BASICS OF NANO TECHNOLOGY – UNIT I

(IV Year-I Semester)

DEPARTMENT OF CHEMICAL ENGINEERING

RGUKT-AP
RK Valley
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Text books:

7. Nano structeres and nano materials – Guozhong Cao, Imperial college press London

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INTRODUCTION:

Stone age

Bronze age

Iron age

Advance
materials

Nano age

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New Technology requirement:

 New materials
 Superior physical, chemical and mechanical properties
 Properties strongly depends on microstructure of materials
 Composition can be changed by altering the microstructure using
thermo-chemical-mechanical methods
 To understand properties requires instruments such as high-resolution
microscopy techniques
Ex: Electron, Atomic force and field ion microscopy

a) Dispersion b) aggregation
 Mechanical properties c) Anisotropic assembly
 Optical properties  No improvement
4 properties
 Electrical
 Thermal properties
What is nano:

 Nano is Greek meaning dwarf or something very small.

 Nano technology deals with small structures or small sized
materials
 A nanometer is one billionth of a meter (10-9m).
 One nm is approximately equivalent to 10 H2 or 5 Silicon
atoms.

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What is nano & Nanotechnology :
 Nanomaterials can be metals, ceramics, polymers or composites.

 one cannot define an exact dimension for the grain size below which
materials can be classified as ‘nano’.

 Most electronic and optical properties vary when the grain size is
reduced typically below 10 nm.

 Their mechanical, chemical and many physical properties begin to vary

significantly from bulk below 50–100 nm.

 Hence, nanomaterials may be classified as those materials which have at

least one of their dimensions in the nanometric range, below which there
is significant variation in the property of interest compared to
microcrystalline materials.

 Nanotechnology can be understood as a technology of design,

fabrication and applications of nanostructures and nanomaterials.
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Objects in different scales:

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History and scope:
• Richard Feynman is often regarded as the first visionary of
nanotechnology.

• “There’s plenty of room at the bottom”

• 29th December 1959, at the annual meeting of the American

Physical Society, opened up a whole new field, known as
‘nanotechnology’

• In 1986 “Engines of Creation: The Coming Era of

Nanotechnology” by Eric Drexler

• The power of chemistry be used to build molecular machines

• The power of an interdisciplinary approach to make

commendable progress in nanoscience and nanotechnology

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Magic number:
• Magic number is defined as the number of atoms in the clusters of critical
sizes with higher stability.

• This effect was initially observed in gaseous metal atoms, in the early 1980s.

• condensation of atoms from a vapour phase on a substrate surface, during

thin film deposition

• Magic numbers based on electronic shells were first observed in mass

spectra of alkali metal clusters.

• The stability of such clusters as a function of the size did not follow a
continuous function.

• It was seen that for some specific number of atoms in the cluster (N), N = 2,
8, 20, 40, 58, 92, etc., the free energy is lower, resulting in stabilization of the
cluster.
• Small clusters of atoms behave quite differently from bulk materials.
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Magic number:
• Bulk properties are scalable only up to a certain critical grain size and
below this limit.
• The behaviour of small clusters of atoms cannot be predicted on the same
mechanistic or heuristic basis.
• Recent work has shown that atomic clusters containing certain magic
numbers of atoms have quite distinct behavior.

Fig: Krypton atoms cluster together in stable Fig: Fullerence or C60.

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sizes of 13, 55, 147, 309, 561,... atoms.
Nano materials are not new
• Nanomaterials have been produced and used by humans for hundreds of years.
• The beautiful ruby red colour of some ancient glass paintings is due to gold and
silver nanoparticles trapped in the glass matrix.
• The decorative glaze or metallic film known as ‘luster’, found on some medieval
pottery, contains metallic spherical nanoparticles dispersed in a complex way in
the glaze, which gives rise to special optical properties.
• Carbon black is a nanostructured material that is used in car tyres to increase the
life of the tyre and impart black colour (1900).
• Fumed silica, a component of silicon rubber, coatings, sealants and adhesives, is
also a nanostructured material (1940).
• Steel (an alloy of iron and carbon) is believed to have been first prepared in India
about 1500 years ago and is popularly known as wootz.
• The high strength of these steels may be due to the presence of these carbon
nanotubes, which are known for their exceptionally large Young’s modulus.

