanomaterials firmly embedded in a

matrix are currently believed to pose only a very slight risk to the health of users and
consumers, the protection of those who work in the companies which manufacture
Nanoparticulate raw materials requires special attention. The German State of Hesse's
Ministry for Economic Affairs, Transport and State Development recently
commissioned a study by the Institute for Applied Ecology in Darmstadt which
confirmed in its action recommendations for the manufacture and use of Nano
materials in the paints and coatings industry that there are significant gaps in
knowledge and information in respect of exposure data and human and
ecotoxicological impact. The report goes on to recommend that companies should be

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guided by the precautionary principle and that preventing inhalation be given top
priority [63].

2.3.5.4 Safety risks of dealing with nano-products on

the construction site

Main product types identified at the market are Nanoparticle improved concrete
and cement materials, Nano-coatings and insulation material. However, these same
products might pose new health and safety risks to the worker on-site, which science
are only just starting to understand. Especially when the work involves the generation
of Nanoparticles or aerosols, Typical activities with possible high risks of exposure to
Nanoparticles are the application of wet or dusty Nano-products, machining dried or
prefab Nano-products and cleaning or maintaining of materials and the equipment
used [2].

2.3.5.5 Towards further co-operation between nano

scientists, nano products

Manufacturer and Building Sector Stakeholders The Nanotech and building sector
have to yet to get to know each other a lot better in order to realize the dramatic
benefits awaiting each of them. The Nanotech community needs to be explored and
explained the enormous economic opportunities in Green Building Design,
Construction and Operation; and demonstrate to Architects, Building Owners,
Contractors, Engineers and others in the $1 trillion per year global building industry
that Nanotech is at this moment beginning to fulfill its promise of healthful benefits
for people and the environment [46].

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CHAPTER 3

FABRICATION OF NANO MATERIALS.

3.1. Fabrication of Nano materials

The ability to fabricate Nanomaterials (often in the form of Nanoparticles) with
strictly controlled size, shape, and crystalline structure, has inspired the application of
Nanochemistry to numerous fields, including catalysis, optics, and electronics. The
use of Nanomaterials in such applications also requires the development of methods
for Nanoparticle assembly or dispersion in various media. Although much progress

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has been realized during the last decades in the development of highly advanced
analytical tools enabling the characterization of Nanostructures and an understanding
of their physical properties, the synthesis of well-defined Nanoparticles has resulted in
several prominent milestones in the progress of Nanoscience, including the discovery
of fullerenes [82], carbon Nanotubes [83, 84], the synthesis of well-defined quantum
dots [85–87] and the shape control of semiconductor CdSe Nanocrystals [88].

However, despite a vigorous expansion in the methods of Nanoparticles synthesis,

it is still difficult to generalize underlying physical or chemical principles behind
existing synthesis strategies to any arbitrary Nanomaterial. A general, mechanistic
understanding of Nanoparticle formation that might guide the development of new
materials remains lacking [89]. Though the synthesis of Nanoparticles with control
over size, shape, and size distribution has been a major part of colloid chemistry for
decades, it remains an intensely studied topic as is evident by a substantial body of
literature. In this chapter, we provide an overview of the main methods that have
proved to be successful for the fabrication of several classes of Nanomaterials:
specifically, oxides, chalcogenides, metals, and fullerenes.

3.1.1 Specificity and Requirements in the Fabrication

Methods of Nanoparticles

Ultra-dispersed systems, such as dispersions of Nanoparticles, are intrinsically

thermo dynamically metastable, in large part due to the very high interfacial areas.
Nanoparticle surface area represents a positive contribution to the free enthalpy of the
system. If the activation energies are not too high, spontaneous evolution of a
Nanoparticle dispersion can occur causing an increase in Nanoparticle size or the
formation of Nanostructured domains and leading to the decrease of the surface area.
Consequently, it follows that:

 An ultra-dispersed system with a high surface energy can be only kinetically

stabilized.

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 Ultrafine powders cannot be synthesized by methods involving energies that

exceed a threshold, but rather through methods of “soft chemistry” that maintain the
forming particles in a metastable state.

 Additives and/or synthesis conditions that reduce the surface energy are needed
to form Nanoparticles stabilized against sintering, recrystallization, and aggregation.

Under these conditions, any solid matter such as metal oxides, chalcogenides,
metals, or carbon can be obtained at the Nanometric scale. Synthesis methods for
Nanoparticles are typically grouped into two categories:

 1- The first involves division of a massive solid into smaller portions. This
“top-down” approach may involve milling or attrition (mecanosynthesis), chemical
methods for breaking specific bonds (e.g., hydrogen bonds) that hold together larger
repeating elements of the bulk solid, and volatilization of a solid by laser ablation,
solar furnace, or some other method, followed by condensation of the volatilized
components.

 2- The second category of Nanoparticle fabrication methods involves

condensation of atoms or molecular entities in a gas phase or in solution. This is the
“bottom-up” approach in which the chemistry of metal complexes in solution holds
an important place. This approach is far more popular in the synthesis of
Nanoparticles, and many methods have been developed to obtain oxides,
chalcogenides, and metals.

The liquid-phase colloidal synthetic approach is an especially powerful tool for

convenient and reproducible shape-controlled synthesis of Nanocrystals not only
because this method allows for the resulting Nanocrystals to be precisely tuned in
terms of their size, shape, crystalline structure, and composition on the Nanometer
scale, but alsobecause it allows them to be dispersed in either an aqueous or a
nonaqueous medium. Moreover, these Nanoparticles can be modified in liquid
suspension by treatment with various chemical species for application and use in a
diverse range of technical or biological systems.

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3.1.2 Oxides

The most widespread route to fabrication of metal oxide Nanoparticles involves

the bottom-up approach by the precipitation in aqueous solution from metal salts.
Organometallic species can also be used in hydrolytic or nonhydrolytic pathways, but
due to their cost and the difficulty in manipulating these compounds, they are used
less frequently and primarily for high-tech applications.

An alternative top-down approach has been demonstrated for aluminum and iron
oxide Nanoparticles; however, it is possible that this methodology could be extended
to other oxides.

3.1.3 From molecular species to Nanoparticles

One approach to the creation of oxide Nanoparticles is to build from the “bottom-
up,” beginning with individual ions or molecular complexes of metals. Variations on
this approach include the hydroxylation of metal cautions in aqueous solutions, the
use of metal alkoxides, nonhydrolytic routes such as those employing metal halides.

3.1.3.1. Hydroxylation of metal cations in aqueous solution and condensation:

Inorganic polymerization. The metal cations issued for the dissolution of salts in
aqueous solution form true coordination complexes in which water molecules form
the coordination sphere. The chemistry of such complexes, and especially their acid
behavior, provides a framework for understanding how the solid (oxide) forms via
inorganic polycondensation [90, 91].

The binding of water molecules to a cation involves an orbital interaction

allowing an electron transfer from a water molecule to a cation following Lewis’s
acid-base concept of the coordination bond. Such a transfer drives the electronic
density of water molecules toward the cation and weakens the O-H bond of the
coordinated water molecules. They are consequently stronger Brønsted acids than the
water molecules in the solvent itself, and they tend to be deprotoned spontaneously
according to the hydrolysis equilibrium:

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[M(H2O)n].z+ + h H2O [M(OH)h(H2O)n-h].(z-h)+ +h H3O+

Or by neutralization with a base:
[M(H2O)n].z+ + h HO- [M(OH)h(H2O)n-h].(z-h)+ +h H2O

In these equilibria, h is the hydroxylation ratio of the cation. It represents the

number of hydroxo ligands (OH) present within the coordination sphere, or the
number of protons eliminated from the coordination sphere of the aqua cation.

The acidity of the aqua cation strongly depends on the strength of the M-O
bond—that is, the magnitude of the electron transfer from oxygen toward the metal.
The acidity can be related to the polarizing character of the cation—that is, the ratio of
formal charge (oxidation state) to its size. The equilibrium constant of the first step of
hydroxylation (h = 1) for many cations where d stands for the M-O distance can be
empirically expressed by [90,91]:

log K ≈ -20 + 11(z/d) = -ΔG° . RT

The hydrolysis rate of cations in aqueous solution also depends strongly on the
pH of the medium because the equilibrium involves the transfer of protons. From the
acidity constants of medium-sized cations [90,92]., a charge-pH diagram was
established [93]. In which three domains are plotted (Figure 3.1). The lower domain
corresponds to the existence of aqua-cations [M(H2O)n].z+ , the upper to oxo-anions
[MOn].(2n-z)- , and the intermediate domain corresponds to hydroxylated complexes
containing at least one hydroxo ligand. These domains are separated by two lines
corresponding to h = 1 and h = 2n-1, respectively. This diagram is a useful guide to
understand the condensation and precipitation phenomena involved in the synthesis of
particles. Condensation between species in solution becomes possible only when they
are hydroxylated.

Therefore, condensation can be initiated by varying the pH of the solution by

addition of a base on an acid (element M with z ≤ 4) or by addition of an acid on a
base (element M with z < 4). Condensation can also be initiated via redox reactions
with elements having several stable oxidation states (Figure 3.1).

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Hydrolysis is, strictly speaking, a neutralization reaction carried out by the water
molecule:

[M(H2O)n].z+ + h H2O → [M(OH)h(H2O)n-h].(z-h)+ + h H+solvated

For this reaction, it has been shown [34].:
ΔH°= (75.2 – 9.6 z) kJ mol-1, ΔS°= ( –148.4 + 73.1 z) J mol-1
And: ΔG°298 = (119.5 – 31.35 z) kJ mol-1

The reaction is spontaneous (ΔG° < 0) for elements of charge equal to or greater
than 4. Therefore, at room temperature, tetravalent elements do not exist as purely
aquo complexes, even in strongly acidic medium. For element with a charge, z,
smaller than 4, ΔG° becomes negative only if the temperature is higher than 298 K.
Therefore, it is necessary to heat the solution in order to carry out hydrolysis of the
cation (forced hydrolysis or thermohydrolysis).

