Nanomaterials

CR-259

Debasish Sarkar, Ph.D

Associate Professor,
Department of Ceramic Engineering
NIT, Rourkela, Orissa, India
Email: dsarkar@nitrkl.ac.in
 Lecture 1
Introduction of Nanomaterials
 The Scale of Things – Nanoworld and More
Things Natural Things Manmade
10-2 m 1 cm
10 mm
MicroElectroMechanical devices
10 -100 mm wide
Human hair
~ 10-50 mm wide 10-3 m 1 millimeter (mm)
Ant
~ 5 mm

10-4 m 0.1 mm
Head of a pin
100 mm 1-2 mm
Red blood cells
Microworld
with white cell
~ 2-5 mm
10-5 m 0.01 mm
10 mm

10-6 m 1 micrometer (mm)

10-7 m 0.1 mm
100 nm
Nanotube electrode Nanotube transistor
~10 nm
Nanoworld

diameter
ATP synthase 0.01 mm
10-8 m
10 nm

10-9 m 1 nanometer (nm)

DNA Carbon nanotube

~2-1/2 nm diameter ~2 nm diameter
Atoms of silicon Quantum corral on copper surface
spacing ~tenths of nm 10-10 m 0.1 nm Corral diameter 14 nm
 Why “nano”
Nanomaterials have superior properties than the
bulk substances :
 Mechanical strength
 Thermal stability
 Catalytic activity
 Electrical conductivity
 Magnetic properties
 Optical properties
 …….

A wide range of applications:

Quantum electronics, nonlinear optics, photonics, sensing,
information storage and processing, adsorbents, catalysis, solar
cells, superplastic ceramics…

New fields:
Nanofabrication, nanodevices, nanobiology, and nanocatalysis
 Nanotechnology and Nanoscience
Nanotechnology:
• A technology
• Design, production, characterization, and
applications of Nanostructured materials
• Also, fundamental understanding of
physical properties and phenomena

Nanoscience:
• Study on fundamental relationships between physical
properties and material dimensions on the nanometer
scale
Study of ‘Nanomaterials’ a gap between these two
 What is Nanomaterial ?
What is nano-material?

Definition: Nanomaterials is the study of how materials behave when their

dimension are reduced to the nanoscale

Two important things:

A. Nanoscale: 1-100 nm
B. Material behaviors: nano-level behaviors and macro-level behaviors
Size of nano
1 nm = 10-3 mm = 10-6mm = 10-9 m = 10-9 yard
Some examples of size from macro to molecular

Size(nm) Examples Terminology

0.1-0.5 Individual chemical bonds Molecular/atomic
0.5-1.0 Small molecules, pores in zeolite Molecular
1-100 Proteins, DNA, inorganic nanoparticles Nano
103-104 Microfluidic channels, MEMS, Devices on Si chip, living Micro
cells (bacteria:1mm; yeast:5mm), human hair (50mm)
>104 Normal bulk matter Macro
 Nanostructured Materials
Classification:

• Nanoparticles (including quantum dots) exhibit quantum size effects

• Nanorods and nanowires
• Thin films
• Bulk materials made of nanoscale building blocks or consisting of
nanoscale nanostructures
 Synthesis of Nanostructure
Accomplished by two approaches.

-- “Bottom Up” method where small building blocks are

produced and assembled into larger structures.
examples: chemical synthesis, laser trapping, self
assembly, colloidal aggregation, etc

-- “Top Down” method where Large object are modified to

give smaller features.
examples: film deposition and growth, nano imprint /
lithography, etching technology, mechanical polishing
Two Different Approaches to Nanofabrication

 Top ⇨ Down:
• Start with the bulk material and
“cut away material” to make the
what you want

 Bottom ⇨ Up:
• 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
Top-down versus Bottom-up
Bottom-up Process - What to control

+
• Colloidally stable nanoparticles
• Reproducible
• Adaptable surface properties
• Easy + cheap
•(Biocompatible or biodegradable systems)
 How to study Nanomaterials

Part I
Basic Materials Science Principles

Materials Processing Microstructure Properties Applications

Part II Part III

 Feature of Nanomaterials
• Nanostructured materials are single phase or multiphase polycrystalline
solids with a typical average size of a few nanometers (1nm = 10-9m),
typically less than 100nm
• The grain sizes are so small, a significant volume fraction of the atoms
resides in grain boundaries.
• Material is characterized by a large number of interfaces in which the atomic
arrangements are different from those of crystal lattice.
• Exhibit different properties from bulk structures
• A nanocrystal, 30-40% atoms in the surface, comprises of two components:
Crystalline Component (C ), and Intercrystalline Component (IC)
•Surface atoms suffer from not so regular positions/distribution of
coordinate/electronic charges
•A redistribution occurs to attend equilibrium configuration (quantum
confinement)
Nanostructured materials can have significantly different
properties, depending on the chosen fabrication route
Grain Boundary vs Particle Diameter
Nanoparticle Synthesis Strategies

