Nanochemistry lectures-part 1

Nanochemistry –part1
College of Science / University of Baghdad/Department of Chemistry
Assis.Prof.Dr.Abdulkareem Mohammed Ali Al-Sammarraie
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Unite one:
Review of chemistry related to nanochemistry
1. The periodic table
The periodic table is an arrangement of the atoms (called elements) that
groups them according to similar properties.
_ The vertical columns are called groups, and the horizontal rows are called
periods.
_ The group 1 is alkali metals, and next to them are alkaline earth metals. The
far right hand side of the periodic table is the noble gases.
_ Emphasizing: From a molecular nanochemistry’s standpoint of view,
atoms in the periodic table are a collection of different basic building units
from which we can make things.
_ In nanotechnology, a subatomic particle called electron plays a very
important role. In another word, nanotechistry is mainly about studying the
impact of electron on material properties at macro-level.

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2. Atomic structure
Three major fundamental subatomic particles: electrons, protons and
neutrons. The protons and neutrons are collectively known as nucleons.
Electrons are tiny, very light particles that have a negative charge. Protons
are much larger and heavier than electrons and have a positive charge.
Neutrons are large and heavy like proton but have no charge.
3.Size of atom
_ Atoms are extremely small and the diameter of a single atom can vary from
0.1-0.5 nanometers. One carbon atom is approximately 0.15 nm in diameter.
_ The atomic size is decreased following the increase of group number, and
increased following the increase of period number.
3. Molecules and phases
Phases (States of Matter) Phases are states that we define by their
properties, such as liquids, gases, and solids.Nanotechnology is largely
concerned with solid phases because the molecules or atoms do not move
around so much and are hence easier to study.

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Solid Keeps shape Keeps
volume
Salt, gold, copper
Liquid Takes shape of
container
Keeps
volume
Water, alcohol, oil
Gas Takes shape of
container
Takes volume
of container
Air, argon,
helium, methane
Plasma – like a gas
of charged
particles.
Takes shape of
container
Takes volume
of container
Stars, nebula,
lightning, plasma
reactors
Molecules:
Molecules are collections of atoms bound to each other that exist in these
phases.
Bonds
- Covalent bond:Covalent bond is a form of chemical bonding that is
characterized by the sharing of pairs of electrons between atoms, or
between atoms and other covalent bonds. In short, attraction-to-
repulsion stability that forms between atoms when they share
electrons is known as covalent bonding. Covalent bonding includes
many kinds of interactions, including δ-bonding, Π-bonding, metal-
metal bonding, agostic interactions, and threecenter two-electron
bonds.
- Ionic bond (or electrovalent bond):Ionic bond is a type of chemical
bond based on electrostatic forces between two oppositely-charged
ions. In ionic bond formation, a metal donates an electron, due to a low
electronegativity, to form a positive ion or cation. In ordinary table salt
(NaCl), the bonds between the sodium and chloride ions are ionic
bonds. Often ionic bonds form between metals and non-metals. The
non-metal atom has an electron configuration just short of a noble gas
structure. They have high electronegativity, and so readily gain

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electrons to form negative ions or anions. The two or more ions are
then attracted to each other by electrostatic forces.
- Metallic bond: Metal atoms typically contain fewer electrons in their
valence shell relative to their period or energy level. These electrons
can be easily lost by the atoms and thereforebecome delocalized and
form a sea of electrons surrounding a giant lattice of positive ions.
Metallic bonds are best characterized by the phrase "a sea of
electrons".
- Van del Walls forces (weak forces): Three types: London forces
(dispersive force), dipole-dipole forces, and hydrogen bonding.
- London forces: 1). Are weakest, but most numerous and influential;
2). Are quantum mechanical (instantaneous electron couplings)
- Hydrogen bond is always involved with hydrogen atom, which is
weaker than covalent, ionic and metallic bonds, but stronger than
London forces and dipole-dipole forces.
Energy of bonds:
Bond Energy (Joules/bond)
Ionic/covelant bonds 4.2 x 10-19
Hydrogen bonds 3.3 x 10-20
London and dipole bonds 3.3 x 10-21
4. Quantum Numbers
There are four numbers that come into the theory of electron clouds as
waves called quantum numbers:
-The first quantum number, n, is the principle energy level. This is the 1 in
1s2. It can have the Values 1, 2, 3, …
-The second quantum number, l, is the sublevel. The nth principle energy
level has n sublevels. it refer to these sublevels by letters: s, p, d, f, g, h, i,
j, k, … Sometimes numbers are used too:0, 1, 2, 3, …(n-1)
-The third quantum number, ml, is the orbital. Every sublevel has one or
more orbitals. The s sublevel has 1 orbital, the p sublevel has 3 orbitals,
the d sublevel has 5 orbitals, etc. These orbital can be indicated by the
number ml = l, l-1, …0, -1, … -l

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-The fourth quantum number, ms, is the spin of the electron. Electrons can
be either spin up or spin down. ms can be either +½ or -½
5. The Uncertainty Principle
The more precisely the position is determined the less precisely the
momentum is known.
Δx Δp ≥ h/2π
where x is location and p is momentum.
We cannot predict exactly what will happen but only assign probabilities.
6.Energy
Energy is the capacity to do work Kinetic Energy is energy of motion
Potential Energy is stored energy Heat is the energy of random motion
Energy and Matter are related through Einstein’s famous equation:
E=mc2
Matter is really just a very compact form of energy
Work and Kinetic Energy
w = f d KE = ½ mv2
Work is defined as applying a force through a distance.
Energy is the capacity of a physical system to do work.
The units of energy are the Joule, J which is the same as kg m2/s2 .
Energy of a photon
E=hγ
E is the energy of the photon, γ is the frequency of the photon, h is Planck’s
constant = 6.626068 x 10-34 m2kg/s.
7.Quantum mechanical effects
_ “energy is discrete, not continuous in a quantum system”.
_ The electronic properties of solids are altered with great reductions in
particle size.

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This effect does not come into play by going from macro to micro
dimensions.
However, it becomes dominant when the nanometer size range is reached.
_ Materials reduced to the nanoscale can suddenly show very different
properties compared to what they exhibit on a macroscale, enabling unique
applications.
a. opaque substances become transparent (copper);
b. inert materials become catalysts (platinum);
c. stable materials turn combustible (aluminum);
d. solids turn into liquids at room temperature (gold);
e. insulators become conductors (silicon).
8. Size concern
The volume of an object decreases as the third power of its linear
dimensions, but the surface area only decreases as its second power.
Because of that, a lot of mini-mechanical devices do not work at the nano
scale.
9. Compounds for nanomaterials
Inorganic compounds: Carbon, Silicon, metal oxides (such as cerium oxide
(CeO2), zinc oxide (ZnO)) etc. Organic compounds: DNA, RNA,
carborhydrate, etc.
10- Definition of Solid-state band theory
Because of the very large number of atoms that interact in a solid material,
the energy levels are so closely spaced that they form bands. The highest
energy filled band, which is analogous to the highest occupied molecular
orbital in a molecule (HOMO), is called the valence band. The next higher
band, which is analogous to the lowest unoccupied molecular orbital
(LUMO) in a molecule, is called the conduction band . The energy separation
between these bands is called the energy gap, Eg.

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The filling of these bands and the size of the energy gap determine if a
material is a conductor (a metal), a semiconductor, or an insulator. In metals
there is no energy gap between filled and unfilled energy levels. A significant
number of electrons are thermally excited into empty levels, creating holes
in the filled band. The electrons in a conduction band and the holes in a
valence band can move throughout the material, allowing it to easily conduct
electricity. In semiconductors Eg is small, but large enough so that a fairly
small number of electrons are in the conduction band due to thermal energy,
and these materials conduct poorly. In insulators Eg is large so that electrons
are not promoted to the conduction band due to thermal energy, and these
materials do not conduct electricity.

