Nano Materials
Nano Materials
Nano Materials
All materials are composed of grains, which in turn comprise many atoms. These grains can be
visible or invisible to the naked eye, depending on their size. Conventional materials have grains
varying in size anywhere from hundreds of microns to centimeters. Nanomaterials, sometimes
called nanopowders when not compressed, have grain sizes in the order of 1-100 nm in at least
one coordinate and normally in three.
Size of nano
Classification:-
Dimension Examples
Phase composition
Single-Phase solids Crystalline, amorphous particles and layers, etc.
Semiconductor nanoparticles or quantum dots are normally prepared chemically via solution-
based routes, often at elevated temperatures and sometimes at elevated pressures (hydro-or
solvo-thermal methods). The most commonly studies quantum dots include metal sulfide or
metal selenide compounds such as CdS, CdSe, InSe, PbS, ZnS, etc.
Surface melting assisted oxidization can be used to directly grow metal oxide nanostructures
without the presence of solution or vapour. Nanostructures of metal oxides such as ZnO, MgO,
TiO2 and SnO2 etc are examples for 2 dimension quantum wires.
Nanolayers
Nanolayers are one of the most important topics within the range of nanotechnology. Through
nanoscale engineering of surfaces and layers, a vast range of functionalities and new physical
effects (e.g. magnetoelectronic or optical) can be achieved. Furthermore, a nanoscale design of
surfaces and layers is often necessary to optimise the interfaces between different material
classes (e.g. compound semiconductors on silicon wafers), and to obtain the desired special
properties. Some application ranges of nanolayers and coatings are summarised in table.
Single-phase solids:-
CuS amorphous nanoparticles are example for single-phase solids, and its inhibit the
proliferation of cancer cells rather than normal cells.
Multi-phase solids:-
A method for coating magnetic nanoparticles with a very thin layer of gold. Because many
biological markers and linkers have been adapted to attach to gold surfaces, a functional coating
of gold allows nanoparticles of other materials to be used with the established markers and
linkers. Magnetic nanoparticles are of particular interest for in vivo imaging and treatment
operations.
Applications:-
(1) Image enhancement in magnetic based diagnostics (such as MRI or other proprietary
techniques).
(2) Cancer imaging and treatment.
Advantages:-
(1) Avoids direct contact between biological tissue and the core nanoparticle material
(2) Permits a wide range of magnetic materials to be used in biological tissue
(3) Simple, rapid, and relatively inexpensive chemical process
Multi-phase system:-
Aerogel is a manufactured material with the lowest bulk density of any known porous solid.[1] It
is derived from a gel in which the liquid component of the gel has been replaced with a gas. The
result is an extremely low-density solid with several remarkable properties, most notably its
effectiveness as a thermal insulator. It is nicknamed frozen smoke, solid smoke, solid air or blue
smoke due to its translucent nature and the way light scatters in the material; however, it feels
like expanded polystyrene to the touch.
Eq:- Carbon aerogels are composed of particles with sizes in the nanometer range, covalently
bonded together. They have high porosity over 50%, with pore diameter under 100 nm and
surface areas ranging between 400-1000 m2/g.
Nanotube (carbon):- 1D fullerene (a convex cage of atoms with only hexagonal and/or
pentagonal faces) with a cylindrical shape. Sheets of graphite rolled up to make a tube. Graphitic
layers seamlessly wrapped to cylinders. A new class of carbon materials consists of closed (SP 2
hybridized) carbon chains, organized on the basis of 12 pentagons and any number of hexagons.
More generally, any tube with nanoscale dimensions, e.g., a boron-nitride-based tube.
Quantum dot (QD):- Nanometer-scale “boxex” for selectively or releasing electrons; the size of
the box can be from 30 to 1000 nm, but more advanced only 1-100 nm across.
Nanofoam:- The new structure was created when physicists bombarded a carbon target with a
laser capable of firing 10000 pulses a second. As the carbon reached temperatures of around
10000oC, it formed an interesting web of carbon tubes, each just 1 nm in diameter.