 Liquid-phase synthesis
 Gas-phase synthesis
 Vapor-phase synthesis

Challenge: The control of nano particle sizes,

distributions and their locations
Liquid-Phase Synthesis

• Coprecipitation
• Sol-gel Processing
• Microemulsions
• Hydrothermal/Solvothermal Synthesis
• Microwave Synthesis
• Sonochemical Synthesis
• Template Synthesis
• Biomimetic Synthesis
Gas-Phase Synthesis

• Supersaturation achieved by vaporizing material into a

background gas, then cooling the gas

– Methods using solid precursors

• Inert Gas Condensation
• Pulsed Laser Ablation
• Spark Discharge Generation
• Ion Sputtering

– Methods using liquid or vapor precursors

• Chemical Vapor Synthesis
• Spray Pyrolysis
• Laser Pyrolysis/ Photochemical Synthesis
• Thermal Plasma Synthesis
• Flame Synthesis
• Flame Spray Pyrolysis
• Low-Temperature Reactive Synthesis
 Vapor-Phase Synthesis
• Same mechanism as liquid-phase reaction

• Elevated temperatures + vacuum (low concentration of growth)

• Vapor phase mixture rendered thermodynamically unstable

relative to formation of desired solid material
– “supersaturated vapor”
– “chemical supersaturation”
– particles nucleate homogeneously if
• Degree of supersaturation is sufficient
• Reaction/ condensation kinetics permit

• Once nucleation occurs, remaining supersaturation is relieved by

condensation, or reaction of vapor-phase molecules on resulting
particles. This initiates particle growth phase.

• Rapid quenching after nucleation prevents particle growth by

removing source of supersaturation, or slowing the kinetics.
 Synthesis of Nanomaterials
Different examples of the preparation of nanostructured materials

Top Down –
Solid Mechanical alloying 3D
Solid High Energy Ball Milling 3D

Bottom Up –
Vapor Inert Gas Condensation 3D
Liquid Sol- Gel 3D
Vapor Chemical Vapor Deposition 3D,2D
Vapor Physical Vapor Deposition 1D
Solid Solid state reaction 3D
Liquid Sonochemical method 3D
Liquid Electrophoretic deposition 1D, 3D
Vapor Plasma Processing 3D
 How temperature affect the material characteristics?
Supercooling is the process of lowering the temperature of a liquid or a gas
below its freezing point, without it becoming a solid.

As a supercooled liquid is cooled to

lower temperatures, its viscosity
increases and the molecules which
comprise it move more and more
slowly.

At some temperature the molecules

will be moving so slowly that they do
not have a chance to rearrange
significantly before the temperature is
lowered further.
Tg depends upon the cooling rate. Typical cooling rates in laboratory experiments are 0.1-100 K/min.

No, glass is not a mineral

Glass does not have a crystal lattice structure. It is best described as an
"amorphous solid" meaning that its atoms are rigidly fixed, but not in an orderly
pattern
Difference Between Amorphous and Crystalline Phase

Micrographs of single crystalline (left) and amorphous (right) materials. Each ‘blob’
represents an atom in this TEM – 4 dots correspond to 1nm for this particular material
 Application of Nanomaterials

No Limitation……..No Specific…….
Just reduce the size (1-100nm),
appear more number of exposed
atoms and achieve different properties
from BULK
Research
World market
Suggestive Books:
1. Gunter Schmid, “Nanoparticles: From Theory to Applications”, Wiley-VCH
Verlag GmbH & Co., 2004.
2. C C Koch, Nanostructured Materials: Processing, Properties and
Applications,William Andrew Publishing, NY, USA, 2007
3. J H Fendler, Nanoparticles and Nanostructured Films, Wiley-VCH, Germany
4. Z L Wang, Characterization of Nanophase Materials, Wiley-VCH,Germany

Course Details and Grading System

Classes will be covered as according to the Course Structure

Marks Assignment Attendance

20 14 6
30 Mid Term (15 x 2 = 30)
50 End Term (25 x 2 = 50)