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Unite two:
Nano definitions and nomenclatures
1-Nano: Greek wards which means dwarf (small man).
2-Nano :In standard international units (SIU) is prefix denotes a
fraction of 10-9
a given unit like nanometer, nanogram, nanolitter
,…...etc,
3-Nanochemistry Confinement of chemical reactions on nanometer
length scale to produce chemical products that are of nanometer
dimensions or Preparation and organization of nanoparticles.
4-Nanoscience is the actual “science” or basic study of systems and
materials at the nanoscale. Nano Science can be defined as the study
of phenomena and manipulation of materials at Atomic, Molecular and
Macromolecular scales where properties differ significantly from those
at a larger scale.
NanoScience is the study and understanding of properties of Nano
Particles.
Prefix,abbreviation Means Power of 10
Giga, G
Mega, M
kilo, k
centi, c
milli, m
micro, µ
nano, n
1 billion
1 million
1 thousand
1/100
1/1,000
1/1,000,000
1/1,000,000,000
109
106
103
10-2
10-3
10-6
10-9

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5-Nanostructured Materials : any material that has a feature or
properties of interest in at least one dimension that is nanoscale (under
100 nm)
6-Nanotechnology is the application of Nanoscience to a broad set of
emerging manufacturing technologies, which control and manipulate
material at the level of atoms and molecules.or is the manipulation of
atoms and/or molecules to produce materials & devices
or Nanotechnology is the “integration of multiple disciplines,
technologies, materials, and processes to enable the creation, assembly,
measurement or manipulation of things at the nano and molecular level
or Nanotechnology is the application of Nanoscience to a broad set of
emerging manufacturing technologies, which control and manipulate
material at the level of atoms and molecules.
Nanotechnology is the manipulation of atoms and/or molecules to
produce materials & devices.
Nanotechnology can be also defined as:
1. Research and technology development at the atomic, molecular or
macromolecular levels, in the length scale of approximately 1 – 100
nanometer range.
2. Creating and using structures, devices and systems that have novel
properties and functions because of their small and/or intermediate
size.
3. Ability to control or manipulate on the atomic scale.
How nano is small ?
To understand how small one nm is let us see few comparisons
1. A Red blood cell is approximately 7000nm wide.
2. Water Molecule is almost 0.3nm across.
3. Human hair which is about 80,000nm wide.

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Human hair
What will happen to the surface area when going to nano scale?
what will happen to the energy levels due to the quantum effects?

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Size dependent properties
Why nanochemistry?
Two principal factors cause the properties of Nano Materials to differ
significantly from other materials.
1.Increased relative surface area.

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2.Quantum confinement effect.
these factors can charge or enhance properties such as reactivity , strength and
electrical characteristics.
Surface Area to Volume ratio
Nano Materials have a relatively larger Surface area when compared to the
same volume or mass of the material produced in a larger form.
Let us consider a Sphere of radius “r”.
Its Surface Area =4πr2.
Its volume= 4/3πr3
Surface Area to Volume Ratio= 3/r.
Thus when the radius of the Sphere decreases , its Surface to Volume ratio
increases.
- Let us consider one Cubic Volume its the Surface Area is 6m2
.
- When it is divided into eight pieces its Surface Area becomes 12m2,
similarly When the same volume is divided into 27 pieces its Surface Area
becomes 18m2.
- Thus we find that when the given volume is divided into smaller pieces
the Surface Area increases.
- Hence as particle size decreases a greater proportion of atoms are found
at the surface compared to those inside.
- Nano particles have a much greater surface area per given volume
compared with larger particles. It makes materials more Chemically
reactive
22
616 mmareasurface 1m

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Quantum Confinement
In Nano materials, the Electronic energy levels are not continuous as in the bulk
but are discrete (finite density of states), because of the confinement of the
electronic Wave function to the physical dimensions of the particles. This
phenomenon is called Quantum confinement.
Unique properties
 Quantum size effects result in unique mechanical, electronic, photonic,
and magnetic properties of nanoscale materials
 Chemical reactivity of nanoscale materials greatly different from more
macroscopic form, e.g., gold
m
2
1 22
128)
2
1
(6 mmareasurface 

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 Vastly increased surface area per unit mass, e.g., upwards of 1000 m2 per
gram
 New chemical forms of common chemical elements, e.g., fullerenes,
nanotubes of carbon, titanium oxide, zinc oxide, other layered
compounds
Between the dimensions on an atomic scale and the normal dimensions,
which characterize bulk material is a size range where condensed matter
exhibits some remarkable specific properties that may be significantly
different from the properties of bulk materials. Some such peculiar
properties are known, but there may be a lot more to be discovered. The
following are just a few examples:
1-melting point and other phase transition temperatures
;Nanomaterials may have a significantly lower melting point or phase
transition temperature and appreciably reduced lattice constants, due to a
huge fraction of surface atoms in the total amount of atoms.
2-colour and other optical properties of nanomaterials can be
significantly different from bulk crystals. For example, the optical absorption
peak of a semiconductor nanoparticle shifts to a short wavelength, due to an
increased band gap. The color of metallic nanoparticles may change with
their sizes due to surface plasmon resonance.
3-Electrical conductivity decreases with a reduced dimension due to
increased surface scattering. However, electrical conductivity of
nanomaterials could also be enhanced appreciably, due to the better
ordering in microstructure, e.g. in polymeric fibrils
4- Chemical properties: ionization potential and electron affinity
5-magnetic properties: when gold and platinum become magnetic
6- Mechanical properties of nanomaterials may reach the theoretical
strength, which are one or two orders of magnitude higher than that of
single crystals in the bulk form. The enhancement in mechanical strength is
simply due to the reduced probability of defects. :CNT’S are 100 times
stronger than steel .

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As an example: The differences between nanogold and bulk gold
Nanogold Bulk gold
1-its melting points depends 1-fixed melting point
size it decreases with decreasing 1150C
on size 400-1150 C
2-can be magnetized 2-Non magnetic
3-chemicaly active so it can used as 3-chemicaly inert
Catalyst
4-can take any colors depending on 4-it is well known yellow color
its sizes (yellow-red-blue-violet)
5-less conductivity 5-more electrically conductive
Other examples:
 Copper which is an opaque substance become transparent.
 Platinum which is an inert material become catalyst.
 Aluminum which is a stable material turns combustible.
 Silicon insulators become conductors.
Comparison: Microstructure vs. Nanostructure
Pink red maroon blue violet

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Microstructure Nanostructure
Physics Semi-classical Quantum mechanical
Electron nature Particle –like Wave-like
E or k-space Continuous Discrete
Current Continuous Quantized
Decision Deterministic Probabilistic
Fabrication Micro-fabrication Nano-fabrication
Surface area volume Small Very large
Packing Low Very high
The reasons for such differences (why nanochemistry?)
Some known properties of nanomaterials are related to different origins:
1-Quantum effect (spatial confinement ) that make the energy gabs more
affected by sizes of particles.
2-Surface area to volume ratio which became very far from bulk materials
and led to make the particles more active (large fraction of surface
atoms large surface energy and ).
3-Particles have more freedom .
4-The effect of electromagnetic waves are more than the Gravity forces.
How to estimate the surface area to volume ratio (S/V) and the specific
surface (S/W(g)):
Example; Calculate the S/V and the S/W of 1 cm3 of spherical nano ZnO
crystals with radius of 6nm, let the density 1.5g/cm3?
Number of particles (NOP) = total volume(v) / (v0)volume of single
particle (4/3 *𝛱*R3)
NOP= 1cm3 * 10 21 (nm/cm)3 / (4/3 * 3.14* (6)3)nm3
=11 * 1017
Total surface area(S) = NOP * surface area of single particle(4*𝛱*R2)
= 11 * 1017 * 4 * 3.14 * (6)2
= 5 * 1020 nm2
= 500 m2
S/V=500m2/cm3
S/W=S/(w=v/d)=500/1.5/1=333.34 m2/g

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Exercise: Calculate the S/V and the S/W of 1 cm3 of cubical nano ZnO
crystals with side length of 6nm, let the density 1.5g/cm3?
Unit three
Nanomaterials classification
There are different ways to describes and classifying nanomaterials ,the
most known such types are;
First-According to the dimensions:
any crystalline particle must take three dimensions (x,y,and z),this
method of classifying nanomaterials depends on how many non nano
dimentions (micro or macro scale)of the x,y,z are existed ;
1- The (0D) zero dimensions nanomaterials are those hav all three dimensions
are at nanoscale or there is no micro-dimension like quantum dots
(ZnO,PbS),nanogold,in another way these nanocrystals exhibit three quantum
confinement because this effect appears with the nanoscale only so 0D
nanocrystals have three quantum confinement.
1cm3 of cubical
particle
1cm3
of spherical
particle
1cm3
of spherical particles
of 6 nm in radius1cm3 of cubical particles
of 6 nm in side length