Nanoclusters:- Nanoscale metal and semiconductor particles are of interest because they mark a
material transition range between quantum and bulk properties. With decreasing particle size,
bulk properties are lost as the continuum of electronic states becomes discrete and as the fraction
of surface atoms becomes large. The electronic and magnetic properties of metallic nanoparticles
and nanoclusters have new characteristics that can be utilized in novel applications.
Manufacturing Process
Vapor condensation:-
This approach is used to make metallic or metal oxide ceramic nanoparticles. It involves
evaporation of solid metal followed by rapid condensation to form nanosized clusters that settle
in the form of a powder. Various approaches to vaporize the metal can be used and variation of
the medium into which the vapor is released affects the nature and size of the particles. Inert
gases are used to prevent oxidation when creating metal nanoparticles, whereas a reactive
oxygen atmosphere is used to produce metal oxide ceramic nanoparticles. The main advantage of
this approach is low contamination levels. Final particle size is controlled by variation of
parameters such as temperature, gas environment and evaporation rate.
In the pulsed-laser deposition (PLD) method, high power laser pulses are used to
evaporate from a target surface such that the stoichiometry of the material is preserved in the
interaction. As a result, a supersonic jet of particles (plume) is directed normal to the target
surface. The plume expands away from the target with a strong forward directed velocity
distribution of different particles. The ablated species condense on the substrate placed opposite
to the target.
The main advantages of PLD are its ability to create high-energy source particles,
permitting high quality film growth at low substrate temperatures, typically ranging from 200 to
800oC, its simple experimental setup, and operation in high ambient gas pressures in the 10 -5-10-1
Torr range.
Sol-Gels:-
The sol-gel process is a wet-chemical technique used primarily for the fabrication of materials
starting from a chemical solution which acts as the precursor for an integrated network (or gel) of
either discrete particles or network polymers. Typical precursors are metal alkoxides and metal
chlorides, which undergo various forms of hydrolysis and polycondensation reactions. The
formation of a metal oxide involves connecting the metal centers with oxo (M-O-M) or hydroxo
(M-OH-M) bridges, therefore generating metal-oxo or metal-hydroxo polymers in solution.
Thus, the sol evolves towards the formation of a gel-like diphasic system containing both a liquid
phase and solid phase whose morphologies range from discrete particles to continuous polymer
networks.
Removal of the remaining liquid (solvent) phase requires a drying process, which is
typically accompanied by a significant amount of shrinkage and densification. The rate at which
the solvent can be removed is ultimately determined by the distribution of porosity in the gel.
The ultimate microstructure of the final component will clearly be strongly influenced by
changes imposed upon the structural template during this phase of processing. Afterwards, a
thermal treatment, or firing process, is often necessary in order to favor further polycondensation
and enhance mechanical properties and structural stability via final sintering, densification and
grain growth. One of the distinct advantages of using this methodology as opposed to the more
traditional processing techniques is that densification is often achieved at a much lower
temperature.
The precursor sol can be either (i) deposited on a substrate to form a film (e.g., by dip
coating or spin coating), (ii) cast into a suitable container with the desired shape or (iii) used to
synthesize powders (e.g., microspheres, nanospheres). The sol-gel approach is a cheap and low
temperature technique that allows for the fine control of the product’s chemical composition.
Even small quantities of dopants, such as organic dues and rare earth elements, can be introduced
in the sol and end up uniformly dispersed in the final product. It can use used as a means of
producing very thin films of metal oxides for various purposes.
Example
Electrodeposition has been used for a long time to make electroplated materials. By carefully
controlling the number of electrons transferred, the weight of material transferred can be
determined in accordance with Faraday’s law of electrolysis. This states that the number of
moles of product formed by an electric current is directly proportional to the number of moles of
electron supplied. Since the quantity of electricity passed (measured in coulombs) is current
(amps) x time (sec) and Faraday’s constant F (96485 coulombs is currently the most accurate
estimate) is the charge per mole of electrons (1 mole of electrons = 96485 coulombs), then the
number of moles of electron is charged supplied/F.