Figure (3.1): Nature of the ligand in the coordination sphere of a cation as function of
its formal charge, z, and the pH of the medium [93]. Possible initiation methods of
condensation reactions are depicted.

The monomeric, electrostatically charged, hydroxylated species

[M(OH)h(H2O)nh].(z-h)+ or [MOn-h(OH)h].(2n-z-h)- are generally observed in solution only
at very low concentrations. More often, they condense and form soluble polynuclear

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species, polycations (h < z), and polyanions (h > z) respectively, in which the cations
are bounded by hydroxo or oxo bridges [91]. These entities are generally of molecular
size, although giant polyanions of molybdenum containing up to 368 Mo ions have
been recently synthesized! [94]. The condensation of neutral complexes with h = z is,
in general, not limited and continues to the formation of a solid.

Hydroxylated complexes condense via two basic mechanisms of nucleophilic

substitution, depending on the nature of the coordination sphere of the cations. In all
cases, the driving force to the condensation is the nucleophilicity of the hydroxo
ligand. The cation must also have an electrophilic character high enough to be
subjected to the nucleophilic attack. Condensation of aquohydroxo complexes
proceeds by elimination of water and formation of hydroxo bridges (olation):

For oxohydroxo complexes, there is no water molecule in the coordination sphere

of the complexes and therefore no leaving group. Condensation has to proceed in this
case via a two-step associative mechanism leading to the formation of oxo bridges
(oxolation):

The hydroxylation rate, h, of the complexes represents their functionality toward

condensation, and it controls the type and the structure of condensed species. It is
obvious that h is a function of the pH of the medium. It’s also depends on the
characteristics of the cation such as size, formal charge, and electronegativity.

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Condensation of hydroxylated and electrically charged complexes (h < z) always

ends at a more or less advanced stage, leaving discrete species in solution, either
polycations or polyanions, depending on whether the monomeric complex is a cation
or an anion. Indeed, electrical charges cannot indefinitely accumulate on a metal -oxo-
polymer, and condensation stops as soon as conditions allowing nucleophilic
substitution are no longer present. As condensation causes water elimination, there is a
change in composition of the reaction product that produces a variation of its average
electronegativity, causing charge redistribution within its structure and, therefore, a
change in the reactivity of the functional groups [91]. Hence, OH ligands in the
growing species may lose their nucleophilic character, and cations may lose their
electrophilic character. Usually, during condensation, the nucleophilic character of
hydroxo ligands cancels in polycations, and the electrophilic character of the cation
cancels in polyanions. Condensation of electrically neutral ions (h = z) continues
always indefinitely until there is precipitation of a solid (hydroxide, oxyhydroxide, or
more or less hydrated oxide) or of a basic salt in the presence of complexing ligands.
Elimination of water from noncharged complexes never leads to a sufficient change in
the average electronegativity to cancel the reactivity of functional groups.

In theory, an hydroxide M(OH)z is formed via endless condensation of aquo-

hydroxo complexes. However, the hydroxide may not be stable. Its spontaneous
dehydration, more or less rapid and extensive, generates an oxyhydroxide

MOx(OH)z-2x or a hydrated oxide MOz/2 . (H2O)x.

The reaction takes place via oxolation in the solid phase with elimination of water
from hydroxo ligands. The reaction is associated with structural changes in order to
preserve the coordination of the cation. Usually, elements with a 2 charge precipitate
as hydroxides and those with a +3 charge as oxyhydroxides (the final stage of
evolution is the oxide). Those of higher charge form oxides of various level of
hydration [95]. This sequence is a clear illustration of the increasing polarization of
the hydroxo ligands by the cation, which is associated with the covalent nature of the
metal-oxygen bond.

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In summary, condensation of cations in solution is initiated when acidity allows

the presence of the hydroxo ligand in the coordination sphere of the cation. This
occurs through addition of a base to aquo complexes of elements of formal charge
equal to or smaller than 4, or through addition of an acid to oxo complexes of
elements of charge equal to or greater than 4 (Figure 3. 2). Two reactions, olation and
oxolation, respectively, ensure the development of condensation. The condensation of
cationic and anionic hydroxylated complexes is always limited. It leads to polycations
and polyanions, respectively. Formation of a solid requires the presence of zero-
charge complexes. It is also possible (although less common) to involve redox
phenomena in order to decrease the formal charge on the metal and force the
appearance, under given acidic conditions, of the hydroxo ligand in the coordination
sphere of the cation.

Hydroxide, oxyhydroxide, or hydrated oxide solid phases obtained via

precipitation are made of particles whose average size may range from a few
Nanometers to a few microns. Particle morphology may vary depending on synthesis
conditions. Moreover, aging in aqueous solution may bring about significant
dimensional, morphological, and structural changes. In order to understand how small
particles form and what role the experimental parameters play on their characteristics
and on evolution, it is useful to review the kinetic aspects of condensation reactions.

The precipitation of a solid involves four kinetic steps [96–98].:

1. Formation of the zero-charge precursor [M(OH)z(H2O)n-z].0, which is able to

condense and form a solid phase. Hydroxylation of the cation is a very fast
acid/base reaction, but the rate of formation of the zerocharge precursor in
solution can largely vary depending on whether the reaction starting from cationic
complexes for example, takes place through addition of a base, thermohydrolysis,
or slow thermal decomposition of a base such as urea.
2. Creation of nuclei, through condensation (olation or oxolation) of zero-charge
precursors. The condensation rate is a function of precursor concentration, and as
long as it is small at the onset of cation hydroxylation, the rate is almost zero

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(zone I, Figure 3. 2a). Beyond a critical concentration Cmin, the condensation rate
increases abruptly and polynuclear entities—the nuclei—are formed in an
“explosive” manner throughout the solution (zone II, Figure 3.2c). Indeed,
nucleation is an abrupt kinetic phenomenon because, since its order is high
compared to the precursor concentration, it is either extremely fast or nonexistent
within a narrow concentration range (Figure 3.2b and 3.2c). If the rate of
generation of the precursor is significantly smaller than the condensation rate,
nucleation sharply reduces the precursor concentration and the condensation rate
decreases equally rapidly. When the precursor condensation is again close to
Cmin, formation of new nuclei is no longer possible.
3. Growth of the nuclei through addition of matter, until the primary particle stage is
reached. This step follows the same chemical mechanisms as nucleation: olation
or oxolation. However, for a concentration close to Cmin, the nucleation rate is
very small and precursors condense preferentially on existing nuclei. Nuclei grow
until the precursor concentration reaches the solution saturation (in other words,
the solubility limit) of the solid phase (zone III, Figure 3.2b,c). Growth, having
kinetics of first or second order, is a somewhat faster process. Precursor
condensation during precipitation is a function of the respective rates of precursor
generation and nucleation. Nucleation and growth phases may therefore be
consecutive or overlap and occur simultaneously if the precursor concentration
stays higher than Cmin.
The number, and therefore the size, of the primary particles that form from a
given quantity of matter is linked to the relative nucleation and growth rates
(Figure 3. 2a).In order to obtain particles of homogeneous size, it is necessary that
the nucleation and growth steps be separated to ensure that a single nucleation
stage takes place, and that growth, via accumulation of all remaining matter, be
controlled. This implies that the nucleation rate should be much greater than the
rate at which the precursor is generated. Under these conditions, nucleation is
very brief and clearly decoupled from the growth phase.

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Figure (3. 2): Change (a) in the number and sizes of particles formed in solution, and
(b) in concentration C of the soluble precursor of the solid phase during precipitation
[99]. Condensation rate, which is zero for C < Cmin, becomes infinite for C ≥ Cmax.
CS is the solubility of the solid phase. (c) Nucleation (n) and growth (g) rates as a
function of precursor concentration in solution.

If the nucleation rate is not high enough compared to the rate of generation of the
precursor, precursor concentration remains higher than Cmin throughout the reaction,
and nucleation and growth are simultaneous. The growth of the first nuclei is much
larger than that of the younger ones, which leads to a large particle size distribution.

4. Nucleation and growth steps form particles under kinetic control following a
reaction path of minimum activation energy under conditions imposed to the
system (acidity, concentration, temperature), but the products are not necessarily
thermodynamically stable. Aging of the suspensions, which may take place over a
very large time scale (hours, days, or months), allows the system to tend toward
or reach stability, and it is often associated with modifications of some physical or
chemical characteristics of the particles. “Ostwald ripening” leads to an increase
in the average particle size and possible aggregation (zone IV, Figure 3.2a).
Aging may also trigger a change in morphology and crystalline structure or even
cause crystallization of amorphous particles. In fact, aging is one of the most

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important phenomena that must be considered, because it determines the

characteristics of the particles after precipitation.

3.1.3.2. Control of particle size, crystalline structure and morphology. There are
different techniques to form the complex of zero charge and to obtain a solid. The
most common method consists of introducing a base into the acid solution of a metal
salt at room temperature. When solutions such as these are mixed, a high
concentration of hydroxylated complexes rapidly forms along with induced local pH
gradients. In homogeneities in the hydrolysis products often present during such a
missing procedure may result in random condensation and the formation of an
amorphous solid with an ill-defined chemical composition. Such a result is
exemplified by the case of ferric ions. They precipitate quasi instaneously at pH ≥ 3
into a poorly defined, highly hydrated phase, called 2-line ferrihydrite [100]. (This
phase takes its name from its X-ray diffraction pattern, which exhibits only two broad
bands.) In similar conditions, Al3+ ions form a transparent amorphous gel [101].

