Unit – V Nanomaterials
Classification of nanomaterials:
Nanomaterials can be defined as materials possessing
dimensions in between 1-100nm at least in one
dimension.
Zero-dimensional (0D), One-dimensional (1D), Two-
dimensional (2D) and Three dimensional
(3D)nanomaterials.
zero-dimensional (0D) nanomaterials all the dimensions
are measured within the nanoscale (no dimensions are
larger than 100nm). Most commonly, 0D nanomaterials
are nanoparticles.
In one-dimensional nanomaterials (1D)
one dimension is outside the nanoscale and the other two
dimensions are less than 100nm. This class includes
nanotubes, nanorods, and nanowires.
In two-dimensional nanomaterials (2D), two
dimensions are outside the nanoscale and the other
dimension is less than 100nm. This class exhibits
plate-like shapes and includes graphene, nanofilms,
nanolayers, and nanocoatings.
Three-dimensional nanomaterials (3D) are materials
that are not confined to the nanoscale in any
dimension. This class can contain bulk powders,
bundles of nanowires, and nanotubes as well as multi
The key differences between nanomaterials and bulk
materials
Two principal factors cause the properties of
nanomaterials to differ significantly from other
materials:
1)increased relative surface area, and
2) quantum effects.
These factors can change or enhance properties
such as reactivity, strength and electrical
characteristics.
Nanomaterials have a relatively larger surface area
when compared to the same volume (or mass) of the
material produced in a larger form. To understand this
we can use a cube as a more realistic geometrical
representation of a quantum dot.
Thus nanoparticles have a
much greater surface area
compared with larger
particles. It makes these
materials more chemically
reactive
Quantum effects:
According to band theory, solid materials have energy bands and
isolated atoms possess discrete energy levels. Nanomaterials are
in intermediate to the above two cases as shown in figure.
For nanomaterials, if the dimensions of potential wells are of the
order of the de-Broglie wavelength of electrons or mean free path
of electrons, then the electrons will behave as quantum particles
and the energy levels of the electrons will change (not remain
continuous but discrete set of energy levels) and ‘e’ will remain
confined to a small region.
Thus when size of the system is small quantum effects are
dominating.
This can affect the
optical, electrical and
magnetic and physical
properties of materials
Synthesis of nanomaterials:
There are two approaches to produce nanomaterial.
Top-down: Top down approach refers to slicing or
successive cutting of a bulk material to get nano-
sized particle. Example: Ball milling, physical vapor
deposition, pulsed laser deposition.
Bottom-up: Bottom up approach refers to the
building up of a material from the bottom: atom by
atom, molecule by molecule or cluster by cluster.
Example: sol-gel processing, chemical vapor
deposition.
Top-down methods:
Ball milling:
Ball milling also called mechanical crushing. The System consists of
one turn disc and two or four bowls rotates in opposite direction.
It is made of stainless steel chamber and several steel or silicon
carbide balls to rotate inside the mill.
When the mill rotates, balls are picked up by the mill wall and rotate
around the wall due to centrifugal force leading to grinding of material
due to frictional effect.
On the other hand there is also reverse rotation of disc
with respect to mill which applies centrifugal force in
opposite direction leading to transition of balls on
opposite walls of mill giving impact effect
In a ball mill most of the reduction is carried out by impact. The
grinding is also carried out with different fluids like ethylene
glycol, butanol and water.
The size of the nanoparticle obtained in this process depends on
many factors like grinding hours, the weight ratio of the steel
balls, fluid media etc.
Ball milling can be used to prepare a wide range of elemental and
oxide powders. For example, iron with particle sizes 10-30nm
can be prepared. A variety of intermetallic compounds based on
nickel, aluminum can be prepared. This method is suitable for
both and wet and dry grinding processes. Since it is a closed
system toxic substances can be milled. There are certain
disadvantages with ball milling method. The nanoparticles
prepared with ball milling are contaminated with material of the
balls. Most
Physical vapor deposition (PVD): (thermal evaporation
environmentally friendly vacuum
deposition techniques consisting of
three fundamental steps (Figure): •
Vaporization of the material from a
solid source assisted by high
temperature vacuum or gaseous
plasma.
• Transportation of the vapor in
vacuum or partial vacuum to the
substrate surface. •
Condensation onto the substrate to
generate thin films.
