ME332 : MATERIAL SCIENCE AND METALLURGY

Unit - I Chapter 2
Dr. Shijo Thomas
Dept: of Mechanical Engineering
Faculty of Engineering - CHRIST (Deemed to be University)
+91-9447745052, +91-9947881017
Shijo.thomas3@gmail.com
NANOMATERIALS
Nanomaterials: Introduction, Synthesis,
Properties, Introduction to Nanotubes
Introduction
Nanomaterials are cornerstones of
nanoscience and nanotechnology.
Nanostructure science and technology is a
broad and interdisciplinary area of
research and development activity that has
been growing explosively worldwide in the
past few years. It has the potential for
revolutionizing the ways in which materials
and products are created and the range
and nature of functionalities that can be
accessed. It is already having a significant
commercial impact, which will assuredly
increase in the future.
Nanotechnology deals with the creation of
USEFUL materials, devices and systems
using the particles of nanometer length
scale and exploitation of NOVEL properties
(physical, chemical, biological) at that
length scale
 Where do you find Nanomaterials?
O Some nanomaterials occur naturally, but of particular interest are engineered
nanomaterials (EN), which are designed for, and already being used in many
commercial products and processes. They can be found in such things as
sunscreens, cosmetics, sporting goods, stain-resistant clothing, tires, electronics, as
well as many other everyday items, and are used in medicine for purposes of
diagnosis, imaging and drug delivery.
O Engineered nanomaterials are resources designed at the molecular (nanometre)
level to take advantage of their small size and novel properties which are generally
not seen in their conventional, bulk counterparts. The two main reasons why
materials at the nano scale can have different properties are increased relative
surface area and new quantum effects. Nanomaterials have a much greater surface
area to volume ratio than their conventional forms, which can lead to greater
chemical reactivity and affect their strength. Also at the nano scale, quantum effects
can become much more important in determining the materials properties and
characteristics, leading to novel optical, electrical and magnetic behaviors.
Nanomaterials
O Nanoscale materials are defined as a set of substances where at least
one dimension is less than approximately 100 nanometers.
O A nanometer is one millionth of a millimeter approximately 100,000
times smaller than the diameter of a human hair.
O They are of interest because at this scale unique optical, magnetic,
electrical, and other properties emerge. These emergent properties
have the potential for great impacts in electronics, medicine, and other
fields.
• Composites made from particles of nano-size ceramics or metals smaller than 100
nanometers can suddenly become much stronger than predicted by existing materials-
science models.

• For example, metals with a so-called grain size of around 10 nanometers are as much
as seven times harder and tougher than their ordinary counterparts with grain sizes in
the micro meter range.

• The Nano particles affects many properties such as

Melting point
Boiling point
Band gap
Optical properties
Electrical properties
Magnetic properties
 The properties of materials can be different at the Nanoscale for two main
reasons:
First, Nanomaterials have a relatively larger surface area when compared to the same mass of material
produced in a larger form.

Nano particles can make materials more chemically reactive and affect their strength or electrical
properties.

Second, quantum effects can begin to dominate the behaviour of matter at the Nanoscale
 Classification of Nanomaterials
Nanoscale materials are divided into three category,
1. Zero dimension – length , breadth and heights are confined at single point.
(for example, Nano dots)
2. One dimension – It has only one parameter either length (or) breadth (or)
height ( example:very thin surface coatings)
3. Two dimensions- it has only length and breadth (for example, nanowires and
nanotubes)
4. Three dimensions -it has all parameter of length, breadth and height. (for
example, Nano Particles).
zero D(atomic clusters, filaments and cluster assemblies),
one D (multilayers),
two D (ultrafine-grained overlayers or buried layers), and
Three D (nanophase materials consisting of equiaxed nanometer sized grains) as shown in the
previous figure
 Classification of Nanomaterials
O Nanomaterials have extremely small size which having at least one dimension
100 nm or less. Nanomaterials can be nanoscale in one dimension (eg. surface
films), two dimensions (eg. strands or fibres), or three dimensions (eg.
particles). They can exist in single, fused, aggregated or agglomerated forms
with spherical, tubular, and irregular shapes. Common types of nanomaterials
include nanotubes, dendrimers, quantum dots and fullerenes. Nanomaterials
have applications in the field of nano technology, and displays different physical
chemical characteristics from normal chemicals (i.e., silver nano, carbon
nanotube, fullerene, photocatalyst, carbon nano, silica).
Based on the size and shape, the Nano
materials are classified as follows
• Nanoparticles
• Nanocapsules
• Nanofibers
• Nanowires
• Fullerenes (carbon 60)
• Nanotubes
• Nanosprings
• Nanobelts
• Quantum dots
• Nanofluids
 Application
Importance of Nanomaterials
(i) Nanophase ceramics are of particular interest because they are more ductile
at elevated temperatures as compared to the coarse-grained ceramics.
(ii) Nanostructured semiconductors are known to show various non-linear
optical properties. Nanostructured semiconductors are used as window layers in
solar cells.
(iii) Nanosized metallic powders have been used for the production of gas tight
materials, dense parts and porous coatings.
(iv) Magnetic nanophase materials
(v) Nanostructured metal clusters in catalytic applications.
 Application
Sunscreens and Cosmetics
• Nanosized titanium dioxide and zinc oxide are currently used in some sunscreens, as
they absorb and reflect ultraviolet (UV) rays.