At pH ≥ 2, Ti4+ ions form an amorphous oxyhydroxide with a composition near to

TiO0.3(OH)3.4 [102]. These solids are formed of very small size particles, around 2–3
nm in diameter, and are strongly metastable. They evolve spontaneously in suspension
more or less quickly to form crystalline Nanoparticles, with possibly an increase in
particle size, releasing simultaneously the lattice energy (and decreasing the surface
energy) to decrease the free enthalpy of the system. The acidity of the suspension
during evolution is the most important parameter to control crystalline structure and
the size of the final particles. Two distinct mechanisms are involved in the
transformation.

When the suspensions are aged at a pH where the solid is partially soluble, the
concentration in solution may be enough to feed nuclei of a more stable crystalline
phase. A transfer of matter occurs via the solution from the soluble amorphous phase
toward a less soluble crystalline phase during a slow dissolution-crystallization
process allowing formation of well-crystallized particles. Such a process is involved in
the formation of goethite, α-Fe(O)(OH), during aging of ferrihydrite in suspension at

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pH < 5 or pH > 10. Because of structural anisotropy of goethite, rod-like particles of

mean dimensions 150×25×15 nm are obtained (Figure 3.3). These particles,
anisotropic in shape, form very stable concentrated suspensions, which behave as
nematic lyotropic liquid crystals exhibiting very interesting magnetic properties [103].
The nematic phase aligns in a very low magnetic field (20 mT for samples 20 mm
thick). The particles orient along the field direction at intensities smaller than 350 mT
but reorient perpendicular to the field beyond 350 mT. This behavior could have
interesting applications.

In similar ranges of acidity, the aluminate gel is transformed into platelets of

hydroxide Al(OH)3, gibbsite at pH < 5, and bayerite at pH > 8 [101]. In a rather acidic
medium (pH< 1), the same dissolution crystallization mechanism transforms the
amorphous titanium oxyhydroxide into elongated TiO2 rutile Nanoparticles. In these
examples, the final size of particles depends on the acidity of the medium: the particle
size increases when the acidity is strong.

300 nm
20 nm

[002]

[110]

150 nm

(a) (b) (c)

Figure (3.3): Particles of (a) goethite α-Fe(O)(OH), (b) gibbsite Al(OH)3, and (c) rutile
TiO2 synthesized in aqueous medium[101].

If the suspensions are aged at an acidity where the solubility of the solid is very
low or at a minimum, the concentration of soluble species in equilibrium with the
solid phase does not allow an efficient transport of matter, and crystallization of the
early amorphous material will occur more easily by a transformation in situ, in the
solid state. The transformation involves the diffusion of ions within the solid with

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partial dehydration, and the formation of crystalline domains of very small size.
Nanoparticles of hematite, α-Fe2O3, are so obtained from ferrihydrite at 6 ≤ pH ≤ 8
[104]. Very small Nanoparticles of boehmite, γ-Al(O)(OH), (around 300 m2 . g-1) are
similarly obtained by aging of aluminate gels at the same pH range (6 to 8) [101].
Although boehmite is not the most thermodynamically stable phase at room
temperature, it is probably kinetically stabilized because the system is constrained to
evolve without heating and transforms on the lowest activation energy path. Between
pH 2 and pH 7, where the solubility of titania is very low, the amorphous solid is
transformed into TiO2 anatase Nanoparticles [102]. Over this acidity range, the
particle size of anatase depends on the pH of precipitation and aging.

Precipitation by addition of a base at room temperature may also lead to stable

crystalline Nanoparticles without involving any transformation by the above
mechanisms. For instance, magnetite Fe3O4 is easily obtained by coprecipitating
aqueous Fe3+ and Fe2+ ions with x = 0.66 [105]. Iron ions are distributed into the
octahedral (Oh) and tetrahedral (Td) sites of the face centered cubic (fcc) stacking of
oxygen according to [(Fe3+)Td(Fe3+Fe2+)OhO4]. Magnetite is characterized by a fast
electron hopping between the iron cations on the octahedral sublattice. Crystallization
of spinel is quasiimmediate at room temperature, and electron transfer between Fe2

and Fe3+ ions plays a fundamental role in the process [106, 107]. In effect, maghemite,
γ–Fe2O3, [(Fe3+)Td(Fe3+5/3V1/3)OhO4]. (where V stands for a cationic vacancy) does not
form directly in solution by precipitation of ferric ions, but a small proportion of Fe2+
( ≤ 10 mol %) induces the crystallization of all the iron into spinel. Studies of the early
precipitate revealed that all Fe2+ ions were incorporated into a Fe2+-ferrihydrite,
forming a short-range ordered, mixed valence material exhibiting fast electron
hopping, as evidenced by Mössbauer spectroscopy [107]. Electron mobility brings
about local structural rearrangements and drives spinel ordering. Besides this
topotactic process, crystallization of spinel can also proceed by dissolution
crystallization, resulting in two families of non-stoichiometric spinel particles
[(FeIII)Td(FeIII1+2z/3FeII1-zVz/3)OhO4]. with very different mean size [106]. The relative
importance of these two pathways depends on the Fe2+ level in the system, and the end

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products of the coprecipitation are single phase only for 0.60 ≤ x ≤ 0.66. The
comparison with the cases where M2+ is different from Fe2+ emphasizes the role of
electron mobility between Fe2+ and Fe3+ ions in the crystallization process. With other
divalent cations, intervalence transfers are negligible and a spinel ferrite forms only by
dissolution crystallization [105]. With x = 0.66, corresponding to stoichiometric
magnetite, the mean particle size is controlled on the range 2–12 nm by the conditions
of the medium, pH and ionic strength (I), imposed by a salt

(8.5 ≤ pH ≤ 12 and 0.5 ≤ I ≤ 3 mol . L-1) (Figure 3.4) [108].

Such an influence of acidity on the particle size is relevant to thermodynamics rather

than kinetics (nucleation and growth processes). Acidity and ionic strength act on
protonation- deprotonation equilibria of surface hydroxylated groups and, hence, on
the electrostatic surface charge. This leads to a change in the chemical composition of
the interface, inducing a decrease of the interfacial tension, γ, as stated by Gibbs’s
law, dγ = -Γidμi,where Γi is the density of adsorbed species i with chemical potential μi
. Finally, the surface contribution, dG = γdA (A is the surface area of the system), to
the free enthalpy of the formation of particles is lowered, allowing the increase in the
system surface area [109].

Due to the high electron mobility in the bulk, magnetite Nanoparticles give rise to
an interesting surface chemistry involving interfacial transfer of ions and/or electrons
and allowing us to consider spinel iron oxide Nanoparticles as refillable
Nanobatteries. Nanoparticles of magnetite are very sensitive to oxidation and
transform into maghemite [(Fe3+)Td(Fe3+5/3V1/3)OhO4]. The high reactivity is obviously
due to the high surface-to-volume ratio, and a controlled synthesis of particles requires
strictly anaerobic conditions. However, aerobic oxidation is not the only way to go to
maghemite. Different interfacial ionic and/or electron transfers that depend on the pH
of the suspension can be involved in the transformation. In basic media, the oxidation
of magnetite proceeds by oxygen reduction at the surface of the particles (electron
transfer only) and coordination of oxide ions, while in acidic medium and anaerobic

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conditions [110]., surface Fe2+ ions are desorbed as hexa-aquo complexes in solution
(electron and ion transfer) according to:
[Fe3+].Td[Fe2.5+2 ].OhO4+ 2H+ → 0.75 [Fe3+].Td[Fe3+5/3V1/3].OhO4 + Fe2+aq + H2O

Figure (3. 4): Electron micrographs of magnetite particles synthesized by precipitation

in water and particle size variation against pH of precipitation [108].

In both cases, the oxidation of Fe2- ions is correlated with the migration of cations
through the lattice framework, creating cationic vacancies in order to maintain the
charge balance (Figure 3.5). The mobility of electrons on the octahedral sublattice
renews the surface ferrous ions allowing the reaction to go to completion. The
oxidation in acidic medium (pH ≈ 2) does not lead to noticeable size variation. A very
interesting technique for obtaining oxide Nanoparticles is the thermolysis (or forced
hydrolysis) of acidic solutions. Heating of a solution to approximately 50–100°C
enables, particularly with trivalent and tetravalent elements (Al, Fe, Cr, Ti, Zr, etc.), a
homogeneous hydrolysis in conditions close to thermodynamic equilibrium [111].
Under such conditions, the slow speed of formation of the hydrolyzed precursors
allows decoupling of the nucleation and growth steps, from a kinetic standpoint. As a
result, narrow particle size distributions can be obtained.

Thermolysis at 90–100°C of acidic ferric solutions (pH ≤ 3) forms hematite [111,

112]. In these conditions, olation and oxolation compete and acidity facilitates
oxolation leading to oxide. The acidity and the nature of the anions are, however,
crucial for the control of the size of particles. At low concentration of chloride
(C < 10-3 mol . L-1), 6-line ferrihydrite forms initially [112, 113]. It transforms into

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hematite during thermolysis, but the particle size depends strongly on the acidity of
the medium (Figure 3.6). At high concentration of chloride, akaganeite, β-Fe(O)(OH),
is first formed [114].

Figure (3. 5): Oxidation mechanism of magnetite to maghemite in acidic medium

[110].

Figure (3. 6): Particles of hematite obtained by thermolysis at 95°C of ferric nitrate
solutions. Influence of the pH of the medium on the mean size of particles [100].

This metastable phase is slowly transformed into hematite during thermolysis, and
large (μm-sized) polycrystalline particles with various morphologies are obtained
depending on the nature of anions in the medium [115–117].