Specific Advantages of electro-deposition for the synthesis of the nano scale materials:-
The synthesis of naonmaterial’s requires an atmospheric deposition process and extreme control
over the deposition. Vapor deposition techniques have been used almost exclusively to produce
these materials. The fact that electrochemical deposition, also being at atomic deposition process,
can be used to synthesis nanocomposites, has generated a great deal of interest in recent years.
The obvious advantage of this century-old process of ED is as follows.
a. Rapidity
b. Low cost
c. Free from porosity
d. High purity
e. Industrial applicability
f. Potential to overcome shape limitations or allows the production of free-standing parts with
complex shapes.
e. Higher deposition rates.
f. Produce coatings on widely differing substrates.
g. Ability to produce structural features with sizes ranging from nm to μm.
h. Easy to control alloy composition.
i. Ability to produce compositions unattainable by other techniques.
j. The possibility of forming of simple low-cost multilayer’s in many different systems, e.g.
Cu/Ni, Ni/Ni-P etc.
k. No Postdeposition treatment.
Ball milling:-
These early nanomaterials were made by a simple method called ball milling, which is better
described as mechanical crushing. In this process, small balls are allowed to rotate around the
inside of a drum and drop with gravity force on to a solid enclosed in the drum. Ball milling
breaks down the structure into nanocrystallites. The significant advantage of this method is that it
can be readily implemented commercially. Ball milling can be used to make a variety of new
carbon types, including carbon nanotubes. It is useful for preparing other types of nanotubes,
such as boron nitride nanotubes and a wide range of elemental and oxide powders. For example,
iron with grain sizes of 13-30 nm can be formed. Other crystallites, such as iron nitrides, can be
made using ammonia gas. Ball milling is the preferred method for preparing metal oxides. Their
used range from pigments to capacitors to coatings to inks. All of these applications rely on the
increased surface to bulk ratio, which alters the chemical properties of the metal oxide.
Natural nanoparticles:-
Some of the most successful materials, called zeolites, have been synthesized by conventional
chemistry, and operate at nanopore size. Phyllosilicates, which consist of layers of silicate
tetrahedral and aluminium octahedral, have potential but consist of many individual stacked
plates. There have been some interesting new developments in altering pore spaces. In a novel
approach, quaternary ammonium salts (surfactants) which form micelles are used as centers
around which silica species condense. These templates are removed by heating to create a
continuous network of pores that mimic the size and shape of the template. The advantage of this
approach is that the pore volume is controlled by the volume fraction of the template
constituents, and the pore size is controlled by the size of the surfactant micelles. This approach
has been used with pillared clays. Interestingly, the porosity of the products depends on the
quantity rather than the size of the surface of the surfactant molecules. These materials have been
called composite clay nanostructures. The quaternary ammonium salts form micelles in the
interlayer regions and the pillaring agents form pillar materials beside them because of the
affinity of surfactant molecules for the surface of the pillar precursors. The micelles act as
templates, preventing the intercalated framework from collapsing during the dehydration process
in which the framework hardens. The surfactants can be removed at temperatures between 150
and 250oC leaving a highly porous product. One interesting applications is to fill these new pores
with organic materials, thereby forming nanosilicocarboalumina composites.
Different surfactants can be used. It appears that the size of the molecule is important, but
in the reverse of what would natively be expected, it is found that larger surfactant molecules
produce smaller pores. A surfactant with large n is expected to have a much stronger interaction
with precursor surface compared to a surfactant with small n. The strong interaction must
influence the formation and configuration of the micelles. The mean diameter of the framework
pores decreases with n because the stronger interaction results in micelles with a smaller
diameter.
Particle size analysis is used to characterize the size distribution of particles in a given
sample. Particle size analysis can be applied to solid materials, suspensions, emulsions and even
aerosols. There are many different methods employed to measure particle size. Some particle
sizing methods can be used for a wide range of samples, but some can only be used for specific
applications. It is quite important to select the most suitable method for different samples as
different methods can produce quite different results for the same material.
