Synthesis of Nanomaterials:

Nanomaterials:
A brief overview
 What is Nanotechnology?

• The study of the controlling of matter on an atomic and

molecular scale. Generally nanotechnology deals with structures
sized between 1 to 100 nanometer in at least one dimension, and
involves developing or modifying materials or devices within
that size.
 Size Matters
• How Big is a Nano?

Nano = 1 billionth;100,000 x’s smaller than the diameter of a human hair.
• Examples of Nanoscale

A cubic micron of water contains about 90 billion atoms. A micron is one thousandth of a
millimeter, and a thousand times larger than a nanometer.

Another way to visualize a nanometer:
1 inch = 25,400,000 nanometers

Units in nanometers (µm)

 Applied Nanotechnology:
Examples of Current Research and Applications

Powders, Coatings, Carbon Nano-Materials,

Materials Science
C-NanoFabrics

Solar Power and PhotoVoltaics, Hydrogen Fuel Cells, LED

Energy
White Light

Genomics, Proteomics, Lab on a Chip,

Medicine/Biotech
C-Nanotubes,BuckyBalls

Electronics MRAM, NRAM, Q-Dots, Q-Bits

Devices Lithography, Dip Pen Lithography, AFM, MEMS

Applications
 Disruptive Apps: Materials

• Fiber that is stronger than spider web

• Metal 100 x’s stronger than steel, 1/6 weight

• Catalysts that respond more quickly and to more agents

• Plastics that conduct electricity

• Coatings that are nearly frictionless –(Shipping Industry)

• Materials that change color and transparency on demand.

• Materials that are self repairing, self cleaning, and never need repainting.

• Nanoscale powders that are five times as light as plastic but provide the
same radiation protection as metal.
 Continue…..

• Fuel cell technology becomes cost effective within 3 years.

• Batteries that store more energy and are much more efficient

• Plastics and paints that will store solar power and convert to energy for $1 per
watt.
 Advances in Nanomaterials
• Nano structures were already found in early meteorites. One of the first scientific report is
the colloidal Au particles synthesized by Michael Faraday as early as 1857.

• By the early 1940’s, precipitated and fumed silica nanoparticles were being manufactured
and sold in USA and Germany as substitute for ultrafine carbon black for rubber
reinforcements.

• Nanosized amorphous silica particles have found large scale applications in many every-
day consumer product, ranging from non-diary coffee creamer to automobile tires, optical
fibers and catalyst support.

• Recently it has been found that Maya blue paint is a nanostructured hybrid material. This
material is made of needle-shaped palygorskite (clay) crystals that form a superlattice
with a period of 1.4nm, with intercalates of amorphous silicate substrate containing
inclusions of metal (Mg) nanoparticles.
 Classification of Nanomaterials

• One dimension----eg. Surface films

• Two dimension----eg. Strands or fibres
• Three dimensions---e.g particles

They can exist in single, fused, aggregated or agglomerated forms

with spherical, tubular and irregular shapes.

Common examples are Fullerenes, nanotubes, dendrimers, quantum

dots etc.
• According to Siegel, nanostructured materials are classified
as Zero dimensional, one dimensional, two dimensional,
three dimensional nanostructures.

(a) 0 D spheres and clusters, (b) 1 D nanofibers, wires, and rods (c)2 D films, plates and networks, (d) 3D nanomaterials
Examples of Nanomaterials

Au nanoparticle Buckminsterfullerene FePt nanosphere

Titanium nanoflower Silver nanocubes SnO2 nanoflower

 Key Terms You Need to Know

• BuckyBalls

• Carbon Nanotubes

• MEMS (Micro Electro Mechanical System)

• Quantum Dots

• Molecular Self Repair/Assembly

• MRAM/Spintronics (Magnetoresistive random access memory)

• Lithography
Nanoscale carbon structures

DCMST
June 2nd, 2011
 Buckminsterfullerene

Molecule consisting of 60 C atoms

sp2 hybridized bonds

Has 20 hexagons, 12 pentagons

Other related structures have 70 or

84 C atoms

from sciencedaily.com

DCMST
June 2nd, 2011
 C60 is named for
Buckminster Fuller
who designed
geodesic domes.