• Nanosized iron oxide is present in some lipsticks as a pigment.

Fuel Cells
The potential use of nano-engineered membranes to intensify catalytic processes could
enable higher-efficiency, small-scale fuel cells.
Displays
• Nanocrystalline zinc selenide, zinc sulphide, cadmium sulphide and lead telluride are
candidates for the next generation of light-emitting phosphors.

• CNTs are being investigated for low voltage field-emission displays; their strength,
sharpness, conductivity and inertness make them potentially very efficient and long-lasting
emitters.
 Application
Batteries
• With the growth in portable electronic equipment (mobile phones, navigation devices, laptop
computers, remote sensors), there is great demand for lightweight, high-energy density
batteries.

• Nanocrystalline materials are candidates for separator plates in batteries because of their foam-
like (aerogel) structure, which can hold considerably more energy than conventional ones.

• Nickel–metal hydride batteries made of nanocrystalline nickel and metal hydrides are
envisioned to require less frequent recharging and to last longer because of their large grain
boundary (surface) area.

Catalysts
In general, nanoparticles have a high surface area, and hence provide higher catalytic activity.
Magnetic Nano Materials applications
Application
• It has been shown that magnets made of nano-crystalline yttrium–samarium–cobalt grains
possess unusual magnetic properties due to their extremely large grain interface area (high
coercivity can be obtained because magnetization flips cannot easily propagate past the grain
boundaries).

• This could lead to applications in motors, analytical instruments like magnetic resonance
imaging (MRI), used widely in hospitals, and micro-sensors.

• Nanoscale-fabricated magnetic materials also have applications in data storage.

• Devices such as computer hard disks storage capacity is increased with Magnetic Nano
materials
Medical Implantation
Application
•Unfortunately, in some cases, the biomedical metal alloys may wear out within the lifetime of
the patient. But Nano materials increases the life time of the implant materials.
.
•Nanocrystalline zirconium oxide (zirconia) is hard, wear resistant, bio-corrosion resistant and
bio-compatible.

•It therefore presents an attractive alternative material for implants.

•Nanocrystalline silicon carbide is a candidate material for artificial heart valves primarily
because of its low weight, high strength and inertness.

Water purification

•Nano-engineered membranes could potentially lead to more energy-efficient water purification

processes, notably in desalination process.
 Application
Military Battle Suits

• Enhanced nanomaterials form the basis of a state-of- the-art „battle suit‟ that is being
developed.