PVD is used in a variety of applications, including
fabrication of microelectronic devices,
interconnects, battery and fuel cell electrodes,
diffusion barriers, optical and conductive coatings,
and surface modifications
Advantages: 1) Atomic level control of chemical
composition 2) It doesn’t require special or toxic
precursors as used in CVD process. Limitations: 1)
Line of sight deposition 2) Low deposition rate 3)
Process requires high temperatures.
Approach
Step 1: Formation of different stable solutions of the alkoxide or
Metal solution. (the sol).
Step 2: Gelation resulting from the formation of an oxide or alcohol
bridged net-work (the gel) by a polycondensation reaction.
Step 3 : Aging of the gel during which the polycondensation
reactions continue until the gel transforms into a solid mass.
(this is accompanied by the contraction of the gel network and
expulsion of solvent from gel pores).
Step 4: Drying of the gel, when water and other volatile liquids are
removed from the gel network.
If isolated by thermal evaporation, then the product is Xerogel.
If it is (the solvent is extracted) under supercritical conditions,
the product is an aerogel.
Step 5: Dehydration during which surface bound M-OH groups
Are removed. Achived by calcining at temp around 800c.
Step 6: Densification and decomposition of the gel at high temp.
The pores of the gel network are collapsed.
The materials are shaped into the desired form like powder, thin flim…
Steps (for Metal oxide compound)
The metal (substance) precursor goes through
1.(Rapid) Hydrolysis ---- to produce the metal hydroxide solution.
[Link] ----- to form 3D gels
[Link] ---- depending on the mode of drying of gel,
Aerogel or Xerogel can be the final product.
4. dehydration.
APPLICATIONS
ADVANTAGES
Chemical Vapour Deposition method:
Precipitation
Cation Solution Anion Solution
Chemical reaction,
Nucleation and
Crystal growth
Precipitation
Centrifuging
Washing
Filtration
Calcination 30
Precipitation
Precursor solutions are prepared by using water
or suitable medium.
A chemical precipitation process consists of
three main steps; (1) chemical reaction, (2)
nucleation and (3) crystal growth.
Chemical reaction occurs among the precursors
Nucleation is initiated by spontaneous
agglomeration of ions
Crystal growth occurs due to diffusion and the
surface reaction.
31
Precipitation
pH of the solution is adjusted to 7 followed by
centrifuge.
After the precipitation, solid mass is washed and
filtered with deionized water.
After successive washes and filtrations, final
powder is collected and gradually dried by
heating.
Chemical precipitation is not a controlled
process in terms of reaction kinetics, the solid
phase nucleation and growth processes. 32
Precipitation
Drawbacks: Non-homogenious particle size
Agglomeration.
Requirements to obtain almost uniform
nanoparticles
(i) High degree of supersaturation,
(ii) Uniform spatial concentration distribution
inside a reactor and
(iii) Uniform growth time for all particles or
crystals. 33
Characterization of nanomaterials:
The commonly used techniques are
Transmission Electron Microscopy (TEM),
Scanning Electron Microscopy (SEM),
X-Ray diffraction (XRD) etc.
X-Ray diffraction (XRD):
X- Ray diffraction is a versatile, non-destructive technique
that reveals detailed information about
the crystallographic structure, composition and size of
materials.
While passing through the crystal x-rays are diffracted by
lattice planes
The Bragg’s condition 2d sinθ = nλ. Where λ is the
wavelength of X-Rays, d is the distance between crystal
planes and θ is the angle of diffraction. The diffraction pattern
is shown in the figure.
The Scherrer
equation can be
written as:
τ - mean size of the ordered
crystallite,
K is shape factor with a value close
to unity, but varies with the actual
shape of the crystallite;
β is the line broadening i.e. Full
width at half the maximum intensity
(FWHM);
θ is the Bragg angle
Scanning Electron Microscope (SEM):
a focused beam of electrons is used to create a magnified
image of a sample. The electron beam is scanned in a
regular pattern across the surface of the sample and the
electrons that come out of the sample are used to create
the image.
[Link] gun consisting of cathode and anode. Electrons
are emitted from heated cathode; a positively charged
electrode (anode) attracts the electrons and accelerates
them into an energetic beam.
2. A series of electromagnetic lenses (condenser lenses)
are used to reduce the diameter of the electron source and
to place a small, focused beam of electrons (or spot) onto
the specimen.
[Link] scan coils used to systematically scan across the
object being viewed.
