NANOCHEMISTRY

BOOKS ON NANOTEHNOLOGY
S.NO. TITLE AUTHOR
1. Nanotechnology: Basic Science and Emerging
Technologies
Mick Wilson
2. Nanotechnology (AIP-Press) Gregory L. Timp
3. Unleashing the Potentials of Nanotechnology Torres Clivia M Sotomayor

4. Nanocomposite Science and Technology Braun Paul V
5. Materials and Processes for Surface and
Interface Engineering
Pauleau Yves
6. A Journey into the Nanoworld Balzani Vincenzo
7. Nanotechnology and Life Jones Richard A L
8. Nanosystems: Molecular Machinery,
Manufacuring and Computation
K. Eric Drexler
CONTENTS
Introduction
Principle
Methods of preparation
Properties
Techniques
Application Areas
Nanoscience
A discipline concerning with making,
manipulating and imaging materials having at
least one spatial dimension in the size range 1
100 nm
Nanotechnology
A device or machine, product or process based
upon individual or multiple integrated
nanoscale components
Nanochemistry
Utilization of synthetic chemistry to make
nanoscale building blocks of different:
Size and shape
Composition
Surface structure
Charge
Functionality.

Hierarchical Assembly
Feature of self-assembly, where primary building blocks
associate into more complex secondary structures that are
integrated into the next size level in the hierarchy. This
organizational scheme continues until the highest level in the
hierarchy is reached.
Characteristic of many self-assembling biological structures.
Few basic types
Nano powder/crystals
Nanotubes
Nanowires
Nanocomposites etc.

Nano powder/crystals
Crystals of nanometer dimensions.
Typical dimensions of 1 to 50 nanometers (nm),
intermediate in size between molecules and bulk
materials.
Exhibit intermediate properties.
Applications as:
o Biochemical tags
o As laser and optical components
o For the preparation of display devices
o For chemical catalysis.

Nanotubes
Hollow carbon tubes of nanometer dimensions.
Constitute a new form of carbon, configurationally equivalent to a
graphite sheet rolled into a hollow tube.
May be synthesized, with sizes ranging from a few microns to a few
nanometers and with thicknesses of many carbon layers down to single-
walled structures.
The unique structure of these nanotubes gives them advantageous
behavior relative to properties, such as electrical and thermal
conductivity, strength, stiffness and toughness.

Nanowires

Very small rods of atoms.
Solid, dense structures, much like a
conventional wire.
Offer the potential for creating very small IC
components.

Nanocomposites
Comprise a large variety of systems composed of dissimilar
components that are mixed at the nanometer scale.

Can be one-, two-, or three-dimensional; organic or inorganic;
crystalline or amorphous.

Behavior is dependent on not only the properties of the
components, but also morphology and interactions between
the individual components, which can give rise to novel
properties not exhibited by the parent materials.

Size reduction from microcomposites to nanocomposites
yields an increase in surface area that is important in
applications, such as mechanically reinforced components,
nonlinear optics, batteries, sensors and catalysts.
Methods of Preparation
By synthesis strategy
By nature of process
By medium of synthesis
1. By synthesis strategy

a. Bottom-Up Strategy:
By the agglomeration of atoms or particles.

b. Top-Down Strategy: (Attrition; like- erosion)
By breaking the larger particles to the nano size.
Generally done by high energy ball milling.

2. By nature of process

a. Physical methods:
Only the size of the particles can be reduced
mechanically.
Physical properties will be changed.
No change in chemical properties.
Just the increase in chemical reactivity due to
increase in surface area.

b. Chemical methods:
Chemical properties get change according to the
chemical route adapted.

3. By medium of synthesis
(i) Gas phase synthesis
(ii) Liquid phase synthesis
(iii)Solid phase synthesis
(i) Gas phase synthesis
Nano particles are formed as a result of
reactions among gaseous molecules, gas
molecule condensation or decomposition.


(ii) Liquid phase synthesis:
most widely used technique
Precipitation in homogeneous medium.

Routes:
a. Chemical precipitation
b. Hydro/solvo-thermal synthesis (Thermal hydrolysis)
c. Sol-gel synthesis
d. Micro-emulsion synthesis or synthesis in reverse
micelles

a. Chemical precipitation
Fast chemical reaction is required to obtain a high degree of
super-saturation of the product to favor homogeneous
nucleation.
Methodology
Scheme of precipitation process.
Reactant A Reactant B
Supersaturated
solution
Nucleation
Crystal growth
Nuclei
Nanoparticles
Mixing
Primary processes
Super-saturation is a state of
a solution that contains more
of the dissolved material that
could be dissolved by
the solvent under normal
circumstances.
b. Hydrothermal synthesis
(Thermal hydrolysis)
Aqueous solutions of metal salts or gels are
treated at elevated temperatures (100-300C) and
pressures above 1 atm.
Size and shape of nanoparticles can be controlled
by changing the conditions of the solutions:
pH
Concentration
Solvent and process conditions (temperature, duration,
etc.).