from unusualife.com

DCMST
June 2nd, 2011
Original report of C60

DCMST
June 2nd, 2011
1996 Nobel Prize in Chemistry
Robert Curl, Sir Harold Kroto, Richard
Smalley “for their discovery of fullerenes”.

from Nobelprize.org

DCMST
June 2nd, 2011
 Carbon nanotubes

Rolled up
sheet of sp2
bonded
carbon atoms

from informaworld.com

DCMST
June 2nd, 2011
Carbon nanotubes can be formed from a
single sheet of C atoms or several sheets

Multiwalled
Single walled
carbon nanotube
carbon nanotube
(several sheets
(single sheet of
of carbon atoms)
carbon atoms)

from rice.edu

DCMST
June 2nd, 2011
Carbon sheets can also be rolled up in different
directions to give different types of nanotubes.

DCMST
June 2nd, 2011
The properties of nanotubes depend on how they
are rolled up

Electrical conductor

Electrical insulator

from phycomp.technion.ac.il

DCMST
June 2nd, 2011
Nanotube sizes also depend on how they are rolled
up

DCMST
June 2nd, 2011
Graphene (single sp2 bonded carbon sheet)

DCMST
June 2nd, 2011
 C atoms in
hexagonal array

from cnx.org

DCMST
June 2nd, 2011
From ncem.lbl.gov
Scale bar 0.2 nm
DCMST
June 2nd, 2011
 Nobel Prize in Physics 2010
Andre Geim and Konstantin Novoselov “for groundbreaking
experiments regarding the two-dimensional material
graphene”.

from Nobelprize.org

DCMST
June 2nd, 2011
Carbon nanostructures

DCMST
June 2nd, 2011
 Carbon Nanotubes
• 4 nm width (smaller diameter than DNA)

• 100x’s stronger than steel 1/6 weight

• Thermal/electrically conductive

• Metallic and Semi-Conductive

 BuckyBalls – C60
• Roundest and most symmetrical molecule known to man

• Compressed – becomes stronger than diamond

• Third major form of pure carbon

• Heat resistance and electrical conductivity

Synthesis
 Synthesis of Nanomaterials
To synthesize nanomaterials, either to assemble atoms together or to dis-assemble (Break or
dissociate) bulk solids into finer pieces until they are constituted of only few atoms.

Synthesis of
Nanomaterials

Top - down Bottom-up

method method
(Destruction) (Construction)
 Synthesis of Nanomaterials

Top - Down
method

High energy Gas Severe plastic

Lithography
Ball Milling condensation deformation
 SYNTHESIS
OF NANOMATERIALS
Bottom
Up
method

Physical Chemical Self-

Plasma Sol-gel Soft-
Vapor Vapor Assembly
Processes Processing Lithography
Deposition Deposition
 Mechanical Grinding (Physical Method)

Mechanical milling is achieved using high energy shaker, planetary ball, or tumbler mills
Energy transferred to the powder from refractory depends on the
• Rotational speed, size and number of the balls
• Ratio of the ball to powder mass
• The time of milling
• Milling atmosphere
Nanoparticle are produced by the shear action during grinding.
 Wet Chemical Synthesis (Chemical Method)
Wet Chemical Synthesis

Top down method Bottom up method

(Electrochemical etching) (Sol-gel)

• In Top down method single crystals are etched in an aqueous solution for producing
nanomaterials, e.g., synthesis of porous silicon by electrochemical etching.
• In Bottom up method (Sol-gel, precipitation etc.) materials containing the desired
precursors are mixed in a controlled fashion to form a colloidal solution.
 Sol-gel process
• The reactions involved in sol-gel chemistry based on the hydrolysis and
condensation of metal alkoxides MOR:
• MOR + H2O MOH +ROH (Hydrolysis)
• MOH + ROM M-O-M + ROH (Condensation)
The process involves the evolution of inorganic networks through the formation of
a colloidal suspension (Sol) and gelation of the sol to form a network in a
continuous liquid phase (gel). The starting material is processed to form a
dispersible oxide and forms a sol in contact with water or dilute acid. Removal of
the liquid from the sol yields the gel, and the sol/gel transition controls the particle
size and the shape. Calcination of the gel produces the oxide.
Schematic representation of sol-gel process of
synthesis of nanomaterials
 Steps of sol-gel process
• Formation of different stable solutions of the alkoxide or solvated metal precursor

• Formation of oxide or alcohol-bridged network (the gel) by a polyconensation or

polyesterification reaction that causes tremendous increase in the viscosity of the solution.