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Thermolysis at 95°C of aluminum nitrate solutions for one week produces

exclusively boehmite, γ-Al(O)(OH), in avoiding the formation of hydroxide Al(OH)3,
which is thermodynamically less stable at this temperature. The change in the acidity
over a large range allows modification of the shape of the Nanoparticles. At pH 4–5,
heating produces fibers or rods around 100 nm in length. The fibers are formed by
aggregation of very small platelets 3 nm thick and 6 nm wide, exhibiting (100) lateral
faces and (010) basal planes. The particles synthesized at pH = 6.5 are pseudo
hexagonal platelets 10–15 nm wide and 4–5 nm thick with (100) and (101) lateral
faces, while those synthesized at pH = 11.5 are diamond-shaped, 10–25 nm wide. The
angle of ~104° between lateral faces corresponds to the angle between the (101) and
(10-1) directions, suggesting (101) lateral faces (Figure 3.7). On the whole acidity
ranges of synthesis, the particles are platelets with the same (010) basal face but with
different lateral faces. Such a change in the nature of lateral faces of particles results
from the change in surface energy induced by the variation in the electrostatic surface
charge density as a function of the pH [109]. This is an important feature of boehmite
particles, because they are the precursor of γ-alumina, γ-Al2O3, largely used as a
catalyst. As the thermal transformation boehmite → γ-alumina is a topotactic
transformation, which maintains the morphology of particle, the control of the shape
of boehmite particles enables the development of corresponding faces on γ-alumina
Nanoparticles and consequently adjustment of their catalytic activity toward a given
reaction [101].

Thermolysis of strongly acidic TiCl4 solutions enables a very efficient structural

and morphological control of titanium oxide Nanoparticles. After heating for one day
at 90°C, TiCl4 in concentrated perchloric acid solutions (HClO4, 1–5 M) forms
mixtures containing various proportions of the different TiO2 polymorphs (anatase,
brookite, and rutile). After heating for one week, the metastable phases, anatase and
brookite, disappear through transformation into rutile with very different shapes
depending on the acidity. This can be explained by the amount of metastable material
transformed into rutile by a dissolution-crystallization process: when the amount of
metastable phases is high, the initial rutile particles are strongly fed and their growth

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leads to elongated rods. It is thus possible to adjust the aspect ratio of rutile
Nanoparticles from around 5:1 to 15:1.

Figure (3.7): TEM micrographs of boehmite Nanoparticles synthesized at (a) pH =

4.5, (b) pH = 6.5, (c) pH = 12 [101].

When TiCl4 is thermolyzed in concentrated hydrochloric acid (HCl 1–5M),

brookite Nanoplatelets are stabilized and it is possible to obtain them as the main
product when the stoichiometries of Cl/Ti and H+/Ti are optimized (Figure 3.8) [118].
Brookite is currently obtained in hydrothermal conditions at elevated temperature in
the form of large particles [119]. Nanoparticles of brookite apparently are never
obtained except as byproducts of various reactions [120]. Quasi-quantitative synthesis
of brookite Nanoparticles seems to result from a specific precursor,
Ti(OH)2Cl2(H2O)2, containing chloride as ligands in the early complexes formed in
solution. It has been proposed [118]. that chloride ligands orient the early stages of
condensation in the formation of brookite. As long as chloride ions are present in
suspension, brookite Nanoparticles remain stable, while if chloride ions are replaced
by perchloric anions, brookite transformation into rutile is complete after several
hours at 90°C.

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These examples underscore the versatility of oxide Nanoparticle chemistry in an

aqueous medium. The main parameter allowing the control of Nanoparticle
morphology (size, crystalline structure) is the acidity of the reaction bath. Astrict
control is consequently critical to obtain welldefined Nanoparticles. It is however
interesting to distinguish two sorts of physico-chemical conditions in these syntheses.
In moderately acidic or basic media, the sign and the density of the electrostatic
surface charge of particles varies as a function of pH due to proton adsorption-
desorption equilibria. This involves a change in chemical composition of the surface
and therefore a change in surface energy of the particle during formation. When the
surface charge density is high (the pH is far from the surface point of zero charge), the
surface energy is strongly decreased. As a consequence, the size of Nanoparticles
decreases because the energetic penalty to develop surface is notably reduced. A semi
quantitative model [109]. works well to account for this size effect for anatase and
magnetite and to explain the change in shape of boehmite Nanoparticles. In strongly
acidic media used for thermolysis, the solubility of the solid is high because the
surface is totally protonated and the ionic atmosphere near the surface of particles
during formation is very likely high and constant, so that the surface energy is always
low. Depending on their structure, some faces can be energetically favored, but
dissolution-crystallization processes very likely play a role in the growth of particles.
Other parameters such as thermolysis temperature, concentration, and presence of
specific ligands have to be taken into account in the describing Nanoparticle
formation.

3.1.3.3. Hydrolysis of metallo-organic compounds. Metallo-organic

compounds, and especially metal alkoxides [121, 122]., are largely involved in so-
called sol-gel chemistry of oxide Nanomaterials [123]. Metal alkoxides are also
precursors of hybrid organic-inorganic materials, because such compounds can be
used to introduce an organic part inside the mineral component [124–127].

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(a) (b)

0.34 nm
5 nm 3 nm
0.34nm 0.34 nm

25 nm (c)

Figure (3. 8): HRTEM micrographs of particles of brookite after one month of
thermolysis at 100°C (TiCl4 0.15 mol dm-3, HCl 3 mol . dm-3); inset, the local electron
diffraction pattern [120].

Sol-gel chemistry mainly involves hydrolysis and condensation reactions of

alkoxides M(OR)z in solution in an alcohol ROH, schematically represented as:

M(OR)z + z H2O → M(OH)z + z ROH → MOz/2 + z/2 H2O

These two reactions, hydroxylation and condensation, proceed by nucleophilic

substitution of alkoxy or hydroxy ligands by hydroxylated species according to:

M(OR)z + x HOX ↔ [M(OR)z-x(OX)x].
x ROH

If X = H, the reaction is a hydroxylation. For X = M, it is a condensation

(oxolation) and if X represents an organic or inorganic ligand, the reaction is a
complexation. There is a deep difference with the processes in aqueous medium where
condensation and complexation are nucleophilic substitutions while hydroxylation is
an acid-base reaction. In organic medium, both hydrolysis and condensation follow an

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associative SN2 mechanism in forming intermediate species in transition states in

which the coordination number of the metal atom is increased. That explains why the
reactivity of metal alkoxides toward hydrolysis and condensation is governed by three
main parameters: the electrophilic character of the metal (its polarizing power), the
steric effect of the alkoxy ligands, and the molecular structure of the metal alkoxide.

Generally, the reactivity of alkoxides toward substitutions increases when the

electronegativity of the metal is low and its size is high. That lowers the covalence of
the M-O bond and enhances the reaction rates. Silicon alkoxides are weakly reactive
in the presence of water (Xsi = 5 1.74) while titanium alkoxides (XTi = 1.32) are very
sensitive to moisture.

Alkoxides of low electronegative elements have to be handled with care, under

dry atmosphere, because traces of water can be enough to provoke precipitation. By
comparison, alkoxides of very electronegative elements such as O = P(OEt)3
(xP=2.11) are quite inert and do not react with water in normal conditions.

The reactivity of metal alkoxides is also very sensitive to the steric hindrance of
the alkoxy groups. It strongly decreases when the size of the OR group increases. For
instance, the rate constant, k, for hydrolysis of Si(OR)4 at 20°C decreases from 5.1 ×
10-2 L . mol-1s-1 for Si(OMe)4 to 0.8 × 10-2 L . mol-1s-1 for Si(OBu)4 and the gelation
time is increased by a factor of 10 (Table 2.2) [120].

Table (3.1): Gelation Time of Silicon Alkoxides as a Function of Alkoxy Groups Si

(OR) 4 at Several Values of pH in Water and in 4-(Dimethylamino) Pyridine (DMAP)
[120].

The acidity of the medium also influences the rate of hydrolysis and condensation
reaction to a great extent as well as the morphology of the products. In an excess of

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water and in acidic medium (pH ≤ 4), the silicon alkoxides form transparent polymeric
gels while in basic medium (pH ≥ 8); the condensation is also accelerated relatively to
the reaction in neutral medium (Table 2.1) and leads to perfectly spherical and
monodispersed particles of hydrated silica, as exemplified by Stöber’s method (Figure
3.9) [127]. These variations reflect the acid or basic catalysis of the involved
reactions.

1.0 nm

(a) (b)

Figure (3. 9): SEM of silica Nanoparticles (23 nm in mean size) synthesized following
Stöber’s method from hydrolysis of Si(OEt)4 in water/ethanol with 5% NH3. (b) SEM
of TiO2 Nanoparticles resulting from hydrolysis of Ti(OEt)4 with water (pH 7) [127].

It is possible to explain the overall structure of the silica polymer by considering

at an early stage of condensation a branched chain of silicic tetrahedra containing
several types of groups:

such a chain being formed by the oxolation reaction:

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One may consider three different reactive groups: terminal or mono coordinated
[A]., branched or tricoordinated [B]., and middle or dicoordinated [C]. Using the
Partial Charges Model [10]., it is possible to estimate the relative partial charges on
the sites A, B, and C (Table 2.3).