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2- The (1D) one dimensions nanomaterials are those have only one dimension
at micro scale like length,and the other remain dimensions such as carbon
nanotubesw, Ni wires, Fe nanorods,..etc,,are at nanoscale but the these
nanomaterials exhibit two quantum confinement;
3-The (2D) two dimensions; (have two micro dimensions) like nano films
(Ag,Au,…),while there is only one direction for the quantum confinement.
4-The (3D) three dimensions (all dimensions are micro-size ) like composite and
clusters (polymers with nanoparticles) polystyrene with nano MgO.
X
Y
Z
X
Y
Z
X
Y
Z

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summary
X
Y
Z

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2-According to the shape:
Nonmaterial’s can takes any shape like spherical, cubical, tubes, wires,
rods ,films ,so they can be named by their shapes;
1-Nanoparticles or nanospheres: like quantum dots (ZnO,PbS),nanogold
2-Nanotubes or nanowires or nanorods: like carbon nanotubesw,Ni wires
3-Nanoscale thin films or ultra-thin films: like nano films (Ag,Au,…)
4-Nanocomposites: a material comprised of many nanoscale inclusions
(such
as nanoparticles)

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3-According to the composition:
Another way can be noticed in some literatures for the nomenclature the
nanomaterialos according to the their elemental composition
1-Carbon Based Materials( hollow spheres, ellipsoids, or tubes. Spherical
and ellipsoidal , Carbon Nanotubes/Fullerenes).
2-Metal Based Materials (quantum dots, nanogold, nanosilver and metal
oxides, such as titanium dioxide).

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CeO2 nano Ag nano Al2O3 stainless steel
nano powder
3-Dendrimers (nanosized polymers built from branched units) like
polyimidomethyimethaacrylate (PMMA).
4- Nanocomposites are materials with a nanoscale structure that improve the
macroscopic properties of products. Typically, nanocomposites are clay,
polymer or carbon, or a combination of these materials with nanoparticle
building blocks. Composites (combine nanoparticles with other
nanoparticles or with larger, bulk-type materials, polystyrene with nano
MgO).

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5- Inorganic-Organic Hybrid Nanoparticles (Polyhedral Silsesquioxanes).
6-Nano-Intermediates like metal alkoxides (titanium isopropoxide),metal
organic compounds, as their uses in producing nanomaterials by sol-gel
process.

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Unit four
Preparation methodologies
There are two main different approaches to fabrication (preparation,
synthesis) ;
The first is; Top – Down approaches: Start with the bulk material and “cut
away material” to make what you want
1-Grinding/Milling
2-Nanolithography
Conventional Mask
Scanning E-Beam,I-Beam
Soft Nanoprinting
spherical

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3-Laser ablation
The second is; Bottom – Up approaches: Building what you want by
assembling it from building blocks ( such as atoms and molecules). Atom-by-
atom, molecule-by-molecule, or cluster-by-cluster
 Sol-gel process
 Single crystal growth
 Electrodeposition/electroplating
 Anodizing
 Molten salt electrolysis
 Hydrothermal
 Polyol
 Colloidal
 Water - oil microemulsions
1-Gaseous phase methods
 CVD chemical vapor deposition and MOCVD
 IGC inert gas condensation
 MBE molecular beam epitaxy and MOVPE
metal oxide vapor phase epitaxy
 ALD atomic layer deposition
 Flame pyrolysis (Combustion)
 Thermolysis
 Ion Implantation
2-liquid phase methods
 MSA molecular self-assembly
 Superamolecular chemistry
 CBD chemical bath deposition

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IGC inert gas condensation
CVD chemical vapor deposition
ALD atomic layer deposition
Flame pyrolysis
(Combustion)

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Ion Implantation
Sol-gel

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Sol-Gel-Processing formation of Me-O-Me bonds in solution .e. Si-O-Si
CBD chemical bath deposition
Colloidal synthesis
The synthesis of colloidal nanomaterials is based on a three-component
system composed of:
precursors, organic surfactants, and solvents
3-solid phase methods
4-biological methods

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Unite five
Chemical Vapor Deposition Techniques (CVD)
Deposition can also take place due to a chemical reaction between some reactants
on the substrate. In this case reactant gases (precursors) are pumped in to a
reaction chamber (reactor). Under the right conditions (T, P), they undergo a
reaction at the substrate. One of the products of the reaction gets deposited on the
substrate. The by-products are pumped out.
The key parameters are chemical (reaction rates, gas transport, diffusion).
Advantages:
1- high growth rates possible
2- can deposit materials which are hard to evaporate
3- Good reproducibility
4- can grow epitaxial films
Disadvantages
1- high temperatures
2- complex processes
3- Toxic and corrosive gasses

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CVD Reaction Types
1- Pyrolysis chemical decomposition or change induced by heat
2- Reduction Any process in which electrons are added to an atom or ion
(as by removing oxygen or adding hydrogen); always occurs
accompanied by oxidation of the reducing agent
3- Oxidation;Is any electrochemical process which involves the formal
oxidation state of an atom or atoms (within a molecule) being increased
by the removal of electrons. E.g. iron(II) can be oxidized to iron(III):
4- Compound formation
4- Disproportionation chemical reaction in which a single substance acts as
both oxidizing and reducing agent, resulting in the production of
dissimilar substances

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6- Reversible transfer
CVD Reactor Types
A- According to the Chamber pressure:
1 - atmospheric-pressure (APCVD);
mass-transport limited region,
fast deposition,
poor step coverage
2- low-pressure (LPCVD)
surface reaction rate limited
excellent purity, uniformity and step coverage
low deposition rates
requires vacuum system
B-according to the Reactor heating type:
1- Hot-wall
Particle contamination (Peel off)
requires periodic cleanup
2 - Cold-wall
no reaction on the wall
difficult to control the real T
C-Plasma-Enhanced CVD
D-FIB-Enhanced CVD

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Unite six
Sol-gel technique
Sol-gel can be defined as the formation of an oxide network through
polycondensation reactions of a molecular precursor in a liquid; The sol-gel
method was developed in the 1960s mainly due to the need of new synthesis
methods in the nuclear industry. A method was needed where dust was
reduced (compared to the ceramic method) and which needed a lower
sintering temperature. In addition, it should be possible to do the synthesis
by remote control. The main benefits of sol–gel processing are the high
purity and uniform nanostructure achievable at low temperatures. And
many other advantages can be achieved such as;
- to “dissolve” the compound in a liquid in order to bring it back as a solid
in a controlled manner.
- Multi component compounds may be prepared with a controlled
stoichiometry by mixing sols of different compounds.
- The sol-gel method prevents the problems with co-precipitation, which
may be inhomogeneous, be a gelation reaction.
- Enables mixing at an atomic level.
- Results in small particles, which are easily sinterable.
- enable production of low temperature phases.
A sol is a stable dispersion of colloidal particles or polymers in a solvent.
The particles may be amorphous or crystalline. An aerosol is particles in a
gas
phase, while a sol is particles in a liquid,
A gel consists of a three dimensional continuous network, which encloses a
liquid phase, In a colloidal gel, the network is built from agglomeration of
colloidal particles
The Colloidal (particulate) gels = agglomeration of dense colloidal particles
Any sol-gel procedure may include the following steps:
1- Hydrolysis of molecules. Formation of a sol.
2- Condensation or sol-gel transformation
For example ; The starting point for formation of a silica gel may be
alkoxides or silanols. These are reacted to siloxane group.