• A short-term development is likely to be energy-absorbing materials that will withstand blast

waves;

• longer-term are those that incorporate sensors to detect or respond to chemical and biological
weapons (for example, responsive nanopores that „close‟ upon detection of a biological agent).
Nano shells as Cancer Therapy - Application
Nano shells are injected into cancer area and
they recognize cancer cells. Then by applying Nano Computing Technology
near-infrared light, the heat generated by the
light-absorbing Nano shells has successfully computers embedded in walls,
killed tumor cells while leaving neighboring cells chairs, clothing, light switches,
intact. cars….; characterized by the
connection of things in the world
with computation.
What are Carbon nanotubes.  a nano material
•Carbon nanotubes (CNTs) are allotropes
of carbon. These cylindrical carbon
molecules have interesting properties
that make them potentially useful in
many applications in nanotechnology,
electronics, optics and other fields of
materials science, as well as potential
uses in architectural fields. They exhibit
extraordinary strength and unique
electrical properties, and are efficient
conductors of heat. Their final usage,
however, may be limited by their potential
toxicity.
O Nanotubes are extremely strong mechanically
and very pure conductors of electric current.
O Applications of the nanotube
include resistors, capacitors, inductors, diodes
and transistors. )
O Due to their nanoscale dimensions, electron
transport in carbon nanotubes will take place
through quantum effects and will only
propagate along the axis of the tube. Because
of this special transport property, carbon
nanotubes are frequently referred to as
O “one-dimensional.”
Strength Properties Properties of CNT
O Carbon nanotubes have the strongest tensile strength of any material
known.
O It also has the highest modulus of elasticity.

Thermal Properties
O All nanotubes are expected to be very good thermal conductors along the tube, but good
insulators laterally to the tube axis.
O It is predicted that carbon nanotubes will be able to transmit up to 6000 watts per meter
per Kelvin at room temperature; compare this to copper, a metal well-known for its good
thermal conductivity, which transmits 385 watts per meter per K.
O The temperature stability of carbon nanotubes is estimated to be up to 2800oC in vacuum
and about 750oC in air.
Environmental Implications of nano materials
O Potential widespread application of nanomaterials in environmental remediation is made
possible by the miniaturization of materials down to the nano-scale.

O However, this same enabling characteristic also influences risk by changing the particles'
potential for mobility, exposure, absorption, reactivity, and toxicity.

O When a nanomaterial is used for environmental remediation, it is intentionally introduced

into the environment to exploit its unique properties.
O Nevertheless, nanomaterials can have side effects, and a risk assessment requires
knowledge of their distribution in the environment and food chain.
Environmental Implications of nano materials
O Risk assessment is required for understanding the nanoparticles’ behavior to evaluate
potential risks associated with nanomaterial use for remediation.

O Side effects associated with the use of nanotechnology, especially environmental risks
associated with residual nanomaterials’ fate and transport in the environment, are not yet
fully explored and understood.

O Uncertainties of the nature and interaction of nanomaterials in the following areas add to
the complexity of risk concerns.
a- Uncertainty in relationship between size, surface area, and surface reactivity
b- Uncertainty in relationship of radionuclide and nanomaterials.
Synthesis and Processing of
Nanomaterials
 1. Mechanical Grinding

O Mechanical milling is typically achieved using high

energy shaker, planetary ball, or tumbler mills. The
energy transferred to the powder from refractory or
steel balls depends on the rotational (vibrational)
speed, size and number of the balls, ratio of the
ball to powder mass, the time of milling and the
milling atmosphere. Nanoparticles are produced by
the shear action during grinding.
2. Wet Chemical Synthesis of Nanomaterials
In principle we can classify the wet chemical synthesis of nanomaterials
into two broad groups:
1. The top down method: where single crystals are etched in an aqueous
solution for producing nanomaterials, For example, the synthesis of
porous silicon by electrochemical etching.
2. The bottom up method: consisting of sol-gel method, precipitation etc.
where materials containing the desired precursors are mixed in a
controlled fashion to form a colloidal solution.
 2.a Sol – gel process
O The sol-gel 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 precursors for synthesizing
these colloids consist usually of a metal or metalloid element surrounded
by various reactive ligands. 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 shape. Calcination of the gel produces the
oxide
Sol gel Synthesis of nano materials
3. Gas phase synthesis of nanomaterials
O Chemical Vapor Deposition
O Chemical Vapor Deposition is the formation of a non-volatile solid film on a substrate
by the reaction of vapor phase chemicals (reactants) that contain the required
constituents.
O The reactant gases are introduced into a reaction chamber and are decomposed and
reacted at a heated surface to form the thin film.
O Fundamental principle is that a chemical reaction takes place between the source
gases.
O The product of that is a solid material that condenses on all surfaces inside the reactor
O Precursor gases (often diluted in carrier gases) are delivered into the reaction
chamber at approximately ambient temperatures.
Chemical Deposition Processes
O Atmospheric Chemical
Vapor Deposition (CVD)
O Wafers are heated
O Chemical gases are
introduced
O A temperature dependent
deposition rate
O Mass transport limited at
higher temperatures
O A CVD apparatus will consist of several basic components:
1. Gas delivery system – For the supply of precursors to the reactor chamber
2. Reactor chamber – Chamber within which deposition takes place
3. Substrate loading mechanism – A system for introducing and removing substrates,
mandrels etc
4. Energy source – Provide the energy/heat that is required to get the precursors to
react/decompose.
5. Vacuum system – A system for removal of all other gaseous species other than those
required for the reaction/deposition.
6. Exhaust system – System for removal of volatile by-products from the reaction chamber.
7. Exhaust treatment systems – In some instances, exhaust gases may not be suitable for
release into the atmosphere and may require treatment or conversion to safe/harmless
compounds.
8. Process control equipment – Gauges, controls etc to monitor process parameters such as
pressure, temperature and time. Alarms and safety devices would also be included in this
category.
 Sequential Steps:

1. Transport of reacting to the substrate surface

2. Absorption of species on the substrate surface
3. Heterogeneous surface reaction catalyzed by the substrate surface.
4. Desorption of gaseous reaction byproducts
5. Transportation of reaction by-products away from the substrate
Coating Characteristics

 CVD coatings are typically:

 Fine grained
 Impervious
 High purity

 CVD coatings are usually only a few microns thick and are
generally deposited at fairly slow rates, usually of the order
of a few hundred microns per hour.
 Designing safer nanoparticles
Nanomaterial
synthesis

Redesign Test Characterizing

Material Properties
Nano-particles
Structure/Property Relationships:
•TEM
Physico-chemical properties and hazards •SEM
Nanoparticles have widely tunable properties - the key is to •XRD
enhance performance and safety at the same time
•AFM
SEM: Scanning Electron Microscope
a type of electron microscope that
produces images of a sample by
scanning it with a focused beam
of electrons. The electrons interact
with atoms in the sample,
producing various signals that
contain information about the
sample's surface topography and
composition.
SEM
 How do we get an image?
Electrons in
Electrons out
or: x-rays out

O In brief: we shoot high-energy electrons and analyze the

out coming electrons/x-rays
 Signals from the sample
Incoming electrons
Secondary electrons
Auger electrons
Backscattered Cathodo-
electrons luminescence (light)
X-rays

Sample MENA3100
 Secondary electrons (SE)
O Generated from the collision between the
incoming electrons and the loosely
bonded outer electrons
O Low energy electrons (~10-50 eV)
O Only SE generated close to surface escape
(topographic information is obtained)
O Number of SE is greater than the number
of incoming electrons

MENA3100
 The most versatile instrument for a
materials scientist?
What can we study in a SEM?
O Topography and morphology
O Chemistry
O Crystallography
“Easy” sample
preparation!!
O Orientation of grains
O In-situ experiments:
“Big” samples!
O Reactions with atmosphere
O Effects of temperature
 Depth of focus
Optical microscopy vs SEM

Screw length: ~ 0.6 cm

• A SEM typically has orders of magnitude better depth of focus

than a optical microscope making SEM suitable for studying
rough surfaces
• The higher magnification, the lower depth of focus
 Topography and morphology
O High depth of focus
SEM Examination of surface
conditions and other physical
properties of commonly used
stainless steel acupuncture needles

SEM
Examination of
defects in steel
 TEM: Transmission Electron Microscope
Transmission electron microscopy (TEM) is a microscopy technique
in which a beam of electrons is transmitted through an ultra-thin
specimen, interacting with the specimen as it passes through it.

TEM forms an image by accelerating a beam of electrons that pass

through the specimen. Electrons are accelerated to 100 KeV or
higher (up to 1MeV), projected onto a thin specimen (less than 200
nm) by means of the condenser lens system, and penetrate the
sample thickness either undeflected or deflected.
The greatest advantages that TEM offers are the high magnification
ranging from 50 to 106 and its ability to provide both image and
diffraction information from a single sample.
Twinning in Gold nano-particles