In an alkaline medium, catalysis involves the first step of the condensation

mechanism—that is, nucleophilic attack by the anionic forms (or OH-). It must take
place preferentially on sites with the highest partial charge—in the middle of the chain
(sites B and C), leading to crosslinked polymers forming dense particles, in agreement
with experimental observation. In an acidic medium, catalysis impacts the second step
of condensation. Elimination of the proton from the alcoholnbridge in the transition
state is eased by the protonation of an OH ligand, which favors formation of the
leaving group (aquo ligand). The OH groups concerned are those located at the ends
of chains, which bear the highest negative partial charge, or even those of the Si(OH)4
monomer. As a result, poorly cross-linked and poorly condensed chains are formed.
Therefore, the morphology of the particles is heavily dependent upon the conditions of
acidity in which condensation takes place. The catalysis of silica condensation may
also be affected by nucleophilic activation using additives such as 4-
dimethylaminopyridine (DMAP, see Table 2.3). Particles and polymers may remain
dispersed in the medium, forming sols, or they can agglomerate and gel more or less
rapidly, depending on the surface charge density of particles and consequently on the
pH of the medium. On either side of pH = 2, gelation is faster because acid or base
catalysis accelerate the condensation rate of Si-OH groups between particles. At pH <
2, the surface charge is too small to provide efficient repulsion between particles. At
pH > 2, base catalysis of oxolation has the same effect, which is maximum for pH = 6.
For pH > 6, the surface charge is high enough for the sol to remain stable.

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Table (3.2): Partial Charge Calculated of the Various Sites into a Chain of Silica
Tetrahedral [127].

The reactivity of metal alkoxides is also deeply influenced by their molecular

structure and complexity that depends on the steric hindrance of the alkoxo ligands,
OR, especially for the transition element alkoxides. Due to the fact that the oxidation
state, z, is generally smaller than the coordination number of the metal, it inhibits
coordination of the metal in the monomeric M(OR)z species. For instance, this occurs
in the case of titanium alkoxide Ti(OiPr)4, which is a monomer in isopropanol. The
coordination of titanium is only four and the reaction with water leads to
instantaneous precipitation of heterogeneous and amorphous titania particles. With
ethoxy ligands, titanium forms oligomeric species [Ti(OEt)4].n (n = 3 in benzene, n =
2 in EtOH) in which the titanium coordination is higher, n = 5 in the trimer, n = 6 in
the dimer because of the formation of a solvate [Ti(OEt)4].2  (EtOH)2.
Monodispersed spherical particles have been synthesized by controlled hydrolysis of a
diluted solution of Ti(OEt)4 in EtOH [128]. The monodispersity clearly results from
slower hydrolysis and condensation reactions with less reactive precursors allowing
decoupling of the nucleation and growth steps. It is however possible to control the
reactivity of low coordinated titanium in the presence of specific ligands. For instance,
hydrolysis at 60°C of titanium butoxide Ti(OBu)4 in the presence of acetylacetone
forms monodispersed 1–5 nm TiO2 anatase Nanoparticles [129]. Avery elegant design
of the shape of anatase Nanospheres and Nanorods is obtained by controlling the rate
of hydrolysis of Ti(OiPr)4 at 80°C in the presence of oleic acid.

In a general way, the rate of reactions and the nature of condensed species
obtained depend also on the hydrolysis ratio defined as h =H2O/M.

 Molecular clusters are formed with very low hydrolysis ratios (h < 1).

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The condensation reactions are relatively limited. Hydrolysis of

[Ti(OEt)4].2  2(EtOH) forms soluble species such as Ti7O4(OEt)20
(h = 0,6), Ti10O8(OEt)24 (h = 0,8) or Ti16O16(OEt)32 (h = 1). A variety of such
clusters have been isolated and characterized by X-ray diffraction. They can assemble
themselves into Nanostructures enabling the formation of hybrid organic-inorganic
materials [130].
 Addition of water in substoichiometric amounts does not allow the
substitution of all alkoxo ligands that otherwise leads to oxopolymers.
Such precursors are well designed for obtaining coatings or thin films. The
residual OR groups can react with surface hydroxyl groups of the substrate
forming covalent bonds. The films are strongly adhesive and the organic
residues can be then eliminated by thermal treatment.
 All alkoxo groups are eliminated in the presence of a large excess of water
(h >>10), leading to oxide Nanoparticles in suspension. Because of the
high dielectric constant of the medium, the surface hydroxylated groups
are mainly ionized allowing formation of sols or gels similar to those
obtained in aqueous solution.
3.1.3.4. Nonhydrolytic routes to oxide Nanoparticles. Nonhydrolytic sol-gel
chemistry has proved to be a promising route to metal oxides, as demonstrated by the
work of Corriu and Vioux on silica, titania, and alumina [131]. It has become a widely
explored approach to synthesize metal oxide Nanoparticles under various conditions
[89].

In nonaqueous media in the absence of surfactant, one possibility is the use of

metal halides and alcohols (Nierderberger). This approach is based on the general
reaction scheme:

≡ M-X
ROH →≡ M-OH + RX

≡ M-OH + ≡ M-X → ≡ M-O-M ≡ + HX

It is widely observed that complexation of water to a transition metal results in an

increase in its Brønsted acidity [90]. Similarly, an increased acidity of water upon

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complexation to main group compounds has been inferred from NMR data. The recent
isolation of a series of amine substituted alcohol complexes [132]. has allowed for an
estimation of the change in the acidity of alcohols upon coordination to a metal.
Complexation of a protic Lewis base (e.g., ROH, R2NH, etc.) results in the increase in
Brønsted acidity discerned by a decrease in pKa of about 7 for the
-proton. This
activation of the coordinated ligand by increasing the formal positive charge on the
-
substituent is analogous to the activation of organic carbonyls toward alkylation
and/or reduction by aluminum alkyls [133–135].

While reaction of primary and secondary alcohols with tetrachlorosilane is the

usual method for preparing tetraalkoxysilanes [121]., the same reaction with tertiary
alcohols and benzylic alcohols form silica and the corresponding alkyl halide, RCl.
The two modes of reaction involve initially the coordination of a lone pair of electrons
of an alcoholic oxygen atom to the silicon center, followed by the cleavage of either
the hydroxyl or alkoxyl group (Figure 3.10). Electron-donor substituent groups in the
alkyl radical direct the process to hydroxylation (pathway b) with the liberation of
RCl) by favoring the nucleophilic attack of chloride on the carbon group, due to its
increased cationic character.

Figure (3.10): Possible reactions for the alcoholysis of MX4.

Hydroxylated species so formed react with unsolvolyzed compound according to:

≡ M-OH + X-M ≡ → ≡ M-O-M ≡ + HX

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Benzyl alcohol seems to be well-designed for synthesis of various oxide

Nanoparticles. Typically, anhydrous metal chloride is introduced in benzyl alcohol
under vigorous stirring in order to avoid precipitation and then the mixture is heated
under stirring for days (2 to 20), depending on the metal chloride. Nanoparticles of
titania (anatase) with size varying from 4 to 8 nm are obtained at temperatures from
40 to 150°C with different concentrations of TiCl4 [136]. In similar conditions, VOCl3
forms Nanorods (approximately 200 × 35 nm) of vanadium oxide and WCl6 forms
platelets (approximately 30 to 100 nm, thickness 5 to 10 nm) of tungsten oxide [137].

Alkyl halide elimination also occurs between metal chloride and metal alkoxide
following the reaction:

≡ M-Cl + RO-M ≡ → ≡ M-O-M ≡ + RCl

Such a reaction between TiX4 and Ti(OR)4 in heptadecane in the presence or

trioctylphosphine oxide (TOPO) at 300°C produces spherical Nanoparticles of TiO2
anatase, around 10 nm in diameter [138]. Here, TOPO acts as a nonselectively
adsorbed surfactant, which slows down the rate of reaction, allows the control of
particle size, and avoids the formation of other TiO2 polymorphs (brookite or rutile).
In the presence of the mixed surfactant system, TOPO and lauric acid (LA), with
increasing ratios LA/TOPO, a spectacular control of the shape of TiO2 anatase
Nanorods is obtained (Figure 3.11). The specifically strong adsorption of LA onto
(001) faces slows down the growth along [001]. directions, thereby inducing growth
along [101]. directions that results in the formation of rods.

Another nonhydrolytic synthesis of oxide Nanoparticles involves thermal

decomposition of metal organic complexes in solution in the presence of surfactant. In
fact, since water may be produced by the thermolysis of the organic derivatives, a
hydrolytic pathway cannot be excluded. One of the most studied approaches involves
the thermolytic decomposition of an inorganic complex at high temperatures. Two
approaches include: the decomposition of Fe(acac)3 or FeCl3 and M(acac)2 salts [140-
142]., and the decomposition of Fe(CO)5 and M(acac)2 salts [143, 144].

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Figure (3.11): HRTEM analyses of TiO2 anatase Nanoparticles and simulated three
dimensional shape of (a) a bullet, (b) a diamond, (c) a short rod, (d) a long rod, and (e)
a branched rod. The long axes of the Nanocrystals are parallel to the c-axis of the
anatase structure, while the Nanocrystals are faceted with (101) faces along the short
axes. Hexagon shapes (the [010]. projection of a truncated octagonal bipyramid)
truncated with two (001) and four (101) faces are observed either at the one end or at
the center of the Nanocrystals. The branched shape is a result of the growth along
(101) directions starting from the hexagon shape. Scale bar = 3 nm, [139].

For simple oxides (e.g., Fe3O4) the precursor (e.g., Fe(acac)3) is added to a
suitable solvent heated to a temperature that allows for the rapid decomposition of the
precursor. The choice of temperature and the temperature control (i.e., variation of the
temperature during the reaction) are important in defining the resulting Nanoparticle
size and size distribution. By this method, highly uniform Nanoparticles can be
obtained (see Figure 3.12)[145].

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Figure (3.12): TEM image of 4 nm Fe3O4 Nanoparticles prepared from the thermal
decomposition of Fe(acac)3[145].