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The condensation process is dynamic, and may be steered in the desired
direction by adjusting the proper parameters.
Parameters which influences the condensation process:
a- Type of precursor
The stability and reactivity of the silicon alkoxides are influenced by a steric
factor. Bulky ligands slow down the hydrolysis:
Reactivity: Si(OMe)4 > Si(OEt)4 > Si(OnPr)4 > Si(OiPr)4
b- The ratio between alkoxide and water (RW); The water ratio, RW.
(OR/H2O)
Si(OR)4 + 2H2O → SiO2 + 4ROH
The reaction states that a water ratio of RW = 2 (OR/H2O) is needed to
convert everything to SiO2. A water ratio of RW=1 leads to complete
hydrolysis but no condensation.
Increasing the water content (i.e. lower RW) will reduce condensation
Reducing the water content increases the condensation
c- Type of catalyst used
The electron density on Si will influence the reaction rate.
Si-R > Si-OR > Si-OH > Si-O-Si
Acid catalyzed reaction demands high electron density
Base catalyzed reaction demands low electron density
This results in:
Acid catalyzed: more straight chains
Base catalyzed: more branched network

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d- Type of solvent and ratio; the polarity, dipolar moment, viscosity,
protolytic/non protolytic properties are important for the reactions taking
place.
Polar solvents stabilize polar gels by hydrogen bonding.
Non-polar solvents are better for systems which are not completely
hydrolyzed.
e- Temperature
f- pH
g- Relative and absolute concentrations of the reactants.
3- Gelation
During reaction, objects will grow. However, a gel may not form As the sol
aggregates the viscosity will increase until a gel is formed. The sol-gel
transition (gel-point) is reached when a continuous network is formed.
The gel-time is determined as the time when it is possible to turn the
container upside-down. All fluid is kept in the gel, and the volume is
maintained.
4- Ageing; structure modifications with time depending on temperature,
solvent and pH conditions When the gel is formed, a large number of sol
particles and clusters will still not have reacted. Ageing of the gel is
therefore a very important stage in the process. The gel point is not a
thermodynamic event
As the viscosity rapidly increase, the solvent is “trapped” inside the
gel.The structure may change considerably with time, depending on pH,
temperature and solvent. The gel is still “alive”. The liquid phase still
contains sol particles and agglomerates, which will continue to react,
and will condense as the gel dries.The gel is originally flexible. Groups
on neighbouring branches will condense, making the gel even more
viscous. This will squeeze out the liquid from the interior of the gel, end
shrinkage occur. This process will continue as long as there is flexibility
in the gel.
5- Drying
Removing of the solvent phase Method influenced by the intended use
of the dried material : When the liquid is removed from the gel several
things may happen. When the liquid in the gel is replaced by air, major
changes to the network structure may occur.
If the structure is maintained, an aerogel is formed If the structure
collapses, a xerogel is formed. Normal drying of the gel leads to

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structural collapse due capillary forces drawing the walls of the pores
together, and reducing the pore size.Cracking may occur when the
tension in the gel is so large that it cannot shrink anymore.Gas will enter
the pores with a thin film of liquid on the walls. This will evaporate and
only isolated spaces with liquid are left.
6- Densification
heating to convert the dried gel to a dense ceramic. For silica gels, the
following reactions occur :
- desorption of physically adsorbed solvent and water from the walls of
micropores (100-200°C)
- decomposition of residual organic groups into CO2 (300- 500°C)
- collapse of small pores (400-500°C)
- collapse of larger pores (700-900°C)
- continued polycondensation (100-700°C)
Sol-gel synthesis may be used to prepare materials with a variety of shapes,
such as porous structures, thin fibers, dense powders and thin films.

36
If the gel is dried by evaporation, then the capillary forces will result in
shrinkage, the gel network will collapse, and a xerogel is formed.
If drying is performed under supercritical conditions, the network structure
may be retained and a gel with large pores may be formed. This is called an
aerogel, and the density will be very low (< 0.005 g/cm3).
Metals may be used for formation of gels, almost as silicon. However, many
metals will form oxides when increasing pH. The water molecules of the
hydrated metal ions are more acidic than for Si, and hydrolyses will occur.
The reactions are moved toward lower pH.
pH < 3 pH > 3 pH >> 3
[Al(H2O)6]3+ [Al(OH)x(H2O)6-x](3-x)+ Al-O-Al
Types of precursors;
1- Metal (Si, Ti, Zr, Al, B…) alkoxides precursors: the metal-organic route
with metal alkoxides in organic solvent are largely used. The reactions
are all similar to the ones above reported for silicon alkoxides. The
mechanism are also similar to the ones described, in the following, for the
silicon alkoxides, based on nucleophilic attack to the central atom.
2- Inorganic salts; also, very often used the inorganic route with metal salts
in aqueous solution (chloride, oxychloride, nitrate..) : much cheaper and
easier to handle than metal alkoxides, but their reactions are more
difficult to control,salts in water give, in fact, solvated cations. The charge
transfer from the bonding orbitals of water molecules to empty d orbitals
of transition metal makes the water molecule more acidic.
General mechanisms in the metal-organic route
Based on the growth of metal oxo polymers in a solvent " inorganic step
polymerization reactions through hydrolysis and condensation of metal
alkoxides M(OR)Z, where M = Si, Ti, Zr, Al, Sn, Ce., OR is an alkoxy group
and Z is the valence or the oxidation state of the metal
first step : hydroxylation upon the hydrolysis of alkoxy groups :

37
M-OR + H2O M-OH + ROH
second step : polycondensation process leading to the formation of
branched oligomers and polymers with a metal oxo based skeleton and
reactive residual hydroxo and alkoxy groups ; 2 competitive mechanisms :
1-Olation: Hydroxy bridges are formed by nucleophilic substitution, where
an OH group attacks and water leaves. It is important that water is not
coordinated too hard to the metal in order for this reaction to occur. The
smaller the charge and the larger the metal ion, the larger the olation rate.
Oxolation is a condensation reaction where an oxo-bridge is formed.
If the metal is under.coordinated, the oxolation happens by fast nucleophilic
addition reactions:A network may be formed via two routes:

38
Applications and limitations of sol-gel techniques
Advantages
1- Sol-gel processes allow the synthesis of ceramics of high purity,
because organometallic alkoxy precursors can be purified by
distillation or recrystallisation
2- high degree of homogeneity, because reagents are mixed at the
molecular level
3- low or high porosity, by using appropriate heat treatment and
firing times
4- the ability to prepare glasses of materials which cannot be
obtained as amorphous solids by cooling from the liquid state
5- the capability of obtaining fully-dense amorphous solids at
temperatures lower by hundreds of centigrade degrees than those
required for conventional compaction/densification or for melting
6- the ability to obtain materials with novel distributions of phases
contained therein...
Disadvantigase (drawbacks);
1- high cost for the majority of alkoxide precursors
2- long processing times
3- volatiles production
4- shrinkage
5- development of stresses leading to fragmentation
Applications;
A-novel glasses produced from gel precursors,The physical properties
of gel-derived glasses are usually closely similar to those of glasses obtained
from the melt. The most attractive feature is the development of novel glass
compositions : CaO-SiO2 or Na2O-ZrO2-SiO2 with high ZrO2
content, which simply cannot be obtained from the melt because the cooling
rate must be very high to avoid detectable crystallization.
B-fibers : using appropriate hydrolysis conditions,continuous fibers may
be drawn from solutions of metal alkoxides and converted to glass fibers by

39
heating (ex : ZrO2-SiO2 or Na2O-ZrO2-SiO2). Fibers can also be prepared by
extruding gelled solutions (colloidal as well as polymeric gels)
through dies of appropriate diameter (ex : polycrystalline alumina,
microcrystalline Al2O3-Cr2O3-SiO2, mullite 3Al2O3& 2SiO2, aluminum
borosilicate 3Al2O3&B2O3&3SiO2)
C-abrasives : after gelation and drying, the material is crushed (a simple
process with frangible dried gel) and sized. The sized powders are then
fired. In this way, Al2O3 abrasive 1 – 18 particles with uniformly dispersed
ZrO2 particles and a very fine grain size (< 300 nm) can be obtained. Such
abrasive particles have superior grinding performance compared with fused
or sintered Al2O3-based abrasives in a number of applications
D-thin films and coating : the permissible drying rates, consistent with the
avoidance of fracture, were evaluated and found to vary inversely with the
thickness of the body being dried. This limitation leads naturally to the main
use of gels in coating applications, where the thickness are small and the
drying rates can be correspondingly high. Some of the coating-type
applications which seem wellsuited
for sol-gel techniques include :
1- antireflection coatings (single layer or multilayer films)
2- absorbing coatings
3- filters for lighting and optical purposes
4- semiconducting coatings
5- protective layers (both chemical and thermal)
6- independent films, prepared by; - " pouring alkoxide solutions onto
liquids which do not mix with the solution and allowing the film to
hydrolyze ,- pouring the solution onto non-wetting surfaces such as
Teflon - forming films using wire rings with solutions of appropriate
viscosity

40

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Unite seven
Nanostructure Identification
As the nanomaterials are not new as for centuries, the preparing & using
nanoparticles during that period were lacking of the powerful instrument
which measure size of particles & correlation of properties. Recently new
techniques are evolved for characterization and analysis of nanomaterials
which gives a revolution to development of nanochemistry and
Nanotechnology. some of these techniques used for analysis &
characterization of nanomaterials include;
1- Diffraction Techniques (XRD); Diffraction techniques are often used in
average particle size analysis as well as structural determination. Some of
the diffraction techniques are;
 X-ray Diffraction (XRD),
 electron diffraction
 small angle X-ray Scattering (SAXS),and
 small angle Neutron scattering (SANS).
2- Electron Microscopy
A- Scanning Electron Microscope(SEM)
B- Transmission Electron Microscope(TEM)
3- Scanning Probe Microscope(SPM)
A- Atomic Force Microscope(AFM)
B- Scanning Tunneling Microscope(STM)
Characteristic Information
 Crystallographic Information(XRD,SEM,AFM)
How the atoms are arranged in the object.
 Topography (SEM,AFM)
The surface features of an object or "how it looks", its texture.
 Morphology(SEM,TEM,AFM)
The shape and size of the particles making up the object.