4. The main part of the machine
(where the object is scanned) is
contained within a sealed
vacuum chamber.
[Link] from the beam hit
the surface of the object and
bounce off it.
6. A detector registers these
scattered electrons from the
specimen and turns them into a
picture.
7. A hugely magnified image of
the object is displayed on a TV
screen
Working:
In a scanning electron microscope, the specimen is exposed to a
narrow electron beam from an electron gun, which rapidly moves over
or scans the surface of the specimen. This causes the release of a
shower of secondary electrons and other types of radiations from the
specimen surface. The intensity of these secondary electrons depends
upon the shape and the chemical composition of the irradiated object.
These electrons are collected by a detector, which generates electronic
signals. These signals are scanned in the manner of a television system
to produce an image on a cathode ray tube (CRT) or by digital camera.
Applications:
1) SEM is used to study the topographical, morphological and
compositional information
2)SEM can detect and analyze surface fractures, provide information in
microstructures
3) SEM examine surface contaminations and reveal information about
chemical compositions
4) SEM provide qualitative chemical analyses and identify crystalline
structures.
Limitations: 1) SEM works in vacuum – only solid state samples can be
characterized; working with liquids is very challenging.
2) The microscope chamber and loadlock have relatively small size - so
the maximal specimen size is tens of centimeters only, cannot be
suitable for large size samples.
3) Electron beam can damage and even destroy organic and biological
samples. So those samples might require special sample preparation
(freezing or coating).
Topography: features on the surface
Morphology: a particular form, shape or structure
Transmission electron microscopy (TEM): In Transmission
Electron Microscope a beam of high energy electrons
transmits through a specimen to produce a magnified image
of an object.
The TEM is made of several main components: electron
source or electron gun, condenser lenses, Vacuum chamber,
objective lens, projection lens and fluorescent screen or TV
monitor as shown in the figure.
1. Electron gun (consisting of cathode and anode) produces
the beam of electrons.
1. Electromagnetic coils (condenser lenses) concentrates
and focus the electrons as a more powerful beam onto
the specimen.
2. The electron beam passes through the specimen which is
kept in a vacuum chamber and "picks up" an image of it.
3. The Objective lens is used to magnify the image.
4. The projection lens used to project the magnified image
onto the phosphorus screen.
6. The image
becomes
visible when
the electron
beam hits a
fluorescent
screen at the
base of the
machine or can
be viewed
directly on a TV
monitor
Working:
The Electron gun uses electromagnetic coils and high
voltages (typically from 100 to 400kV) to accelerate the
electrons to very high speeds. The specimen to be
examined is prepared as an extremely thin dry film is
placed in a vacuum chamber in the path of electrons.
The electrons transmit through the specimen and out
the other side, where objective lens and projection lens
magnify and focus them to form an image on screen
(for immediate viewing) or on a photographic plate (for
making a permanent record of the image).
TEM Analysis:
There can be
[Link] electrons: The intensity of the unscattered “e”s
is inversely proportional to the thickness of the sample.
2. Elastically Scattered ”e”: They follow Bragg’s law, 2d sinθ =nλ
By collecting the data, one can get information about the orientation,
atomic arrangement and Phase present.
3. Inelastically Scattered “e”: Give information regarding compositional
and bonding.
Applications:
1)TEM provides topographical, morphological, compositional and
crystalline information of the specimen.
2)TEMs effectively magnify the image by a million times to a
molecular level, making it possible to analyze structure and
texture.
3)TEMs can be used in semiconductor analysis in production and
the manufacturing of computer and silicon chips.
Limitations:
1)TEMs are large and very expensive.
2)Laborious sample preparation.
3)Samples are small enough to fit in the chamber and are to be
electron transparent and able to tolerate the vacuum.
4)Images produced are black and white
SEM TEM
Type of electrons •Scattered, scanning •Transmitted electrons
electrons
High tension •~1–30 kV •~60–300 kV
Specimen thickness •Any •Typically <150 nm
Type of info •3D image of surface •2D projection image of
inner structure
Max. magnification •Up to ~1–2 million times •More than 50 million
times
Max. FOV •Large •Limited
Optimal spatial •~0.5 nm •<50 pm
resolution
Image formation •Electrons are captured •Direct imaging on
and counted by fluorescent screen or PC
detectors, image on PC screen with CCD
screen
Operation •Little or no sample •Laborious sample
preparation, easy to use preparation, trained users
required