In addition to simple metal oxides (MxOy) a range of mixed metal oxides can also
be prepared. For example, Nanospheres and Nanocubes of cobalt ferrite can be
obtained from cobalt and iron acetylacetonates, Co(acac)2 and Fe(acac)3 in solution in
phenylether and hexadecanediol in the presence of oleic acid and oleylamine . Heating
at 260°C forms CoFe2O4 spherical Nanocrystals with a diameter of 5 nm. These
Nanocrystals serve as seeds for a new growth as the second step of the synthesis,
giving perfect Nanocubes from 8 to 12 nm, depending on the conditions. Nanocubes
in the 8 nm range can also be used as seeds to obtain spheres (Figure 3.13)[145]. The
tuning of the shape of ferrite Nanocrystals is managed by the parameters of growth,
such as heating rate, temperature, reaction time, ratio of seed to precursors, and ratio
of oleic acid, acting as surfactant stabilizing the Nanocrystal, to oleylamine providing
basic conditions needed for the formation of spinel oxide. Variations in the
morphology of numerous oxide Nanocrystals, including Nanocrystals of Fe, Co, Mn
ferrites, Co3O4, Cr2O3, MnO, NiO, ZnO, and others, have been obtained by pyrolysis
of metal carboxylates in the presence of different fatty acids (oleic, myristic) [142–
146].

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Figure (3.13): (a) TEM micrographs with the scale bar as 50 nm of cubic CoFe2O4
Nanocrystals. (b) HRTEM micrographs showing a 12-nm cubic CoFe2O4 Nanocrystal
and (c) an 8-nm spherical CoFe2O4 Nanocrystal [145].

Metal carbonyl complexes are also interesting precursors to synthesize uniform

metal oxide Nanoparticles. Thermal decomposition at 100°C of iron pentacarbonyl,
Fe(CO)5, in octyl ether in the presence of oleic acid forms iron Nanoparticles which
are then transformed to monodisperse spherical γ-Fe2O3 Nanoparticles by
trimethylamine oxide acting as a mild oxidant (Figure 3.14) [148]. Particle size can be
varied from 4 to 16 nm by controlling the molar ratio Fe(CO)5 to oleic acid.

Thermal decomposition of Fe(CO)5 in solution containing dodecylamine as a

capping ligand and under aerobic conditions forms also γ-Fe2O3 Nanoparticles with
diamond, sphere, and triangle shapes with similar 12-nm size [149]. Uniform-sized
MnO Nanospheres and Nanorods are obtained by heating at 300°C the mixture of
Mn2(CO)10 with oleylamine in trioctylphosphine (TOP) [150]. The size of
Nanospheres can be varied from 5 to 40 nm depending on the duration of heating,
using phosphines both as solvent and stabilizing agent (Figure 3.14). With TOP, 10
nm MnO particles can be obtained. If the surfactant complex is rapidly injected into a
solution of TOP at 330°C, Nanorods 8 × 140 nm of MnO are produced. In fact, these
rods are polycrystalline. They are formed by an aggregation of spheres with oriented
attachment and having a core shell structure with a thin Mn3O4 shell. Heating of
W(CO)6 at 270°C for 2 hours in trimethylamine oxide in the presence of oleylamine

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forms uniform Nanorods of tungsten oxide with an X-ray diffraction pattern matching
the W18O49 reflections [149]. The lengths of the Nanorods are controlled by the
temperature and the amount of oleylamine.

100 nm
50 nm
(a) (b)

(c) 50 nm

Figure (3.14): TEM image of (a) a two-dimensional hexagonal assembly of 11nm

γ-Fe2O3 Nanocrystallites (from Hyeon 2001) and (b) 8 × 140 nm sized MnO Nanorods
(from Park 2004a), (c) 75 ± 20 nm tungsten oxide Nanorods [149].

3.1.4. From minerals to materials

As discussed earlier, precursor sol-gels are traditionally prepared via the

hydrolysis of metal compounds. This “bottom-up” approach of reacting small
inorganic molecules to form oligomeric and polymeric materials is a common
approach for a wide range of metal and nonmetal oxides.

However, in the case of aluminum oxide Nanoparticles, the relative rate of the
hydrolysis and condensation reactions often makes particle size control difficult. The
aluminum-based sol-gels formed during the hydrolysis of aluminum compounds

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belong to a general class of compounds: alumoxanes. The term alumoxane is often

given to aluminum oxide macromolecules formed by the hydrolysis of aluminum
compounds or salts, AlX3 where X = R, OR, OSiR3, or O2CR; however, it may also be
used for any species containing an oxo (O2-) bridge binding (at least) two aluminum
atoms—that is, Al-O-Al. Alumoxanes were first reported in 1958 by Andrianov and
Zhadanov [151]., however, they have since been prepared with a wide variety of
substituents on aluminum. The structure of alumoxanes was proposed to consist of
linear or cyclic chains (Figure 3.15) analogous to that of poly-siloxanes [153]. Strictly
speaking, the classification of alumoxanes as polymers is slightly misleading since
they are not polymeric per se, but exist as three-dimensional cage structures [154–
156]. For example, siloxy-alumoxanes, [Al(O)(OH)x(OSiR3)1-x].n, consist of an
aluminum-oxygen Nanoparticle ore structure (Figure 3.15c) analogous to that found in
the mineral boehmite, [Al(O)(OH)].n, with a siloxide substituted periphery [157–159].
Based on the knowledge of the boehmite-like Nanoparticle core structure of
hydrolytically stable alumoxanes, it was proposed that alumoxanes could be prepared
directly from the mineral boehmite. Such a “top-down” approach represented a
departure from the traditional synthetic methodologies.

Figure (3.15): Structural models proposed (a and b) and observed (c) for aluminum
oxide Nanoparticles formed from the hydrolysis of aluminum compounds[153].

Assuming that hydrolytically stable alumoxanes have the boehmite-like core

structure (Figure 3.15c), it would seem logical that they could be prepared directly
from the mineral boehmite. The type of capping ligand used in such a process must be
able to abstract and stabilize a small fragment of the solid-state material. In the siloxy-

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alumoxanes it was demonstrated that the “organic” unit itself contains aluminum, as
shown in (Figure 3.16a.) Thus, in order to prepare the siloxy-alumoxane the “ligand”
[Al(OH)2(OSiR3)2].-, would be required as a bridging group; adding this unit clearly
presents a significant synthetic challenge. However, the carboxylate anion, [RCO2].-,
is an isoelectronic and structural analog of the organic periphery found in our siloxy-
alumoxanes (Figure 3.16) [160].

Thus, it has been shown that carboxylic acids (RCO2H) react with boehmite,
[Al(O)(OH)].n, to yield the appropriate carboxy-alumoxane:

HO2CR
[Al(O)(OH)].n ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ [Al(O)x(OH)y(O2CR)z].n

Initial syntheses were carried out using the acid as the solvent or xylene [160,
161]., however, subsequent research demonstrated the use of water as a solvent and
acetic acid as the most convenient capping agent [162]. A solventless synthesis has
also been developed [163]. Thus, the synthesis of alumoxane Nanoparticles may be
summarized as involving the reaction between dirt (boehmite), vinegar (acetic acid),
and water. The function of the acid is twofold. First, to cleave the mineral lattice and
“carve out” Nano scale fragment, and second, to provide a chemical cap to the
fragment (Figure 3.17) [162].

Figure (3.16): Structural relationship of the capping ligand for (a) siloxy and (b)
carboxylate alumoxane Nanoparticles [162].

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Figure (3.17): Pictorial representation of the reaction of boehmite with carboxylic

acids [163].
The carboxylate-alumoxane Nanoparticles prepared from the reaction of boehmite
and carboxylic acids are air and water stable. The soluble carboxylate-alumoxanes can
be dip-coated, spin-coated, and spray-coated onto various substrates. The physical
properties of the alumoxanes are highly dependent on the identity of the substituents.
The size of the alumoxane Nanoparticles is dependent on the substituents, the reaction
conditions (concentration, temperature, time, etc.), and the pH of the reaction solution
(Figure 3.18) [164]. Unlike other forms of oxide Nanoparticle, the alumoxanes are not
monodispersed but have a range of particle sizes.

Figure (3.18): Unimodal analysis plot showing the change in average particle size
with increasing pH for each of the five carboxylatealumoxanes: acetic acid-alumoxane
( ), methoxy(ethoxy)acetic acidalumoxane (o), and methoxy(ethoxyethoxy)acetic
acid-alumoxane ( )[164].

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Figure (3.19): Schematic representation of the exchange reaction that occurs between
a metal complex and the core of the alumoxane Nanoparticle [165].

Also, unlike other metal oxide Nanoparticles, the core of the alumoxane can
undergo a low temperature reaction that allows for the incorporation of other metals
(e.g., Ti, La, Mo, V, Ca). This occurs by reaction of metal acetylacetenoates
[M(acac)n]. with the carboxylate alumoxane (Figure 3.19) [165–167].

The reason for the particular stability and usefulness of carboxylic acids in the
cleavage of the boehmite structure is due to the particular bridging binding mode the
carboxylate ligand adopts in aluminum-oxide systems [168].

Using a combination of X-ray crystallography and ab initio calculations it has

been shown that the carboxylate ligand is therefore near perfectly suited to bind to the
(100) surface of boehmite (Al . . . Al = 3.70 Å), and hence stabilize the boehmite-like
core in carboxylate alumoxanes (Figure 3.20) [169].

Given the analogous structure of Fe(O)(OH) (lepidocrocite) to boehmite, it is not

surprising that the iron analog of alumoxane Nanoparticles (i.e., ferroxanes) is readily
prepared. First prepared by Cortalezzi et al [170], ferroxanes have been extensively
characterized, and have shown identical structural features to alumoxanes and undergo
similar exchange reactions [171].

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Figure (3.20): Total energy calculation of a carboxylic acid interacting with an Al2
unit as a function of the Al    Al distance.
The Al    Al distances present on the (100) and (211) crystallographic planes of
boehmite are marked [168].

3.2. Structural Behavior of Nano Material

3.2.1 Introduction

Recently, the technology of particles of small sizes has attracted considerable

scientific interest due to their new potential uses. The particles of small sizes can
result in improved properties from conventional grain-size materials of the same
chemical composition. Thus, industries may be able to design new products that
function at high levels.