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Early applications of nanotechnology: Nano-gold
• Materials in the nanometre-scale exhibit uniquely different physical,
chemical and mechanical properties compared to bulk materials.
• Gold, under ordinary conditions is a yellow, inert metal, capable of
conducting electricity.
• However, when the pieces are broken down about a million times, into bits
just a few nanometres wide, almost every characteristic changes.
• Nano-gold no longer glitters with a golden yellow metallic lustre.
• Reflected light of gold nanoparticles varies in colour, depending upon their
dimensions.
• Gold NPs appearance:
 50 nm in diameter appear blue or purple,
 at 25 nm they are red, and
 at 1 nm they are orange

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Early applications of nanotechnology: Nano-Gold
• the varying colours of nano-gold here used in ancient days for making
tinted glass and the Roman Lycurgus cup.

• The melting point of gold also drops by almost 50% when the grain size is
reduced below 10 nm
• When size is nm, the gold become highly reactive.
• Similar changes have been observed in different nanomaterials with a
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variety of other properties like magnetism and conductivity.
Publications on nanotechnology

In India the Government has constituted the Nano Science and Technology Initiative
(NSTI) as a thrust activity of the DST.
already supported research in this field to the tune of Rs. 200 crores over the last five
years
In the current five year plan, this has been enhanced by about five times.

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CAN SMALL THINGS MAKE A BIG DIFFERENCE

Why is the study of nanomaterials gaining wide importance and increased scientific attention?

So what if the dimensions of a material are in the nanometric scale?

Can small things make a big difference?

Change in properties of Ni as grain size is changed from 10 μm to 10 nm

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CAN SMALL THINGS MAKE A BIG DIFFERENCE

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CAN SMALL THINGS MAKE A BIG DIFFERENCE

Fig. The hypothetical structure of a Fig. Increase in the intercrystalline region

nanomaterial. The black circles indicate (grainboundaries) and triple junctions
atoms in the grain, while the white circles with decrease in grain size of
indicate atoms at thegrain boundaries. nanomaterials.

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CAN SMALL THINGS MAKE A BIG DIFFERENCE

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CAN SMALL THINGS MAKE A BIG DIFFERENCE

• Quantum confinement can also lead to different electromagnetic and

optical properties of a material.

• Due to the Gibbs–Thomson effect, the melting point of a free-standing

particle is lowered if it is a few nanometres in size.

• Due to quantum mechanical forces that are exhibited at these length

scales, nanomaterials may become better electrical conductors, be able
to transfer heat better, etc.

• Quantum dots are the best example of quantum confinement effects

leading to bandgap tuning, etc

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Classification of Nanostructured materials:

Growth Product/
Dimension
Media shape

Nanoparticles
0D Vapor phase
(Colloids)

Nano rods,
1D Liquid Phase
wires

2D Solid Phase Thin films

Hybrid growth Nano

3D structured
(VLS) bulk

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Classification of Nanostructured materials:

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Fascinating Nanostructures:

Nanowires :
 These can be defined as 1D nanostructures with nanometric width
dimensions

 Aspect ratios (the ratio between length and width) of 1000 or more
 Nanowires properties deviating from bulk behaviour, due to quantum
confinement in the lateral dimension.
 Fabricated nanowires such as
 metals (Au, Ni, Pt)
 semiconductors (InP, Si, GaN)
 and insulators (SiO2, TiO2)
 Applications:
 electronic, opto-electronic
 nano-electromechanical sensors and devices
 Alter the growth parameters of nanowires into a helical22formation.
Fascinating Nanostructures:

Nano rods :
 These differ from nanowires in their aspect ratio.
 Standard aspect ratios for nanorods are 3–5.
 nanorods have all their dimensions in the range 1–100 nm and hence are 3D
nanostructures.