• Aging of the gel during which the polycondnsation reactions continue until the gel transform into

a solid mass. This is accompanied by contraction of the gel network and expansion of solvent from

gel pores.

• Drying the gel, when water and other volatile liquid are removed from the gel network. This

process involves fundamental change in the structure of the gel.

• Dehydration, during which surface bound M-OH groups are removed, thereby stabilising the gel

againest rehydration. This is achieved by heating at temperature up to 800 ºC.

• Densification and decomposition of the gels at high temperature. The pores of the gel network are

collapsed, the remaining organic species are volatilized.

 Advantages and disadvantages of sol-gel process
• The advantage is possibility of synthesizing nanomatallic inorganic materials like

glasses, glass ceramics or ceramic materials at very low temperatures compared to

high temperature process required by melting glass or firing ceramics.

• One of the main advantages is to synthesize monosized nano particles by any bottom

up approach.

• The major difficulty is controlling the growth of the particles and then stopping the

newly formed particles from agglomerating.

• Other technical issues are ensuring the reactions are complete so that no unwanted

reactant is left on the product and completely removing any growth aids that may

have been used in the process.

• Production rate of nano powders are very low.

 Liquid solid reactions (precipitation)
• In this method, ultrafine particles of the desired materials are produced by
precipitation from a solution. The presence of desired nuclei in the solution is
a necessary condition to initiate the process. TiO2 powders with particle sizes
in the range 70-300 nm have been prepared from titanium tetraisopropoxide
by this method. Similarly ZnS powders may be produced by reaction of
aqueous zinc salt solutions with thioacetamide.

Hydrothermal synthesis
• It is based on the ability of water an aqueous solutions to dilute the substances
at high temperatures and pressures, which are practically insoluble under
normal condition. These include oxides, silicates and sulphides. Autoclaves are
used for this purposes because they can withstand high temperature and
pressure for long period of time. The possible advantages of the process over
the other are the ability to create crystalline phase that are not stable at the
melting point. This method is used for the synthesis of materials which have
high vapor pressure near their melting point.
 Gas phase synthesis of nanomaterials
• This method allow elegant way to control process parameter in order to be
able to produce size, shape, and chemical composition controlled
nanostructures.

• In conventional chemical vapor deposition (CVD) synthesis, gaseous

products either are allowed to react homogeneously or heterogeneously
depending on a particular application.

1. In homogeneous CVD, particles form in the gas phase and diffuse towards
a cold surface due to thermophoretic forces, and can either be scrapped of
from the cold surface to give nano powders or deposited on to a substrate
to yield what is called ‘particulate films’.

2. In heterogeneous CVD, the solid is formed on the solid surface, which

catalyses the reaction and a dense film is formed.
 Advantages of gas phase processes

• An excellent control of size, shape, crystallinity and chemical

composition .
• Highly pure materials can be obtained
• Multicomponent systems are relatively easy to form
• Easy control of the reaction mechanisms
Most of the synthesis routes are based on the production of
small clusters that can aggregate to form nano particles.
 Furnace
• The simplest fashion to produce nano particles is by heating the desired
material in a heat resistant crucible containing the desired material. This
process is appropriate only for materials that have a high vapor pressure at
the heated temperatures that can be as high as 2000 C. Energy is introduced
in the precursor. The atoms are evaporated in to an atmosphere, which is
either inert or reactive. The synthesis procedure includes steps like
• Material with low vapor pressure fed into the furnace in the form of
organometallic precursor
• The hot atoms lose energy by collision with the atoms of the cold gas
• Undergoes condensation into small clusters via homogeneous nucleation

