BASICS OF NANO-MATERIALS

CONTENTS
• Nano- materials –definition, types
• Fullerenes
• Inorganic Particles
• Applications of Nano materials
• Manufacturing Methods—Top down and bottom up approaches
• Sol-Gel process
• High energy milling( ball milling)
• Inert gas condensation
• Laser ablation
• Flame pyrolysis.
CLASSIFICATION OF NANO-MATERIALS
• Nano-materials generally fall into two categories– Fullerenes ,
inorganic particles.
• FULLERENS:
• They are allotropes of carbon, which are Graphene sheets rolled into tubes or hollow spheres.
Spherical fullerenes are also called Bucky balls and cylindrical ones are called as nanotubes or
Bucky tubes. Fullerenes are similar in structure to Graphite, but they may have pentagonal
rings.
• The first fullerene discovered was BUCKMINISTER FULLERENE C60 IN 1985. They had their
shape similar to a geodesic dome( for earthquake resistant structures), designed by RICHARD
BUCKMINISTER FULLER (an architectural modeller).
• CARBON NANOTUBES : They are allotropes of Carbon with cylindrical nanostructure. They are
classified as single walled and multi walled nanotubes. They are efficient conductors of heat.
They possess unique electrical properties. They possess good strength and flexibility. They are
used in electronics, optics applications.
• INORGANIC PARTICLES: Nanoparticles sized between 1 and 100nm are available in different
forms such as clusters, metal nanoparticles, colloids( nanoparticles in suspended form in
liquid phase), nanocrystals( nm sized single crystals), quantum dots( tiny particles of semi
conductor materials) etc.,
WHY THE PROPERTIES OF NANOMATERIALS ARE DIFFERENT ?
• Two main reasons exist for the properties of nanomaterials to be different from
other materials:
• Increased relative surface area—Nanomaterials have relatively larger surface area
compared to the larger form of the material, for the same volume.
consider a sphere of radius “r”
It’s surface area = 4∏r2 ; It’s volume = (4/3) ∏r3 ; surface area to volume ratio= 3/r
→ when the radius of sphere is decreased, it’s surface area to volume ratio will be
increased.
→hence, as particle size is decreased, a greater proportion of atoms are found at the
surface compared to those inside. It makes nanomaterials, chemically more reactive. In
some cases, materials that are inert in their larger form are reactive when produced in their
nanoscale form.
• Increased quantum effects: when the material is in sufficiently small size, typically 10nm
or less, organization of energy levels( into which electrons can climb or fall) will change .
Specifically, the phenomenon results from electrons and holes being squeezed into a
dimension, that approaches a critical quantum measurement, called the “ excitation Bohr
radius”. These can affect the optical, electrical and magnetic behaviour of materials at
nanoscale.
APPLICATIONS OF NANO MATERIALS:
• Cutting tools- made of nano crystalline materials, such as tungsten carbide,
tantalum carbide, titanium carbide, are more wear and erosion resistant.
• Nano metric ceramics exhibit increased ductility and superplastic deformation
behaviour.
• Carbon nano particles act as fillers in a matrix; for ex- they are used as filler to
reinforce car tyres.
• Clay particle based composites- containing plastics and nano sized flakes of clay
are also finding applications in car bumpers.
• Nano coating of highly activated titanium dioxide is highly hydrophobic( water
repellent). Hence, used as self cleaning windows.
• Magnets made of nano crystalline yttrium- samarium- cobalt grains possesses
unusual magnetic properties due to their extremely large grain interface area.
High coercivity can be achieved, because magnetization changes can not easily
propagate past the grain boundaries. This could lead to applications, such as
motors and analytical instruments like MRI.
• Nano particles have high surface area, hence used as efficient catalysts.
• Smart magnetic fluids are used as vacuum seals, viscous dampers, cooling fluids,
magnetic separators etc.,
• Nano- engineered membranes could lead to more energy efficient water
purification processes such as Reverse osmosis systems.
• Nano particles react with pollutants in soil and ground water and transform
them into harmless compounds. For ex- iron particles will transform chlorinated
hydrocarbons( carcinogens) into less harmful end products in ground water.
• By controlling porosity at nanoscale, enhanced textiles such as breathable, water
proof, stain resistant fabrics are developed in polymers and inorganics.
• Paints that change colour in response to change in temperature or chemical
environment etc., have become possible.
• Nano sized titanium dioxide and zinc oxide are used in sunscreens, as they absorb
and reflect U/V rays and yet are transparent to visible light.
• Nano sized iron oxide is used in lip sticks as pigment.
• Nano spheres of inorganic materials are used as lubricants, as they behave like
nano sized ball bearings.
• Nano crystalline Zirconium oxide is hard, wear resistant, and biocompatible.
Hence, used as Medical implant material. Similarly, nano crystalline silicon
carbide has low weight, high strength and inertness, hence used as artificial heart
valves.
• With more atoms on surface, the surface pressure changes, hence
inter atomic spacing decreases, by decreasing the particle size. Due to
variations in surface free energy, melting point decreases by
decreasing the particle size.
• Small particles are more magnetic than the bulk material.
• Higher young’s modulus, higher hardness and strength, superplastic
behaviour in brittle ceramics.
SYNTHESIS METHODS
• Top down techniques– produce very small structures from larger
pieces of material. Ex : mechanical crushing of solid into fine nano
powder ( ball milling).
• Ball milling