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 Composition(XRD,XRF,AAS)
The elements and compounds that the object is composed of and the
relative amounts of them;
1- X-ray Diffraction (XRD)
X-rays are electromagnetic waves with a wavelength in the range of
interatomic distances (0.1-100 Å).
This match of length scales makes them suitable for the study of crystalline
materials. For single-phase materials the crystal structure can be obtained
directly using X-Ray diffraction (XRD). With the help of a database of known
structures XRD can be used for phase identification. Also crystal size, strain
and preferred orientation of polycrystalline materials can be measured. The
related technique of X-ray reflection enables accurate determination of film
thickness.
the uses and applications are;
1- phase identification
2- texture or preferential orientation
3- crystallite size and residual stress
4- in-situ temperature and pressure studies
5- high resolution diffraction
6- layer thickness measurements
Principles
When X-ray radiation is directed on a sample, the X-rays are scattered
(“diffracted”) by electrons present in the material. If the atoms in the

43
material are arranged in a regular structure, i.e. if the material is crystalline,
this scattering results in maxima and minima in the diffracted intensity. The
signal maxima follow Bragg’s law
nλ = 2d sinΘ
example; λ = 1.54 Ǻ,,2Ө=38
d= 1.54 Ǻ / ( 2 * Sin ( 38 / 2 ) ) = 2.35 Ǻ
Here n is an integer, λ is the X-ray wavelength, d is the distance between
crystal lattice planes and Θ is the diffraction angle.
When the intensity of detected X-rays is plotted as a function of angle Θ an
X-ray diffraction pattern is obtained, which is characteristic for the sample
material thin layers of only a few nanometers can be investigated.
Phase identification can be done by matching the XRD pattern with reference
patterns of pure substances.
The width of a diffraction peak is influenced by the crystallite size: a large
crystallite size causes sharp reflections, whereas a small size leads to broad
reflections. The effect crystal size can have on an XRD pattern is shown in
the figure below.

44
The working steps of XRD are shown in the following diagram;
Calculation of crystalline size (thickness) by Scherrer equation;
t = thickness of crystallite
K = constant dependent on crystallite shape (0.89)
l = x-ray wavelength
B = FWHM (full width at half max) or integral breadth
ӨB = Bragg angle
Note;20%-30% accuracy at best.
Example; λ = 1.54 Ǻ,2Ө=98.25,B=0.1°
B = (0.1°)*π/180 = 0.00174
t = 0.89*λ / (B Cos θB)= 0.89*1.54 Ǻ / ( 0.00174 * Cos (98.25/ 2 ) )
= 1200 Ǻ
BB
K
t


cos



45
2- Electron Microscope (SEM & TEM)
- Electron microscopes are scientific instruments that use a
beam of energetic electrons to examine objects on a very fine
scale.
- Electron microscopes were developed due to the
limitations of Light Microscopes which are limited by the
physics of light.
- In the early 1930's this theoretical limit had been reached and
there was a scientific desire to see the fine details of the
interior structures of organic cells (nucleus,
mitochondria...etc.).
- This required 10,000x plus magnification which was not possible
using current optical microscopes.
Comparison of OM,TEM and SEM

46
The transmission electron microscope (TEM) was the first type of Electron
Microscope to be developed and is patterned exactly on the light
transmission microscope except that a focused beam of electrons is used
instead of light to "see through" the specimen
The SEM has a large depth of field, which allows a large amount of
the sample to be in focus at one time and produces an image that
is a good representation of the three-dimensional sample.
The combination of higher magnification, larger depth of field,
greaterresolution,compositional and crystallographic information
makes the SEM one of the most heavily used instruments in
academic/national lab research areas and industry.

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Electron Microscope Components;
1. Electron optical column consists of:
– electron source to produce electrons
– magnetic lenses to de-magnify the beam
– magnetic coils to control and modify the beam
– apertures to define the beam, prevent electron spray,etc.
2. Vacuum systems consists of:
–sample chamber which “holds” vacuum, pumps to produce vacuum
– valves to control vacuum, gauges to monitor vacuum
3. Signal Detection & Display consists of:
– detectors which collect the signal
– electronics which produce an image from the signal
4- Infrastructure Requirements: Power Supply, Cooling system,Vibration-
free floor,Room free of ambient magnetic and electric fields

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3- Scanning Probe Microscopy (SPM)
Scanning probe microscopy covers several related technologies for imaging
and measuring surfaces on a fine scale, down to the level of molecules and
groups of atoms. At the other end of the scale, a scan may cover a distance of
several micrometers in the x and y directions few micrometers in the z
direction. SPM technologies share the concept of ;
1- scanning an extremely sharp tip (3-50 nm radius of curvature) across
the object surface.
2- The tip is mounted on a flexible cantilever, allowing the tip to follow
the surface profile .
3- When the tip moves in proximity to the investigated object, forces of
interaction between the tip and the surface influence the movement of
the cantilever.
4- These movements are detected by selective sensors. Various
interactions can be studied depending on the mechanics of the probe.
The two most common scanning probe techniques are:
First; Atomic Force Microscopy (AFM) measures the interaction force
between the tip and surface. The tip may be dragged across the surface, or
may vibrate as it moves. The interaction force will depend on the nature of
the sample, the probe tip and the distance between them.
Second;Scanning Tunneling Microscopy (STM) measures a weak
electrical current flowing between tip and sample as they are held a very
distance apart
Atomic Force Microscopy
The Atomic Force Microscope was developed to overcome a basic drawback
with STM - that it can only image conducting or semiconducting surfaces.
The AFM, however, has the advantage of imaging almost any type of surface,
including polymers, ceramics, composites, glass, and biological samples.
Most AFMs use a laser beam deflection system, where a laser is reflected
from the back of the reflective AFM lever and onto a position-sensitive
detector. AFM tips and cantilevers are microfabricated from Si or Si3N4.
Typical tip radius is from a few to 10s of nm.

49
Beam deflection system, using a laser and photodector to measure the
beam position.
Because the atomic force microscope relies on the forces between the tip
and sample, knowing these forces is important for proper imaging. The force
is not measured directly, but calculated by measuring the deflection of the
lever, and knowing the stiffness of the cantilever. Hook’s law gives
F = -kz,
where F is the force, k is the stiffness of the lever, and z is the distance the
lever is bent.
Operation Modes of AFM
1-Contact Mode; contact mode is widely used for small, high-speed atomic
resolution scans and is known as variable-deflection mode. As the tip is
raster-scanned across the surface, it is deflected as it moves over the surface
corrugation. In constant force mode, the tip is constantly adjusted to
maintain a constant deflection, and therefore constant height above the

50
surface because the tip is in hard contact with the surface, the stiffness of the
lever needs to be less that the effective spring constant holding atoms
together, which is on the order of 1 - 10 nN/nm. Most contact mode levers
have a spring constant of < 1N/m.
2-Noncontact mode“tapping mode”; Noncontact use of an oscillating
cantilever. A stiff cantilever is oscillated in the attractive regime, meaning
that the tip is quite close to the sample, but not touching it (hence,
“noncontact”). The forces between the tip and sample are quite low, on the
order of pN (10 -12 N). The detection scheme is based on measuring changes
to the resonant frequency or amplitude of the cantilever.
Part of the oscillation extends into the repulsive regime, so the tip
intermittently touches or “taps” the surface. Very stiff cantilevers are
typically used, as tips can get “stuck” in the water contamination layer.The
advantage of tapping the surface is improved lateral resolution on soft
samples. Lateral forces such as drag, common in contact mode, are virtually
eliminated. For poorly adsorbed specimens on a substrate surface the
advantage is clearly seen.