The studies about this field focused on many ways such as the compressive
strength, flexure performance, high temperature resistance, permeability and etc …..

Some of the widely reported nano particles in cement concrete industries s are
based on Titanium dioxide (TiO2), Nano silica (SiO2), Alumina (Al2O3), ZrO2, Carbon
nano tube (CNT) nano clay, etc. Currently, the most active research areas dealing with

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cement and concrete are: understanding of the hydration of cement particles and the
use of nano-size ingredients such as alumina and silica particles.

The studies reported following general conclusions:

1- Replacement of steel cables by much stronger carbon nanotubes in suspension
bridges and cable-stayed bridges.
2- Use of nano-silica, to produce dense cement composite materials.
3- Incorporation of resistive carbon nanofibers in concrete roads in snowy areas.
4- Incorporation of nano-titania, to produce photocatalytic concrete.
5- Use of nano-calcite particles in sealants to protect the structures from
aggressive elements of the surrounding environment.
6- Use of nano-clays in concrete to enhance its plasticity and flow ability.
7- Urban air quality could be improved by if the civil structures are treated with
nano TiO2.
Although, several studies are reported, there is no clear mechanism on the Form-
Structure-Function of materials as it’s intended to use them in cement or concrete.
Further studies based on the assessment of nano particles with respect to their high
surface to volume ratio, stability and their structural elucidation when combined with
other cementitious materials have to be studied in detail [172].

3.2.2 Effect of adding nano materials on the compressive

strength of the concrete.

1- The results of the studies indicate that sonication enhanced the effect of
nanoCaCO3 in improving the early-age hardened properties of pastes compared to
blending. Sonicated nano CaCO3 led to a more pronounced acceleration in rate of
hydration of cement pastes compared to blend. A 5% addition of sonicated nano
CaCO3 completely offset the delay in setting caused by a 50% fly ash replacement of
cement. And sonicated nano CaCO3 led to a greater improvement in the 3 and 7d
compressive strength of cement pastes with 30% fly ash replacement compared to
blend [173].

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2- The early-age compressive strength of fly ash-cement mortars can be greatly

improved by the addition of CNS: the higher the dosage, the greater the improvement.
However, CNS adversely affects strength gain at later ages: the higher the dosage, the
greater the reduction in rate of strength.

3- Addition of nano-materials increased the 7-day and 28-day compressive

strength of cement-fly ash pastes. Nano-silica was most effective in increasing the 7-
day compressive strength of cement-fly ash pastes. However, nano-silica modified
paste showed the lowest 28-day compressive strength among all nanomaterials
modified cement-fly ash pastes. This may be attributed to the high pozzolanic
reactivity of nano-silica as well as its effect on the Ca/Si ratio of CSH gel. Nano-
limestone modified paste showed the lowest 7-day compressive strength but the
highest 28-day compressive strength among all nano-materials modified cement-fly
ash pastes [173].

4- The experimental results of tensile and compressive strength it is expected that

adding of Fe2O3 nanoparticles up to 3% by weight of cement can act as a filler for
strengthening the micro structure of cement and also reduces the quantity and size of
Ca(OH)2 crystals and fill the voids of C-S-H gel structure and finally structure of
hydrated product is compacted and denser. With the increase of nanoparticles quantity
up to 5% there is decrease in nanoparticles distance and Ca(OH)2 crystal due to
limited space cannot grow to appropriate size. This factor along with the agglomerated
nanoparticles causes the mechanical properties of the sample 5NF is lower than the
ordinary mortar sample [174].

5- Application of effective superplasticizer helps disperse such agglomerates and,

for certain nano-SiO2 products, improve the strength of portland cement mortars at all
ages of hardening, reaching 90-day compressive strength of up to 144.8 MPa. It can
be concluded that high-temperature treatment (at 400°C and higher) of nano-SiO2
adversely affects the performance of these additives and must be avoided.
Ultrasonification was found to be effective to restore the performance of thermally
treated nano-SiO2, but it was not a very effective disagglomeration method for

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“standard” nanoparticles dried at 70°C. Apparently, the application of the ultrasonic

treatment of higher dispersion energy can overcome this obstacle. Further research is
required to modify the sol-gel method in order to avoid the formation of agglomerates
(such as the development of nano-SiO2 products in liquid state, application of
surfactants, ultrasonification and microwave drying), and to achieve better dispersion
of developed nano-SiO2. Additional work is necessary to investigate the effect of
synthesized nano-SiO2 on the hydration of portland cement based systems [175].

6- The replacement of cement by lime sludge is fixed throughout as 20 % except

control paste/mortar. In addition to the replacement of lime sludge, silica fume by 3
and 6 % and nanosilica by 1.5 and 3 % are incorporated in cement paste and mortar.
The phase changes due to the thermal effect of all the 28-day water-cured composite
pastes are monitored by XRD and thermal analysis by TG-DTG. Unstressed residual
compressive strength tests are used in this study for the mortars. Results show that the
incorporation of lime sludge – silica fume cement composites with cement
replacement level up to 26 % increases the compressive strength significantly at
ambient temperature as well as after 2-h exposure to 500 °C compared to control
mortars, but spalling of mortars occurs at 800 °C after 28 days of water curing. In the
case of lime sludge– nanosilica cement composites, the residual compressive strength
reduces considerably at all the temperatures, but there is no occurrence of spalling
[176].

7-Another research studied effect of elevated temperature on of high strength

concrete (HSC) modified with nano-Silica (nS) and on its compressive and tensile
strengths, spalling, and mass loss [177].

That research studied the effect of elevated temperature on the compressive and
tensile strength, spalling, and mass loss of HSC modified with nS. Six sample
mixtures contained varying amounts of nS and two samples did not contain nS are
considered in the experimental program. The mechanical properties of the modified
HSC were measured by heating 150- 300mm sample cylinders of concrete to 400,
600and 800 °C at a rate of 20 C/min. The obtained results demonstrate that nS

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efficiently used in HSC can improve its mechanical properties at elevated temperature.
The results show that the presence of nS increased residual compressive and tensile
strengths and spalling and mass loss are decreased aspenetrability increased [177].

8-The hardened pastes made of OPC– nano- metakaolin blends containing 4%, 6%
and 10% NMK showed higher compressive strength values as compared to those of
the neat OPC paste. The optimum substitution of OPC by NMK is 10% [178].

9-One study is concerned with the synthesizing of Cu-Zn nano ferrite particles in
the laboratory applying simple techniques. The morphology of the synthesized nano-
particles was analyzed using Transmission Electron Microscopy (TEM), and the
minerals were identified using X-ray diffraction (XRD). The nano material was used
to replace 1- 4 percent by weight of Portland cement in cement pastes and mortars.
The microstructure and compressive strength of the composites were then evaluated.
The microstructure was characterized by means of Scanning Electron Microscope
(SEM) analysis and the compressive strength was evaluated at 7 and 28 days. While
some specimens were tested at normal temperature, other specimens were tested after
2-hour exposure at elevated temperatures of 200oC and 400oC. The results showed
that it was possible to synthesize nano-particles having an average size of 12
nanometers. Also, the test results revealed that the optimum content of the nano-ferrite
was 1% to produce the maximum increase in the compressive strength. Adding the
optimum dose of nanoparticles helped to produce a denser microstructure. The paste
and mortar specimens showed general tendency to lose strength after exposure to the
elevated temperatures [179].

The addition of ultrafine barium sulfate enhances the hydration properties of OPC
up to 15 wt% replacements and Addition of 2.5 wt % ultrafine barium sulfate
increases the strength of OPC more than 20% [179].

Indirect tensile and compressive strength tests showed valuable enhancement in

mechanical properties of CNTCC with increasing CNT loading ratio. The
microstructure of the CNTCC was characterized by means of scanning electron
microscope (SEM) analysis, while the mineralogy was analyzed by means of a

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differential scanning calorimeter (DSC). The addition of CNT by about 0.04%

enhanced the indirect tensile strength to about 52%, compression strength to about
48% and hardness to about 232.6%. This is due to uniformly dispersion of CNT and
the effect of bridging up the cracks in the composite [180].

3.2.3 Effect of high temperature on the concrete.

Under normal conditions, most concrete structures are subjected to a range of

temperature no more severe than that imposed by ambient environmental conditions.
However, there are important cases where these structures may be exposed to much
higher temperatures (e.g., jet aircraft engine blasts, building fires, chemical and
metallurgical industrial applications in which the concrete is in close proximity to
furnaces, and some nuclear power-related postulated accident conditions). Concrete’s
thermal properties are more complex than for most materials because not only is the
concrete a composite material whose constituents have different properties, but its
properties also depend on moisture and porosity. Exposure of concrete to elevated
temperature affects its mechanical and physical properties. Elements could distort and
displace, and, under certain conditions, the concrete surfaces could spall due to the
buildup of steam pressure. Because thermally induced dimensional changes, loss of
structural integrity, and release of moisture and gases resulting from the migration of
free water could adversely affect plant operations and safety, a complete
understanding of the behavior of concrete under long-term elevated temperature
exposure as well as both during and after a thermal excursion resulting from a
postulated design-basis accident condition is essential for reliable design evaluations
and assessments. Because the properties of concrete change with respect to time and
the environment to which it is exposed, an assessment of the effects of concrete aging
is also important in performing safety evaluations. Presented in the following sections
of this report is a review of the effects of elevated temperature on concrete materials,
concrete materials for elevated-temperature service, code and design considerations
for reinforced concrete structures exposed to elevated temperature, and the
performance of selected structural members subjected to elevated temperature. Under

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normal conditions, most concrete structures are subjected to a range of temperature no

more severe than that imposed by ambient environmental conditions. However, there
are important cases where these structures may experience much higher temperatures
(e.g., jet aircraft engine blasts, building fires, chemical and metallurgical industrial
applications in which the concrete is in close proximity to furnaces, and some nuclear
power-related postulated accident conditions)[181].