• Bottom up techniques-produces big structures by assembling atoms

to atoms or molecules to molecules.
• Plasma arc Method—
• Chemical vapour deposition method—
• Sol-gel method--
Ball Milling
• Small balls are allowed to rotate around the inside of drum and then
repeatedly strike on a solid and crush it into nano crystallites. It can
be used to prepare a range of elemental and metal oxide powders.
Plasma Arc method
• Plasma is an ionized gas. To produce plasma, a potential difference is
applied between the electrodes. The Helium or argon gas( at low
pressure of 50-700 mbar) between the electrodes gets ionized and
results in electric discharge. An arc passes from one electrode to
another electrode( gap is 1mm).Positively charged ions pass to the
cathode and get deposited in the form of nano particles. This method
is used to carbon nanotubes, by using carbon electrodes.
Chemical Vapour Deposition
• A metal organic precursor is introduced into the hot zone of the reactor
using mass flow controller. The precursor is vapourised by either resistive
or inductive heating. The carrier gas such as Ar or Neon carries hot atoms
to the reaction chamber. The hot atoms collide with cold atoms and
undergo condensation through nucleation and form small clusters.. In side
reaction chamber other reactants are added to control the reaction rate.
Then, the clusters are allowed to condense on a moving belt arrangement
with scrapper to collect the nano particles.
• Size of particle can be controlled by rate of evaporation, rate of cluster
formation and rate of condensation.
• Higher yield of nanoparticles in ceramics like carbides and nitrides is
possible.
• Mixtures of nano particles, coated nano particles can also bbe produced.
Sol-gel method
• A metal or metalloid element is surrounded by various reactive ligands; to
convert it into a dispersible oxide, it is added with water / dilute acid. This
colloidal suspension, is now called sol.
• It is then added with alcohol, to ensure a poly-condensation process to
take place. After poly -condensation, it becomes a gel. Poly-condensation
reaction increases viscosity of the solution. It is then subjected to ageing
process called synerisis, to convert gel into a solid mass. This is
accompanied by contraction of gel network and expulsion of solvent from
the Gel. In this Ostwald ripening causes smaller particles to be consumed
by bigger particles, in growth process.
• Drying results in dehydration( removal of water & other volatile liquids)
• Calcining is done at 8000C on monolith, to remove M-OH groups, so that
no rehydration will take place. Densification of the Gel is done to get the
final part.
• Best advantage of this process is that one can get mono sized nano
particles.
WORK BOOK QUESTIONS
Q1/P110} Nano materials are
a) organic materials b) inorganic materials
c) Both a) and b) d) none of these
Q2/p110} Ordinary Glass, quantized with semiconductor colloids,
results in improvement in
a) optical performance b) chemical performance
c) Biodegradability d) none of these
Q3/p110} Identify nano-materials from the following:
a) Nanotubes b) Dendrimers
c) quantum dots & fullerenes d)all the above
Q4/p110} Nanostructured materials are
a) Zero-Dimensional b) one-dimensional
c) two & three dimensional d) all the above
Q5/p110} Window layers in solar cells are made of
a) nanostructured semi-conductors b)single crystal materials
c) monolithic materials d) none of these
Q6/p110} Ferro-fluids used for high density information storage are made of
a) Magnetic nano-composite b) Laminated composites
c) Dispersion strengthened alloys d) None of these
Q7/p110} nanostructured MnO2 is used in
a) Rechargeable batteries b) Magnetic refrigeration
c) cutting tools d) none of these
Q8/p110} High content of inorganic particles in polymer composites results in
a) increase in dielectric constant
b) decrease in dielectric constant
c)increase in section modulus
d) none of these
Q9/p110} In sol-gel process used for synthesis of nano-materials, the term gel refers
to
a) a suspension b) a liquid
b) a solid d) none of these
Q10/pp110} In sol-gel process used for synthesis of nano-materials, ‘ Ostwald
ripening’ refers to
a) smaller particles consumed by larger particles during growth
b) Larger particles consumed by smaller particles during growth
c) Precipitation of smaller particles from larger particles during growth.
d) none of these.
Q11/p110} Microbial fuel cells used in the conversion of domestic and
industrial waste into electricity are made of carbon nano-
tubes, because they possesses
a) high surface area b) high chemical stability
c) proliferates hydrogen producing bacteria efficiently
d) all the above.
Q12/p110} Nano phase ceramics are more ductile at high temperatures
than coarse grain structures( true/false)
Q13/p110} Carbon nanotubes are typical example of
a) Zero dimensional nanomaterials
b) one-dimensional nanomaterials
c) two dimensional nanomaterials
d) three dimensional nanomaterials.
• PRACTICE TEST:
1. Match the following:

Nanoscale materials Examples

1. one dimension A. quantum dots
2. Two dimensions B. Nanowires & nanotubes

3. Three dimensions C. Thin films

CODES:
a) 1- A , 2- B , 3- C b) 1- C, 2-B, 3-A c) 1- B, 2-C, 3- A d) None.

2. Consider the following statements and identify incorrect statement(s):

1.Carbon nanotubes are allotropes of Carbon with spherical nanostructure.
2.They are members of Fullerene structural family.
3.They exhibit extraordinary strength and Unique electrical properties.
4.They are efficient conductors of heat.
CODES:
a)1 only b) 2 only c) 4 only d) none of these.
3. Consider the following methods of manufacturing nanomaterials:
1.Chemical vapour deposition
2.Ball milling
3.Sol-Gel method
4.Nanolithography
From the above, identify the bottom-up fabrication method(s), uing the codes given below:
a)1,2 b) 1, 3 c) 2,3 d) 2, 4

4.Consider the following statements and identify correct statement(s):

1. Nano-crystalline Zirconium Oxide is used for Implants
2. Nano-crystalline silicon carbide is used for artificial heart valves.
3. Nano-crystalline Yittrium- Samarium-Cobalt is used in applications like Magnetic Resonance imaging.
4. Nano-crystalline ceramics are used in ball bearings and valve lifters.
CODES:
a)1,2 b) 1,2,3 c) 1,2,3,4 d) 3 only.

5. Young’s modulus of single walled nano-tubes is about

a)1 kilopascal b) 1 millipascal c) 1 terapascal d) 1 gigapascal
• ANSWERS TO PRACTICE TEST:
QUESTION
NO.
1 2 3 4 5
ANSWER b b c c
a
IMPORTANT POINTS:
 Nanoparticles of even non-magnetic solid are found to be magnetic. It has been found theoretically and
experimentally that the magnetism is special to small sizes and disappears in clusters containing more than
80 atoms. At small sizes, the clusters become spontaneously magnetic.
 Nano- crystalline materials will have lower young’s modulus than conventional materials, due to the
presence of extrinsic defects and cracks.
 Magnets made of Nano-crystalline Yittrium- Samarium-Cobalt grains possess unusual magnetic
properties, due to their extremely large grain interface area. High coercivity is obtained because
magnetization flips cannot easily propagate past the grain boundaries. This leads to applications in
MOTORS, analytical instruments like Magnetic Resonance Imaging (MRI).
 Nanoparticles react with pollutants in soil and ground water and transform them into harmless
compounds. Iron nanoparticles transform chlorinated hydrocarbons (which are carcinogens) into less
harmful end products in ground water.
• Improved control of porosity at the nano-scale has important applications, like enhanced textiles
such as breathable, waterproof and stain resistant fabrics, in polymers and organics.
• Nano-sized titanium dioxide and Zinc oxide are used in SUN SCREENS. They absorb U/V rays and
yet are transparent to visible light.
• Nano-sized iron oxide is used as pigment in lipsticks.
• Nano-spheres of inorganic materials could be used as Lubricants.
• Nano-crystalline Zirconium Oxide is used as material for Implants, because it is hard, wear
resistant and biocompatible.
• Nano-crystalline silicon carbide is used for artificial heart valves, primarily because of its low
weight, high strength and inertness.
• Since, hydrogen absorbing capacity increases with decrease of size of nanoparticles,
nanoparticles of NI, Pd, Pt are useful in hydrogen storage devices.