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Scanning-Tunneling Microscope
STM provides atomic-scale resolution of surfaces and is also being
developed to move atoms on surfaces. STM relies on a purely quantum-
mechanical phenomenon: tunneling. The main components are drawn in ;
A limitation of the STM is the requirement for a conducting sample. The STM
relies on the fact that electrons near surfaces have wave functions which
decay into the vacuum outside the surface boundary the microscope consists
on a conducting tip(W or Pt-Ir) connected to a current-measuring circuit.
When the tip is in close proximity to the surface (=1 nm), the decaying wave
function from the surface could overlap with the tip, i.e., the surface electron
has a finite probability of being in the tip. Since the latter is conducting, the
electron under a voltage _eld (1-10 V) can then move creating a current. This
current is known as a tunneling current whose magnitude (as for all
tunneling currents) is very sensitive to the surface{tip separation.
The STM has also been used to carry out chemical reactions on surfaces. This
relies on a tip{sample interaction. The force can be either attractive or
repulsive.

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Unite Eight
Important Historical Events in Nanoscience
Early examples
Early examples of nanostructured materials were based on craftsmen’s empirical
understanding and manipulation of materials. Use of high heat was one common
step in their processes to produce these materials with novel properties.
4th Century:
The Lycurgus Cup (Rome) is an example of dichroic glass; colloidal gold and
silver in the glass allow it to look opaque green when lit from outside but
translucent red when light shines through the inside.
9th-17th Centuries:
Glowing, glittering “luster” ceramic glazes used in the Islamic world, and
later in Europe, contained silver or copper or other metallic nanoparticles.
6th-15th Centuries:
Polychrome
lustreware bowl,
9th C, Iraq,
British Museum

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Vibrant stained glass windows in European cathedrals owed their rich colors to
nanoparticles of gold chloride and other metal oxides and chlorides; gold
nanoparticles also acted as photocatalytic air purifiers.
13th-18th Centurties:
“Damascus” saber blades contained carbon nanotubes and cementite
nanowires—an ultrahigh-carbon steel formulation that gave them strength,
resilience, the ability to hold a keen edge, and a visible moiré pattern in the steel
that give the blades their name.
(Left) A Damascus saber (photo by Tina Fineberg for The New York Times).
(Right) High-resolution transmission electron microscopy image of carbon
nanotubes in a genuine Damascus sabre after dissolution in hydrochloric acid,
showing remnants of cementite nanowires encapsulated by carbon nanotubes
(scale bar, 5 nm)
1857
The South
rose window
of Notre
Dame
Cathedral,
ca 1250

54
Michael Faraday discovers colloid gold
This suspension of gold nanoparticles in solution was totally transparent in some
lighting, but in other lighting conditions could produce differently coloured
solutions of ‘ruby, green, violet or blue.
1905
Albert Einstein explains the existence of colloids
This theory was confirmed by the experiments of Jean-Baptiste Perrin, which
contributed toward Perrin’s 1926 Nobel prize.
1931
Max knoll &Ernst Ruska: invented Electron microscope
1932

55
Langmuir discovers layers of atoms one molecule thick
Langmuir established the existence of monolayers (layers of atoms or molecules
one atom thick). These monolayers have peculiar two-dimensional qualities, and
led to the development of a totally transparent glass produced by forming a thin
film of fluorine compound on the surface. He was awarded the Nobel prize in
1932 for this work on thin films.
1956
Arthur von Hippel at MIT introduced many concepts of—and coined the
term—“molecular engineering” as applied to dielectrics, ferroelectrics, and
piezoelectrics
1958
Jack Kilby of Texas Instruments originated the concept of, designed, and
built the first integrated circuit, for which he received the Nobel Prize in
2000.
1959
Feynman suggests that there is ‘plenty of room’ to work at the nanoscale
Richard P. Feynman gave a ground-breaking speech ‘There’s plenty of room at
the bottom’ where he discussed the possibility of controlling materials at the level
of atoms and molecules – this was the first vision of the possibilities of science
and technology at the nanoscale. He became a Nobel laureate in 1965.

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1965
Intel co-founder Gordon Moore described in Electronics magazine several
trends he foresaw in the field of electronics. One trend now known as “Moore’s
Law,” described the density of transistors on an integrated chip (IC) doubling
every 12 months (later amended to every 2 years). Moore also saw chip sizes and
costs shrinking with their growing functionality—with a transformational effect
on the ways people live and work. That the basic trend Moore envisioned has
continued for 50 years is to a large extent due to the semiconductor industry’s
increasing reliance on nanotechnology as ICs and transistors have approached
atomic dimensions.
Moore’s Laws:
Gordon Moore, one of the founders of the Intel corporation, came up with two
empirical laws to describe the amazing advances in integrated circuit
electronics.
Moore’s first law says that the amount of space required to install a transistor on
a chip shrinks by roughly half every 18 months.
Moore’s second law. the cost of building a chip manufacturing plant doubles
with every other chip generation, or roughly every 36 months.

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1974
Norio Taniguchi (University of Tokyo )The word ‘nanotechnology’ first used
The term ‘nanotechnology’ was coined in 1974 .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 nm (nanometre).
1981
IBM invent a machine which can move single atoms around
Gerd Binning and Heinrich Rohrer invented the Scanning Tunneling Microscope
(STM) at IBM. They were awarded the Nobel prize in 1986 for this work.at the
Zurich Research Lab in 1981
1985

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A new form of carbon is discovered: C60
Richard Smalley, Robert Curl and Harold Kroto discovered C60 for which they
were awarded the Nobel Prize in 1996. C60 is more commonly known as a
buckyball as the 60 carbon atoms are arranged into a sphere made of 12
pentagons and 20 hexagons (exactly like a football).
Robert F. Curl Jr Sir Harold W. Kroto Richard E. Smalley
1986
K.Eric Drexler: writing with a STM tool.
1990
IBM demonstrate ability to control the position of atoms IBM logo in atoms
IBM research scientist Don Eigler showed that the position of atoms could be
controlled precisely. Using the STM he maneuvered 35 xenon atoms on a nickel

59
surface so that they spelled out ‘IBM’. This was achieved at high vacuum and in
the supercooled temperature of liquid helium.
1991
Carbon nanotubes discovered
Sumino Iijima discovered a process to make ‘graphitic carbon needles ranging
from 4nm to 30nm in diameter and 1 micron in length.
1992
C.T. Kresge and colleagues at Mobil Oil discovered the nanostructured
catalytic materials MCM-41 and MCM-48, now used heavily in refining crude
oil as well as for drug delivery, water treatment, and other varied applications.
1993
Professor Richard E. Smalley envisioned the first nanotechnology center in
the world.
1993
First high-quality quantum dots prepared
Murray, Norris and Bawendi synthesise the first high quality quantum dots of
nearly monodisperse CdS CdSe and CdTe quantum dots are very small particles
with interesting optical properties.
1997
Lucent Technologies fabricated the ‘nanotransistor’
It was only 60nm wide and 1.2nm thick

60
1999–early 2000’s:
Consumer products making use of nanotechnology began appearing in the
marketplace, including lightweight nanotechnology-enabled automobile bumpers
that resist denting and scratching, golf balls that fly straighter, tennis rackets that
are stiffer (therefore, the ball rebounds faster), baseball bats with better flex and
"kick," nano-silver antibacterial socks, clear sunscreens, wrinkle- and stain-
resistant clothing, deep-penetrating therapeutic cosmetics, scratch-resistant glass
coatings, faster-recharging batteries for cordless electric tools, and improved
displays for televisions, cell phones, and digital cameras.
2000
Lucent Technologies with Oxford University created the first DNA motor
2000
Eigler et all: Construction of quantum mirrors

61
2001
Prototype fuel cell made using nanotubes
Nanohorns, irregularly shaped nanotubes, were developed as fuel cell for
hydrogen-based fuel such as methanol. They group together creating a high
surface area ideal for catalysts. NEC corporation announced that the latest
generation weigh under 2 pounds, when fully fuelled, and power a laptop for 5
hours before needing refuelling.
2001
Florian Bambers: Soldering of nanotube with e-beam.
2002
Stain-repellent trousers reach the high street
Clothing embedded with nanoparticles that produce a stain-repellent coating has
been developed. Nano-care™ khakis have the fabric fibres coated with
nanowhiskers 10–100nm in length. This new stain-repellent fabric is available
from a number of high street retailers and is available in trousers, shirts and ties.