Particle size analysis is a very important test and is used for quality control in many
different industries. In just about industry where milling or grinding is used, particle size is a
critical factor in determining the efficiency of manufacturing process and performance of the
final product.
Laser diffraction has become one of the most commonly used particle sizing methods,
especially for particles in the range of 0.5 to 1000 microns. It works on the principle that when a
beam of light (a laser) is scattered by a group of particles, the angle of light scattering is
inversely proportional to a particle size (smaller the particle size, the larger the angle of light
scattering). Laser diffraction has become very popular it can be applied to many different sample
types, including dry powders, suspensions, emulsions and even aerosols. It is also a very fast,
reliable and reproducible technique and can measure over a very wide size range.
Applications:-
Some of the important applications and technologies based on the nanomaterials are the
following:
Nanopowders offer a unique opportunity for semiconductor packaging. Alumina and silica
powders can be used for electronic chips, to dissipate heat faster. Nanoparticles can be added to
polymers and adhesives and make them electrically conductive, and the melting point of metals
can be significantly reduced if the particles are small enough, giving more freedom to
microelectronic manufacturing processes. In addition, the residual magnetism of a magnet and
the band gap of a semiconductor strongly depend on the size of the component crystals.
(2). Nanocomposites:-
Experimental work has generally shown that virtually all types and classes of nanocomposite
materials lead to new and improved properties, when compared to their macrocomposite
counterparts. Therefore, nanocomposites promise new applications in many fields such as
mechanically-reinforced lightweight components, non-linear optics, battery cathodes and ionics,
nanowires, sensors and other systems.
Nanocarbon:
Nanocarbons are Carbon-based materials that can be bonded at the molecular level in
differing ways to achieve unique properties. This family of materials includes Nanotubes,
buckytubes, fullerenes & more.
The development into nanocarbon manipulation & control is vital for the production &
creation of nanomachines & nanobots. Through the successful creation of molecular level
machines we will be able to program these machines to do the molecular manipulation for us, the
beginning of the molecular age.
Fullerenes:-
The structure of C60 is a truncated (T=3) icosahedran, which resembles a soccer ball of
the type made of twenty hexagons and twelve pentagons, with a carbon atom at the vertices of
each polygon and a bond along each polygon edge. The vander walls diameter of a C60 molecule
is about 1 nanometer (nm). The nucleus to nucleus diameter of a C 60 molecule is about 0.7 nm.
The C60 molecule has two bond lengths. The 6:6 ring bonds (between two hexagons) can be
considered “double bonds” and are shorter than the 6:5 bonds (between a hexagon and a
pentagon). Its average bond length is 1.4 angstroms.
Structure:-
The bonding in carbon nanotubes is SP 2, with each atom joined to three neighbors, as in
graphite. The tubes can therefore be considered as rolled-up grapheme sheets (grapheme is an
individual graphite layer).
Synthesis:-
The arc-evaporation method, which produces the best quality nanotubes, involves passing
a current of about 50 amps between two graphite electrodes in an atmosphere of helium. This
causes the graphite to vaporise, some of it condensing on the walls of the reaction vessel and
some of it on cathode. It is the deposit on the cathode which contains the carbon nanotubes.
Single-walled nanotubes are produced when Co and Ni or some other metal is added to
the anode. It has been known since the 1950s, if not earlier, that carbon nanotubes can also be
made by passing a carbon-containing gas, such as a hydrocarbon, over a catalyst. The catalyst
consists of nano-sized particles of metal usually Fe, Co or Ni. These particles catalyze the
breakdown of the gaseous molecules into carbon, and a tube then begins to grow with a metal
particle at the tip.
It was shown in 1996 that single-walled nanotubes can also be produces catalytically. The
perfection of carbon nanotubes produced in this way has generally been poorer than those made
by arc-evaporation, but great improvements in the technique have been made in recent years. The
big advantage of catalytic synthesis over arc-evaporation is that it can be scaled up for volume
production. The third important method for making carbon nanotubes involves using a powerful
laser to vaporize a metal-graphite target. This can be used to produce single-walled tubes with
high yield.