Under normal conditions, most concrete structures are subjected to a range of

temperature no more severe than that imposed by ambient environmental conditions.
However, there are important cases where these structures may experience much
higher temperatures (e.g., jet aircraft engine blasts, building fires, chemical and
metallurgical industrial applications in which the concrete is in close proximity to
furnaces, and some nuclear power-related postulated accident conditions). The
performance of Portland cement-based materials under elevated temperature exposure
is very complicated and difficult to characterize. Concrete’s thermal properties are
more complex than for most materials because not only is the concrete a composite
material whose constituents have different properties, but also its properties depend on
moisture and porosity. Exposure of concrete to elevated temperature affects its
mechanical and physical properties. The changes in properties result from three
processes that take place at elevated temperature:

(1) Phase transformations (e.g., loss of free water at about 100˚C, decomposition
of calcium hydroxide at about 450°C, and crystal transformation of quartz at 573°C ),
and

(2) pore structure evolution (e.g., volume and surfaces of pores increase up to a
temperature of about 500°C and then decrease with further temperature increase, and

(3) Coupled thermo-hydro-chemo-mechanical processes (e.g., temperature

gradients leading to thermal stresses, multiphase transport of water, and chemical
changes that affect pore pressure and structure) provides a summary of the
physiochemical processes in Portland cement concrete during heating.

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Under thermal loading elements could distort and displace, and, under certain
conditions, the concrete surfaces could spall due to the buildup of steam pressure.
Because thermally-induced dimensional changes, loss of structural integrity, and
release of moisture and gases resulting from the migration of free water could
adversely affect plant operations and safety, a complete understanding of the behavior
of concrete under long-term elevated temperature exposure as well as both during and
after a thermal excursion resulting from a postulated design-basis accident condition is
essential for reliable design evaluations and assessments [182].

Although concrete is recognized as an excellent thermal-resistant material among

various construction materials, critical deterioration of concrete is observed when it is
exposed to high temperature like as in the case of fire. A number of physical and
chemical nonreversible changes occur in concrete when subjected to high temperature.
Concrete damage due to high temperature includes weight loss, reductions in strength
and modulus of elasticity, and formation of cracks and large pores [183]. The fire
resistance capacity of concrete is complicated because not only is concrete a
composite material with components having different thermal characteristics, it also
has properties that depend on porosity and moisture. As the cement paste is exposed to
increasing temperatures the following process takes place:

(1) The expulsion of evaporable water at a temperature of 100 °C,

(2) The beginning of the dehydratation of the hydrates of calcium silicate at 180 °C,
(3) The decomposition of calcium hydroxide at a temperature of 500 °C and
(4) The decomposition of hydrate calcium silicate begins around 700°C.

The alterations produced by high temperatures are more evident when the
temperature exceeds 500°C. At this temperature level, most changes experienced by
concrete can be considered to be irreversible [184]. Fibers have extensively been used
to improve the ductility of concrete. Recently, it has been found that a number of
fibers can also improve the residual properties of concrete after exposure to elevated
temperatures. Several studies carried out by different authors [185-186] show that
concrete thermal stability is improved by incorporating PP fibers to the mix. PP fibers

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have been used to considerably reduce the amount of spalling and cracking and to
enhance the residual strength [187-188]. Since the fibers melt at approximately 160–
170 °C, they produce expansion channels. The additional porosity and small channels
created by PP fibers melting may lower internal vapor pressure in the concrete and
reduce the likelihood of spalling, according to Noumowe [189]. But minimal or even
negative effects of PP fibers on the residual performance of the heated concrete were
also observed. The additional porosity due to the melting of PP fibers can lead to a
decrease of the residual mechanical performances of concretes.

It is well established that mechanical properties of concrete are adversely affected

by thermal exposure [190-195]. NSC typically loses between 10 to 20% of its original
compressive strength when heated to300 °C, and between 60 to 75% at 600 °C.
Elastic modulus decreases in a similar fashion. For High strength concrete, higher
rates of strength loss, as much as 40% of the original strength was observed at
temperatures below 450 °C. However, what is more important about High strength
concrete is the occurrence of explosive spalling when it is subjected to rapid heating.
It has been theorized that the higher susceptibility of High strength concrete to
explosive spalling is due, in part, to its lower permeability, which limits the ability of
water vapor to escape from the pores. This results in a build-up of pore pressure
within the cement paste. As heating increases, the pore pressure also increases. This
increase in vapor pressure continues until the internal stresses become so large as to
result in sudden, explosive spalling. Spalling, however, has been observed on an
inconsistent basis. Often, explosive spalling has occurred to only a few concrete
specimens from a larger group of specimens that were subjected to identical testing
conditions. This erratic behavior makes it difficult to predict with certainty when
concrete will fail by explosive spalling. Given the potential benefits of concrete and its
increased usage, questions about its fire performance need to be resolved. Also, the
applicability of existing fire-design provisions, which were developed mostly from the
results of fire tests on NSC, to HSC needs to be evaluated. To address these issues, a
workshop, entitled International Workshop on Fire Performance of HSC, was
convened by the Building and Fire Research Laboratory at NIST [196].

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The participants included international and U.S. experts who have been involved
with studies of fire-exposed concrete. The specimens were kept covered in a
controlled chamber at 20 ± 2 °C for 24 h until demoulding. Thereafter, specimens
were placed in water at 20 °C and 60% RH until the 28th days. Later, they were kept in
air until 56thday in laboratory where the relative humidity and the temperature were
about 60% and 20 °C respectively. At the 56th day after the specimens placed in an
electric furnace in which temperature is increased to the desired temperatures at a rate
of 1 °C/min, and they were kept at maximum temperature for 3 h. At the end of 3 h
exposure to the maximum temperature the power was turn off and the specimens were
remained until the furnace cooled down to room temperature to prevent the thermal
shock to the specimens.

During the heating period moisture in the test specimens was allowed to escape
freely. The applied heating curve was not the standard fire time–temperature curve but
a heating–cooling cycle close to RILEM recommendations [197]. The test specimens
were subjected to 200, 400, 600, 800 °C, and the variation of compressive strength,
ultrasonic pulse velocity and weight of SCC specimens were compared to that
observed at 20°C. After the specimens cooled to room temperature they were taken
out of the furnace and their residual compressive strength and ultrasonic pulse
velocity, along with the weight values were determined. Thereafter, for each type of
concrete the residual properties were compared to the properties of unheated control
specimens. Six specimens of each mix type and heating cycle, three of them with PP
fibers and the rest without PP fibers, were tested for loss in weight, the reduction of
ultrasonic pulse velocity and loss in compressive strength.

Immediately after cooling of the heated specimens, crack pattern on the SCC
surfaces were inspected. Weight losses were determined by weighing specimens with
a precision balance. The velocity of the propagation of ultrasound pulses was
measured according to ASTM C 597 [198] by direct transmission using a Controls
E48 ultrasound device. These measures the time of propagation of ultrasound pulses
in a sample in the range (0.1–9999.9) is with a precision of 0.1 s. The transducers used
were 50 mm in diameter, and had maximum resonant frequencies, as measured in our

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laboratory, of 54 kHz. Concrete is generally regarded as a fire resistant material.

However, a number of researchers have reported that the performance of high strength
concrete in fire is different from that of normal strength concrete [199-201].

Spalling mostly occurs in high strength concrete at elevated temperatures. In

some cases, high strength concrete structural members in fire can collapse due to the
concrete spalling. According to moisture clog theory [202-204], spalling occurs due to
the high pressure induced by water vapor inside concrete in fire. The likelihood of
extremely increased pressure in high strength concrete is attributed to its low
permeability, which impedes the flow of vapor inside and outside concrete. Since high
strength concrete has this disadvantage in fire, various spalling resistance methods
have been studied by many researchers. Poon et al. [205] added metakaolin in
concrete and concluded that the addition of the metakaolin adversely caused severe
spalling. Hernndez-Olivares and Barluenga [206] used solid particles, recycled from
crumbed used truck tires and found that the inclusion of rubber with 3% improved fire
performance but decreased its strength. Terro [207] incorporated fine glass to replace
10% of the fine aggregate. This concrete performed better than the control concrete,
up to 700°C, but the residual compressive strength reduced to 50% after the fire test.
A number of researchers have proposed the most efficient mitigating method, the
addition of synthetic fibers with low melting point. In particular, researchers have
found that the addition of polypropylene fibers (melted at 160–170 °C) in concrete
increases the internal porosity and provides pathways for vapor to evacuate [208-211].

However, there is still concern in relation to residual compressive strength. Fiber

addition alone cannot help concrete to retain its strength after fire exposure [212-214],
thus limit the possible applicability of fiber addition in practice. The current study is
the final stage of a long term project in Korea. The research was initiated in 2002 at
Cheongju University to develop an effective technique to protect high strength
concrete from spalling in fire [215]. Number of alternative techniques was studied in
2002 project, and some of them were chosen and were applied to larger specimens as
part of research in the national project commenced in 2005 that aimed to develop
multi-functional high strength concrete [216]. This final stage involved a field

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application. According to the new code legislated by the Ministry of Land, Transport
and Maritime Affairs, Korea 2008, high strength concrete, defined as concrete with
strength more than 50 MPa, must have the fire resistant protection.

In this long term project mentioned above four options were considered as
spalling protection methods for concrete construction:
(1) Use of low water to cement ratio;
(2) Use of fibre reinforcement;
(3) Use of fireproof covering materials (thermal barriers) and
(4) Use of lateral confinement along with fibre addition.

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