62
2003
Prototype nano-solar cells produced
Prototype solar cells have been made by Nanosolar Inc. in California. They use
conducting polymers and nano-based particles. These cells are also produced in
flexible sheets, making them suitable for many applications.
2004
Intel launches the Pentium iv ‘PRESCOFT’ processor based on 90 nm
technology.
2005
Erik Winfree and Paul Rothemund from the California Institute of Technology
developed theories for DNA-based computation and “algorithmic self-
assembly” in which computations are embedded in the process of nanocrystal
growth.
2006:
James Tour and colleagues at Rice University built a nanoscale car made of
oligo(phenylene ethynylene) with alkynyl axles and four spherical C60 fullerene
(buckyball) wheels. In response to increases in temperature, the nanocar moved
about on a gold surface as a result of the buckyball wheels turning, as in a
conventional car. At temperatures above 300°C it moved around too fast for the
chemists to keep track of it.
2007:
Angela Belcher and colleagues at MIT built a lithium-ion battery with a
common type of virus that is nonharmful to humans, using a low-cost and
environmentally benign process. The batteries have the same energy capacity and
power performance as state-of-the-art rechargeable batteries being considered to

63
power plug-in hybrid cars, and they could also be used to power personal
electronic devices. (Image at right.)
2009–2010:
Nadrian Seeman and colleagues at New York University created several DNA-
like robotic nanoscale assembly devices. One is a process for creating 3D DNA
structures using synthetic sequences of DNA crystals that can be programmed to
self-assemble using “sticky ends” and placement in a set order and
orientation. Nanoelectronics could benefit: the flexibility and density that 3D
nanoscale components allow could enable assembly of parts that are smaller,
more complex, and more closely spaced. Another Seeman creation (with
colleagues at China’s Nanjing University) is a “DNA assembly line.” For this
work, Seeman shared the Kavli Prize in Nanoscience in 2010.
2010
IBM used a silicon tip measuring only a few nanometers at its apex (similar to
the tips used in atomic force microscopes) to chisel away material from a
substrate to create a complete nanoscale 3D relief map of the world one-one-
thousandth the size of a grain of salt—in 2 minutes and 23 seconds. This activity
demonstrated a powerful patterning methodology for generating nanoscale
patterns and structures as small as 15 nanometers at greatly reduced cost and
complexity, opening up new prospects for fields such as electronics,
optoelectronics, and medicine. (Image below.)
2013
Stanford researchers develop the first carbon nanotube computer.

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Unite nine
Application of nanomaterials
A basic understanding of physics and chemistry, and some knowledge of
materials science, is necessary to understand the properties and behavior of
nanomaterials, the unique properties of nanomaterials encourage belief that
they can be applied in a wide range of fields,
The main such properties include;
1- Large surface area to volume
2- Electrical conductivity
3- Chemical properties
4- Thermal properties
5- Wetting properties
6- Magnetic properties
7- Mechanical properties
8- Optical properties
9- Biological properties

65

66
Examples of the established applications of nanomaterials; ,
- microelectronics,
- synthetic rubber,
- catalytic compounds,
- photographic supplies,
- inks and pigments,
- coatings and adhesives,
- ultrafine polishing compounds,
- UV absorbers for sun screens,
- synthetic bone,
- ferrofluids,
- optical fiber cladding, and cosmetics.
- fabrics and their treatments,
- sports equipment,
- flat panel displays,
- drug delivery systems, and
- pharmaceutics.
- filtration,
- dental materials,
- surface disinfectants,
- diesel and fuel additives,
- hazardous chemical
neutralizers,
- automotive components,
- electronics,
- scientific instruments

67
An materials with nano special properties may introduces in many application as
example the Nanofluids are a relatively new class of fluids which consist of a
base fluid with nano-sized particles (1–100 nm) suspended within
Applications of nanofluids
1-Transportation (Engine cooling/vehicle thermal management)
2-Electronics cooling
3-Defens & Space
4-Nuclear systems cooling
5-Heat exchanger
6-Biomedicine
7-Other applications (heat pipes, fuel cell, Solar water heating, chillers, domestic
refrigerator, Diesel combustion, Drilling, Lubrications, Thermal storage,…)
In more details and according to the types of application the following points
can be described;
1-Electronics
Microelectronics.
Many of the current microelectronics applications are already at a nanoscale
During the last four decades, the smallest feature of a transistor shrunk from
10 µm down to 30 nm. The ultimate objective of microelectronics fabrication
is to make electronic circuit elements that are nanoscopic. For example, by
achieving a significant reduction in the size of circuit elements, the
microprocessors (or better said, nanoprocessors) that contain these
components could run faster and incorporate more logic gates, thereby
enabling computations at far higher speeds.

68
CNTs are exciting alternatives to conventional doped semiconductor crystals
due to their varied electronic properties, ranging from metallic, to
semiconducting, to superconducting.
Displays.
The resolution of a television or a monitor improves with reduction of pixel
size. The use of nanocrystalline materials can greatly enhance resolution and
may significantly reduce cost.
Also, flat-panel displays constructed with nanomaterials may possess much
higher brightness and contrast than conventional displays owing to the
enhanced electrical and optical properties of the new materials. CNTs are
being investigated for low voltage field-emission displays. Their combination
of mechanical and electrical properties makes them potentially very
attractive for long life emitters.
Thin carbon NTs have ideal geometry for electron emission due to their
smallest atomistic tip radius that result in turn to a high electric field
strength, in order of magnitude greater than a work function of electrons.
Moreover CNTs are known to exhibit; the high strength, melting
temperature, resistance to aggressive media as graphite, and are able to
work in technical vacuum. Cold emitter on base of CNTs was proposed to be
a key element for the future flat panel TV set as being the alternative for hot
emitters on base of electron-beam tube, that make possible to avoid high
dangerous asseverated 20–30 kV voltages. At ambient temperature the
CNT are able to emit electrons and current of the same density as the
standard tungsten cathode operating at high temperatures and voltages. Set-
up of light panel display on base of CNTs clamped at cathode and oriented in
the anode direction

69
Data storage.
Devices, such as computer hard-disks function based on their ability to
magnetize a small area of a spinning disk to record information, are
established nano-applications. Discs and tapes containing engineered
nanomaterials can store large amounts of information. Future avenues
for magnetic recording that will drastically increase the capability of data
storage include spintronics and nanowires.
High energy density batteries.
New nanomaterials show promising properties as anode and cathode
materials in lithium-ion batteries, having higher capacity and better cycle life
than their larger-particle equivalents . Among them are: aerogel
intercalation electrode materials, nanocrystalline alloys, nanosized
composite materials, carbon nanotubes, and nanosized transitionmetal
oxides.
High-sensitivity sensors.
Due to their high surface area and increased reactivity, nanomaterials
could be employed as sensors for detecting various parameters, such as
electrical resistivity, chemical activity, magnetic permeability, thermal
conductivity, and capacitance.
2-Transportation and telecommunication
Car tires.
Nanoparticles of carbon black ranging between 10 nm - 500 nm act as a filler
in the polymer matrix of tires, and are used for mechanical reinforcement.
Car bumpers.
Clay particle based composites containing plastics and nano-sized clay are
used to make car exteriors that are lighter and twice as resistant to scratches
than usual materials .
3-Imaging
Scanning microscope imaging.
SWCNTs have been used as probe tips for atomic-force microscopy imaging
of antibodies, DNA, etc. Nanotubes are ideal probe tips for scanning
microscopy due to their small diameter (which maximizes resolution), high
aspect ratio, and stiffness.