 Applications:

 display technologies:
the reflectivity of the rods can be changed by changing their orientation with
an applied electric field
 micromechanical switches 23
Fascinating Nanostructures:
Nano shells :
 These are structures where the nanocrystalline particles are coated with a thin layer of a
different material with thickness in nanometric dimensions.
Applications:
 Gold nanoshells coated on dielectric silica nanoparticles have been widely studied in drug
research.
 It is possible to vary the light absorption and emission characteristics of gold nano shells
by controlling the thickness and size of the nanoparticles.
 Study of plasmon resonance wavelength shift as a function of nanoshell composition for a
gold/silica nanoshell with a 100-nm core, demonstrates the ability to tune the optical
resonance of nanoshells to a desired wavelength.
 This property is critical in nano-drug delivery for in vivo therapeutic Applications.
 Nanoshells can also find application in nanomedical diagnostic tools, for example, in
thermal imaging.
 By attaching certain antibodies to such nanostructures, it is possible to provide site
specificity
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 example, for selective segregation of such nanoparticles in cancerous or tumour cells.
Fascinating Nanostructures:
Nano tubes :
 These are tubes with diameters in the nanoscale.
 carbon nanotubes are by far the most important group.
 A single-walled carbon nanotube (SWCNT) is obtained by rolling a sheet of graphite (a
hexagonal lattice of carbon) into a cylinder.
 Typical diameters of SWCNTs are in the range of 0.7–1.4 nm and their length can be
several micrometres.
 Multi-walled carbon nanotubes (MWCNTs) can be regarded as a coaxial assembly of
SWCNTs.
 MWCNTs have their diameters in the range of 5–50 nm.
 Carbon nanotubes also exhibit good nano-mechanical properties due to their high
Young’s modulus.
 The modulus of single-walled (1210 GPa) and multi-walled (1260 GPa) carbon nanotubes
is now established as a world record as the highest known modulus for any material.
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Fascinating Nanostructures:
Nano tubes :

Fig: Schematic illustration of nanotubes.

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Fascinating Nanostructures:

Nanofluids :
These are fluids (e.g. water, ethylene glycol, lubricants) with dispersions of
nanosized particles (e.g. carbon, metals, metal oxides, etc.).
 Synthesized Nanofluids
 magnetic nanofluids (ferrofluids)
 and thermal nanofluids
o Improvements in energy efficiency and convective heat transfer
o Thermal conductivity of the fluids has been enhanced to as high as
150%
 Applications:
drug delivery magnetic storage media
refrigerant chillers electronic manufacturing
Cosmetics Pharmaceuticals
power generation air-conditioning
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Nano Fantasies:

Nano-guitar :
 It is the world’s smallest guitar and is 10 μm long (about the size of a single cell) with six
strings, each about 50 nm wide.
 Researchers made this device at the Cornell Nanofabrication Facility, bringing micro-
electromechanical devices (MEMS) to an even smaller scale—the nano-sized world.

Nano-balance :

 It is small enough to weigh viruses and other submicron-scale particles.

 It works on the principle of variation in resonance frequency of the nanotube by
changing its mass.
 By knowing the resonance frequency of pure nanotubes, the mass of attached particles
can be studied.
 A nano-balance could be useful for determining the mass of objects on the femtogram
to picogram range.

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Applications of Nano Materials:

Nanomaterials are finding application in cosmetics, textiles, healthcare, tissue

engineering, catalysis, functional coatings, medical diagnosis and therapeutics,
sensors and communication engineering, water and air pollution treatment.