During synthesis the precursors react in the gas phase and form a compound
with the material that is separately injected in the reaction chamber.
Because of its inherent simplicity, it is possible to scale up this process from
laboratory (mg/day) to industrial scales (tons/day)
 Schematic representation of gas phase process of
single phase nanomaterials from a heated crucible
 Flame assisted ultrasonic spray pyrolysis
• In this process precursors are nebulized and then unwanted components are burnt in
a flame to get required materials. ZrO2 has been obtained by this method from a
precursor of Zr(CH3 CH2 CH2O)4.
• This process is mainly used for synthesis of fumed silica.
• Silicon tetrachloride is heated in an oxy-hydrogen flame to give highly dispersed
silica. The resulting amorphous powder consists of spherical particles with sizes in
the range 7-40 nm.
• In combustion flame synthesis mixture of acetylene and oxygen or hydrogen and
oxygen supplies the energy to initiate the pyrolysis of precursor. This process is
widely used for industrial production of powders in large quantities, such as carbon
black, fumed silica, and titanium dioxide.
• At high pressure, highly agglomerated powders are produced which is
disadvantageous for subsequent processing. The basic ides for low pressure flame
synthesis is to reduce agglomeration. Aerosol scientists widely use this process.
• Exact control of the flame produces a flat flame front. Due to oxidative atmosphere
of the flame, this synthesis process is limited to the formation of the oxides.
Schematic diagram of flame assisted ultrasonic
spray pyrolysis
 Gas condensation processing (GPC)

• Gas condensation was the first technique used to synthesize nano crystalline
metals and alloys.
• In this process a metallic or inorganic material is vaporised using thermal
evaporation sources such as crucibles, electron beam evaporation devices or
sputtering sources in an atmosphere of 1-50 mbar He, or other inert gases.
• Cluster form in the vicinity of the source by homogeneous nucleation in the
gas phase and grow by coalescence and incorporation of atoms from the gas
phase.
• The cluster or particle size depends critically on the residence time of the
particles in the growth system and can be influenced by the gas pressure,
kind of inert gas, and the evaporation rate/vapor pressure of the evaporating
material.
• The size of nanoparticles increases with increase in gas pressure, vapor
pressure and mass of the inert gas.
 Continued…

• A rotating cylinder cooled with liquid nitrogen was employed for the particle
collection.

• Nanoparticles are removed from the surface of the cylinder by means of a scraper.

• This method is better suited for larger scale synthesis of nano powders.

• A major advantage is the improved control over the particle sizes.

• The control of the composition of the elements is difficult, reproducibility is poor

and the, method is extremely slow.

• Ti to TiO2 or ZrO to ZrO2 nanocrystalline oxide powders are formed by this

process, but quantities have so far been limited to a laboratory scale.
 Chemical vapour condensation (CVC)
• This technique involves pyrolysis of vapors of metal organic precursors in a
reduced pressure atmosphere.

• Nanoparticles of ZrO2, Y2O3, have been produced by this method.

• The evaporative source used in GPC is replaced by a hot reactor in the

Chemical vapor condensation method.

• Nanosized particles metals and ceramics can be obtained in good amounts

by adjusting the residence time of the precursor molecules, changing the gas
flow rate, pressure difference between the precursor delivery system and
the main chamber and the temperature of the reactor.

• The production capacities in CVC process are much higher than GPC
system.
• In addition to the formation of nanoparticles of a single precursor The
CVC reactor can also be used for the synthesis of mixture of nanoparticles
of two phases by supplying two precursors at the front end of the reactor,
and

• Coated nanoparticles like n-ZrO2 coated with n-Al2O3 or vice versa, by

supplying a second precursor at the second stage of the reactor.
Schematic diagram of set up for GPC system followed by consolidation in a
mechnical press or collection in an appropriate solvent media
 Laser ablation
• This method is extensively used for preparation of nanoparticles and
particulate films.

• In this process a laser beam is used as the primary excitation source of

ablation for generating clusters directly from solid sample.

• The small dimension of the particles and the possibility to form thick films
make this process an efficient tool for the production of ceramic particles
and coatings.

• Synthesis of ZrO2, SnO2 nanoparticls thick films are synthesized using this
process.