Properties:-
The strength of the SP2 carbon-carbon bonds gives carbon nanotubes amazing mechanical
properties. The stiffness of a material is measured in terms of its Young’s modulus, the rate of
change of stress with applied strain. The young’s modulus of the best nanotubes can be as high
as 1000 GPa which is approximately 5 x higher than steel. These properties, coupled with the
lightness of carbon nanotubes, give them great potential in applications such as aerospace. It has
even suggested that nanotubes could be used in the “space elevator”, an Earth-to-space cable first
proposed by Arthur C. Clarke.
The electronic properties of carbon nanotubes are also extraordinary. Especially notable
is the fact that nanotubes can be metallic or semiconducting depending on their structure. Thus,
some nanotubes have conductivities higher than that of copper, while others behave more like
silicon. There is great interest in the possibility of constructing nanoscale electronic devices from
nanotubes, and some progress is being made in this area. However, in order to construct a useful
device we would need to arrange many thousands of nanotubes in a defined pattern, and we do
not yet have the degree of control necessary to achieve this. There are several areas of
technology where carbon nanotubes are already being used. These include flat-panel displays,
scanning probe microscopes and sensing devices. The unique properties of carbon nanotubes will
undoubtedly lead to many more applications.
(i) Single-walled:-
Most single-walled nanotubes (SWNT) have a diameter of close to 1 nanometer, with a tube
length that can be many millions of times longer. Single-walled nanotubes are an important
variety of carbon nanotube because they exhibit electric properties that are not shared by the
multi-walled carbon nanotube (MWNT) variants. The most basic building block of these systems
is the electric wire, and SWNTs can be excellent conductors.
(ii) Multi-Walled:-
Multi-walled nanotubes (MWNT) consist of multiple rolled layers (concentric tubes) of graphite.
There are two models which can be used to describe the structures of multi-walled nanotubes.
This is especially important when functionalization is required (this means grafting of chemical
functions at the surface of the nanotubes) to add new properties to the CNT. In the case of
SWNT, covalent functionalization will break some C=C double bonds, leaving "holes" in the
structure on the nanotube and thus modifying both its mechanical and electrical properties. In the
case of DWNT, only the outer wall is modified.
Applications:-
Carbon nanotubes are largely used in the research & development of nanomachines, new
nanofiber & nanostructures. Some of its applications are:
3. Reinforced Elastomers:- Carbon blacks are widely used for reinforcing rubbers in tyres and
other industrial rubbers. Currently, reinforced rubber contains high loading of fillers (more than
50% wt.) for increasing stiffness and strength. At the same time, they lack elasticity for some
applications. CNTs developed by Nano have overcome this problem. By addition of 5-10% of
multi-wall nano carbon tubes will give you similar level of stiffness and strength in high
performance elastomers along with improved elasticity, offering a new balance of mechanical
properties that cannot be matched with conventional fillers.
4. Conductive Plastics:- The use of nano carbon tubes for antistatic and conductive applications
in polymer is already a commercial reality and is growing in sectors such as electronics and the
automotive industry. The loading for achieving electrical percolation with multi-wall nano
carbon tubes can be 5-10 times lower than with conductive carbon black grades. Similar
comparisons are made in thermoset resins like epoxies but at much lower loading. The geometric
aspect ratio of carbon nanotubes is typically superior to 100 compared to short carbon fiber (<30)
and carbonblack (>1) in the final product (e.g. injection moulded part). This explains the lower
content needed for a given resistivity.
REFERENCE:-
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Kannangara, Geoff Smith, Micchelle Simmons, Burkhard Raguse
(2). “Nanotechnology global strategies, industry trends and applications.” By Jurgen Schulte
(3). “Introduction to nanotechnology.” By Charles P. Poole, Jr. Frank J. Owens
(4). “Nano materials” By A.K. Bandyopadhyay
(5). Nanotechnology applications telecommunications networking By Daniel minolid
(6). Science at the Nanoscale; By Chin Wee Shong, Sow Chorng Haur and Andrew TS Wee.