70
Molecular-recognition AFM tips.
SWCNTs with attached biomolecules are attached to AFM tips, and used for
“molecular-recognition” in order to study chemical forces between
molecules
4-Biomedical applications
Nanoscaffolds.
Nanofiber scaffolds can be used to regenerate central nervous system cells
and possible other organs. Experiments performed on a hamster with
severed optic tract demonstrated the regeneration of axonal tissue initiated
by a peptide nanofibers scaffold
Antimicrobial nanopowders and coatings.
Certain nanopowders, possess antimicrobial properties.When these
powders contact cells of E. coli, or other bacteria species and
viruses, over 90% are killed within a few minutes. Due to their antimicrobial
effect, nanoparticle of silver and titanium dioxide (<100nm) are assessed as
coatings for surgical masks .
Bioseparation.
Nanotube membranes can act as channels for highly selective transport of
molecules and ions between solutions that are present on both side of the
membrane . For example, membranes containing nanotubes with inside
diameters of molecular dimensions (less than 1 nm) separate small
molecules on the basis of molecular size, while nanotubes with larger inside
diameters (20–60 nm) can be used to separate proteins .
Drug delivery.
The ability of nanoparticles to target and penetrate specific organs and cells
contributes to their toxicity, however, this ability may be exploited in
nanomedicine. Nanospheres composed of biodegradable polymers can
incorporated drugs, allowing the timed release of the drug as the polymer
degrades . When particles are set to degrade in an acid microenvironment,
such as tumor cells or around inflammation sites, this allows site-specific or
targeted drug delivery.

71
Nanocrystals as Fluorescent Biological Labels
Biofunctional devices based on magnetic nanoparticles
• Delivery and controlled release of therapeutics
• Bioswitches for organ function
• Imaging
Biocompatible magnetic nanocrystals with reactive moieties on the surface
were generated by means of a “one-pot” reaction and used directly in cancer
detection by being coupled with a specific cancer-targeting antibodyand the
magnetic nanocrystals have potential application in MRI.
Magnetic nanoparticles
serving as biodetection
agents

72
Tissue Engineering
Nano/micro particles, including living animal cells, bacteria, and colloidal
gold (100 nm), can be optically guided and deposited in arbitrarily defined
three-dimensional arrays, a process called “laser-guided direct-writing.”
Detection of Chemical and Biological Warfare Agents
One technique uses atomic force microscopy with a sandwich immunoassay
attaching magnetic beads to a microfabricated cantilever sensitive to small
displacements.
BioCOM Chip
Respirocytes: A Mechanical Artifical Red Blood Cell
Fixing Damaged Blood Cells

73
In the Near Future:
Humanoid Shaped Nanorobots
5- Cosmetics
Titanium dioxide and zinc oxide become transparent to visible light when
formed at the nanoscale, however are able to absorb and reflect UV light,
being currently used in sunscreens and in the cosmetic industry.
6-Coatings
Nanomaterials have been used for very thin coatings for decades, if not
centuries. Today thin coatings are used in a vast range of applications,
including architectural glass, microelectronics, anticounterfeit devices,
optoelectronic devices, and catalytically active surfaces. Structured coatings

74
with nanometer-scale features in more than one dimension promise to be an
important foundational technology for the future.
Self-cleaning windows.
Self-cleaning windows have been demonstrated that are coated in
highly hydrophobic titanium dioxide. The titanium dioxide nanoparticles
speed up, in the presence of water and sunlight, the breakdown of dirt and
bacteria that can then be washed off the glass moreeasily.
Scratch resistant materials.
Nanoscale intermediate layers between the hard outer layer and the
substrate material significantly improve wear and scratch resistant coatings.
The intermediate layers are designed to give a good bonding and graded
matching of mechanical and thermal properties, leading to improved
adhesion.
7- Textiles.
Nanoparticles have already been used in coating textiles such as nylon, to
provide antimicrobial characteristics , Also the control of porosity at the
nanoscale and surface roughness in a variety of polymers and inorganic
materials led to ultrahydrophobic - waterproof
Another list of field of applications are shown below;
1-Power/Energy
 Dye-sensitized solar cells (e.g. using TiO2)
 Hydrogen storage (e.g. using metal hydrides)
 Improved anode and cathode materials for solid oxide fuel cells
 Thermal control fluids (e.g. using Cu)
 Environmental catalysts (e.g. ceria as diesel additive to improve
combustion efficiency)
 Automotive catalytic converters

75
 Miniaturised varistors (e.g. doped ZnO)
 Fuel cell catalysts (e.g. platinum in PEM cells)
 Conducting polymers for bipolar plates in fuel cells
 Improved electrodes in batteries and supercapacitors (increased
capacity, more rapid charging)
 Increased efficiency of hydrogen generation from water (e.g. from
solar)
 Catalysts for gas to liquid technologies, coal gasification
technologies,biodiesel and other synthetic fuels, etc,
1- Healthcare/medical
 Targeted drug delivery
 Alternative drug and vaccine delivery mechanisms (e.g. inhalation,
oralin place of injection).
 Bone growth promoters
 Cancer treatments
 Biocompatible coatings for implants
 Sunscreens (e.g. using ZnO and TiO2) / cosmetics
 Biolabeling and detection (e.g. using Au)
 Carriers for drugs with low water solubility
 Fungicides (e.g. using ZnO)
 MRI contrast agents (e.g. using superparamagnetic iron oxide)
 New dental composites
 Biological binding agents (e.g. for high phosphate levels)
 Antiviral, antibacterial (e.g. Ag), anti-spore non-chemical creams and
 powders (using surface tension energy on the nanoscale to destroy
biological particles)

76
2- Engineering
 Cutting tool bits (e.g. WC, TaC, TIC, Co)
 Spark plugs (e.g. using nanoscale metal and ceramic powders)
 Chemical sensors
 Molecular sieves
 Wear-resistant / abrasion-resistant coatings (e.g. using alumina, Y-
Zr2O3)
 Nanoclay-reinforced polymer composites
 Lubricants and sealants / hydraulic additives (e.g. Cu MoS2)
 Pigments
 Self-cleaning glass (e.g. using TiO2)
 Propellants (e.g. using Al)
 Structural and physical enhancement of polymers and composites
 Enhanced thermal spray coating techniques (e.g. based on TiO2, TiC-
Co)
 Inks: conducting, magnetic, etc. (using metal powders)
 Flame retardant polymer formulations
 Rubber composites such as car tyres (e.g. carbon black)
 Anti-scattering layers in photographic film
3- Consumer goods
 Anti-counterfeit devices
 Barrier packaging using silicates
 Ski wax
 White goods (e.g. anti-scratch, easy-cleaning coatings, etc.)
 Glass coatings for anti-glare, anti-misting mirrors (e.g. using TiO2)
 Sports goods: tennis balls, rackets (e.g. using nanoclays)
 Water- and stain-repellent textiles
 Pyrotechnics and explosives (e.g. using Al)

77
 Additives in paints (e.g. anti-bleaching effect, scratch resistance, etc.)
 Tiles coated (e.g. anti-scratch using alumina)
4- Environmental
 Water treatment (photo-catalyst treatments, e.g. using TiO2)
 Self-cleaning glass (e.g. using TiO2 based nanostructured coatings)
 Anti-reflection coatings
 Sanitary ware
 Soil remediation (e.g. using Fe)
 Controlled delivery of herbicides and pesticides
 Anti-fouling coatings (reduce chemical use)
5- Electronics
 Nanoscale magnetic particles for high-density data storage
 EMI shielding using conducting and magnetic materials
 Electronic circuits (e.g. using Cu, Al)
 Display technologies including field-emission devices (e.g. using
 conducting oxides)
 Ferro-fluids (e.g. using magnetic materials)
 Optoelectronics devices such as switches (e.g. using rare-earth-
dopedceramics)
 Conductive coatings and fabrics (e.g. using rare-earth-doped ceramics)
 Chemical mechanical planarization - CMP (e.g. using alumina,
silica,ceria)
 Coatings and joining materials for optical fibres (e.g. based in Si)
 solar cells - similar requirements to both coating and catalyst
applications
 improved electrodes - similar to catalytic applications
 antibacterials, antivirals, antifungals - similar to catalytic applications
 sensors - similar to medical applications (strict size and morphology
 constraints but the value lies in the system/device as a whole)
 pigments / inks - similar to coatings
 propellants / explosives - similar to catalysts
 data storage media similar to coatings

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