• Synthesis of other materials such as lithium manganate, silicon and carbon

has also been carried out by this technique.
 Thermolysis

• This method involves solvent free pyrolysis of a suitable precursor

material. One of the oldest nanomaterials, activated charcoal is
prepared using this method. Precursor materials are pyrolyzed at
600-900 °C in the absence of air to obtain charcoal of specific
surface area.
• In the process the materials are carbonized in oxidizing atmosphere
of CO2,O2 or steam at 600-1200 °C and activation is carried using
chemicals such as KOH, NaOH, ZnCl2 or phosphoric acid.
 Solvothermal synthesis
• This is a versatile method for synthesizing nanomaterials at temperatures
below 200 C. This technique enables synthesis of crystalline products at
low temperature and also helps in control the size and morphology of the
resultant products.
Electrodeposition
• This technique involves creation of solid materials from electrochemical
reactions in liquid. A conducting substance is placed in liquid containing
electrolytes. When a potential is applied, redox reaction takes place and
the material is deposited as thin film at the cathode. Semiconductor ZnO
nanotube arrays are synthesized by direct electrochemical deposition from
aqueous solutions into the pore channels of anodically-formed alumina .
Applications of Nanomaterial
Based Products
Automotive industry
Engineering
Medicine
Cosmetics
Textile
Sports
Chemical industry
Electronic industry
 LOTUS – SELF CLEANING
Super
hydrophobicity
- Self cleaning

Water lily
SEM
Surface roughness – Self cleaning

Applications -

Rinsing with water Water drops – clean surface

 PEACOCK FEATHER
• Nano structured
particles

• Cleaning
surface

Applications
• Color never fade

• Scratch free
 NANOTECHNOLOGY –
FUEL CELL

Atlantic – Aprilia fuel cell bike

Photovoltaic cell

Hydrogen

Fuel Cell
NANOTECHNOLOGY – COSMETIC APPLICATIONS

Herbal liposome for cosmetic applications

Titanium oxide

Acne treatment
Before treatment After treatment
PLAR - Nanotechnology
NANO MATERIAL - OPTICAL PROPERTIES
Applications

Gold (Bulk) Nano Gold colloids

Au – Cancer Treatments
 NANO- TEXTILE APPLICATIONS

Nano tie and scarf Nano Jacket

Student’s uniform
 CHARACTERIZATION AND
DETECTION TECHNIQUES
• Essential requirements for the development, manufacturing
and commercialization of nanomaterials is their physical,
chemical and biological properties on a nanoscale level

• For determination of atomic structure and chemical

composition of solid or liquid nanomaterials –
spectroscopic methods, X-ray and Neutron diffraction

• For determination of size and shape – Electron

microcopies (SEM or TEM)
HIGH DEPTH OF FIELD

Optical Scanning Electron

Microscope Microscope

NANOMATERIAL
TRANSMISSION ELECTRON MICROSCOPE

JEM-2100F
 WORKING PRINCIPLE OF AFM

Photo detector

Laser Beam

Cantilever
Tip

Line Scan
Surface www.shef.ac.uk/~htsl/afm.htm

Tip Atoms

Force Atomic Force Microscope

Surface Atoms
 Meaning of Nanoparticles

Factor Prefix Symbol

o 10-1 deci d
o 10-2 centi c
o 10-3 milli m
o 10-6 micro µ
o 10-9 nano n GOLD
NANOPARTICLES
o 10-12 pico p Actually the nanoparticles are
particles with sized between 100
o 10-15 femto f and 1 nanometers
 Principle of Catalysis
• Catalyst is a substance that
increases the rate of a chemical
reaction by reducing the activation
energy and alter the required
reaction temperature
• Catalyst provide a site for the
reactants to be activated and
interacted together while leaving
the catalyst surface unchanged
after the reaction
• Catalyst surface must have high
active energy, right structure and
enough spaces
Catalyst Markets
 Meaning of ‘Nano’ for Catalysis

Activity of a catalyst Surface area of catalyst

For conventional catalyst - Direct relation between activity and area of the catalyst

Nanosize imparts special properties to the material by its structural and electronic
changes.
Bcz in case of nanoparticles activity is the function of electronic and structural
function.

Cubic (7.2 nm) Spherical(4.8)

(More active) (Less active)
Catalyst Development
Catalytic processes in an oil refinery
Refinery Catalysts
Nanaocatalysis Research
Nanaocatalysis Research

• Nanocatalyst has high surface area,

high surface-to-volume ratio
compared to bulk materials
• Yields higher atomic utilization ratio
• Surface electronic and steric
properties change
• Doping of heteroatoms over
nanocatalysts has greater impact
Nanaocatalyts - Industrial Application