Hydrothermal synthesis is a technique of crystallizing substances from high-
temperature aqueous solutions at high vapor pressures; also termed "hydrothermal
method". The term "hydrothermal" is of geologic origin.

It is a method of synthesis of single crystals.

The crystal growth is performed an autoclave.

At the hotter end the nutrient solute dissolves, while at the cooler end it is deposited on a
seed crystal, growing the desired crystal.

Possible advantages
The ability to create crystalline phases.

Materials which have a high vapor pressure near their melting points can also be grown by
the hydrothermal method.

The method is also particularly suitable for the growth of large good-quality crystals while
maintaining good control over their composition.

Disadvantages of the method include the need of expensive autoclaves, and the impossibility
of observing the crystal as it grows.
c. Sol- Gel synthesis
Process involves the alkoxide hydrolysis and a condensation
reaction.
M(OR)
x
+ yH-OH M(OR)
x-y
(OH)
y
+ yROH

Partially hydrolysed species are then linked to form M-O-M
bonds by condensation via dehydration or dealcoholation.
-M-OH + HO-M- -M-O-M- + H
2
O
-M-OH + RO-M- -M-O-M- + ROH

So, the process involving hydrolysis, polymerization,
nucleation and growth condenses the molecular units together
into small clusters called sols, eventually leading to the
formation of an insoluble three dimensional network, the gel.

The sol-gel process is a wet-chemical technique
starting from a chemical solution, which acts as the precursor for an integrated
network (or gel) of either discrete particles or network polymers.
Typical precursors are metal alkoxides and metal chlorides, which
undergo hydrolysis and polycondensation reactions to form either a network
"elastic solid" or colloidal suspension
Formation of a metal oxide involves connecting the metal centers with oxo (M-O-
M) or hydroxo (M-OH-M) bridges to generate metal-oxo or metal-hydroxo
polymers in solution.
The sol evolves toward the formation of a gel-like diphasic system containing both
a liquid phase and solid phase whose morphologies range from discrete particles
to continuous polymer networks.
In the case of the colloid, a significant amount of fluid may need to be
removed initially for the gel-like properties to be recognized.
The most simple method is to allow time for sedimentation to occur, and
then pour off the remaining liquid. Centrifugation can also be used to
accelerate the process of phase separation.
Removal of the remaining liquid (solvent) phase requires a drying process.
The rate at which the solvent can be removed is ultimately determined by
the distribution of porosity in the gel.
The sol-gel approach is a cheap and low-temperature technique that
allows for the fine control of the products chemical composition.

d. Micro-emulsion synthesis
Microemulsions: Thermodynamically stable, optically clear
dispersions of two immiscible liquids, such as water and oil.
They are formed, when a surfactant lowers the oil/water interfacial
tension allowing thermal motions to spontaneously disperse the two
immiscible phases.
Reverse micelles are molecular self assemblies from surfactants which
have a spherical shape with a hydrophillic core and a hydrophobic tail
on the sphere surface.
Most popular method to prepare Nano-sized inorganic particles as
oxides.

(iii) Solid phase synthesis
Nanoparticles are formed directly from solids or semisolids
(viscous liquids).
It belongs to top-down approach.

i) Mechanical Milling:
Mechanical forces, involved in high energy ball milling,
are used to break bulk material down to bring it to nano-
level.

ii) Mechano-chemical method:
Involves the physical reduction in the material size as
well as the milling energy is used to initiate the chemical
reaction between the materials that are being milled.

Properties
Surface area: Large.

Reactivity: High due to the unsaturated bonds on their pristine
surfaces.

Basic properties: Properties of materials change as:
- their size approaches the nanoscale.
- percentage of atoms at the surface of a material becomes significant.
Example- Gold nanoparticles melt at much lower temperatures (~300
C for 2.5 nm size) than the gold slabs (1064C).

Optical properties: Often possess unexpected optical properties as
they are small enough to confine their electrons and produce quantum
effects. Example- Gold nanoparticles appear deep red to black in
solution.

Techniques
Scanning tunneling microscope (STM)
Atomic force microscope (AFM)
Scanning electron microscopy (SEM)
Transmission electron microscopy (TEM)
X-ray diffraction (XRD), etc.


Application Areas
Medicine
Diagnosis
Drug delivery
Tissue engineering
Environment
Catalysis
Filtration
Energy
Computers
Aerospace
Refineries
Vehicle manufacturing
Food packaging
Optics
Textiles
Cosmetics