Electronic devices :

 The days of massive computer stations occupying an entire room with huge punch
cards to process each program.
 Today’s multi-functional laptops and palmtops are more user friendly, faster, handy
and have large memory capacities.
 Mobile phones, pocket-sized memory storage devices and the widely used MP3
players, iPods and iPads are perhaps the most convincing benefits of nanotechnology.
 All this has been possible due to the shrinking sizes of electronic devices enabled by
nanotechnology.

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Applications of Nano Materials:

 Miniaturization is the mantra of the electronics industry, which is driving research on

reduction in the size of transistors, resistors, capacitors, etc.
 Moore’s Law, an empirical observation made in 1965, states that the number of
transistors on an integrated circuit for a minimum component cost doubles every 24
months.

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Applications of Nano Materials:
 Nanostructures hold promise for the development of non-volatile, radiation hard,
highdensity (terabit/cm2) memory with nanosecond read/write times.
 While one terabit per square centimetre sounds astronomically large, a single movie,
The Lord of the Rings, required 27 terabytes (about 200 terabits) for the first instalment
alone.
 Researchers at IBM Zurich have been working on a novel memory device based on a
mechanical storage method.
 This system, called ‘Millipede’, uses an array of microcantilevers to create a pattern of
nanoindentations in a polymer medium.
 This method has demonstrated storage densities as large as 1Tb/in2.

carbon-nanotube based memory concepts:

 The giant magnetoresistance (GMR) effect has led to a strong increase in the data storage
density of hard disks and made the gigabyte range possible.
 Tunnelling magnetoresistance (TMR) is very similar to GMR and is based on the spin
dependent tunnelling of electrons through adjacent ferromagnetic layers.
 Both GMR and TMR effects can be used to create a non-volatile memory
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such as the magnetic random access memory.
Applications of Nano Materials:

Opto-electronic devices :
 Opto-electronic devices convert electricity to light and vice versa.
 They have broad bandwidth and efficiency,
Application :
LEDs (light emitting diodes) OLEDs (organic LEDs)
LCDs (liquid crystal displays) laser diodes
CMOS (complementary metal CCD (charge-coupled device)
oxide semiconductor)
photodetectors solar cells

Opto-electronic devices coupled with optical fibres have been extensively used
in the fabrication of TFT (thin film transistor)-LCD laptop PC screens, automobile
illuminations, mobile phone backlighting, VCD/DVD players, tele
communications and data communications (broadband communications),
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biotechnology (BioPhotonics), and digital cameras.
Applications of Nano Materials:

Quantum computers:
 Lasers produced from nanoscale quantum dots are being fabricated.
 The wavelength of the laser is reported to depend on the diameter of the
quantum dot.
 Quantum dot lasers are cheaper and offer higher beam quality than
conventional laser diodes.
 With the ability to synthesize quantum dots on a commercial scale, it has
become possible to exploit the laws of quantum mechanics for novel quantum
computers, using fast quantum algorithms.
 Quantum computers can perform several computations at the same time and
are much faster.
 This class of computers would be useful to solve specific problems and
supplement digital computation.

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Applications of Nano Materials:

Insulation:
 Aerogels are nanomaterials synthesized by the sol-gel process.
 which are porous, foam-like and extremely light-weight, and yet can withstand about
100 times their weight.
 They are currently being used for insulation in offices, homes, etc.
 They are also being used in ‘smart’ windows, which darken on a sunny day and
lighten on a cloudy day.

Phosphors :
The use of nanophosphors such as zinc selenide, zinc sulphide, cadmium
sulphide and lead telluride is expected to make high-definition televisions
(HDTVs), personal computers.
Carbon nanotubes have been used for the production of displays with low
energy consumption, primarily due to their higher efficiency field emission
properties.
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Applications of Nano Materials:

Cutting tools:
 Microdrills consists of drill bits with diameter less than the thickness of human hair
 Used in the miniaturization of microelectronic circuits, are required to have
enhanced wear resistance.
 Nanocrystalline carbides and nitrides are harder and wear-resistant, and hence
are currently being used in these microdrills.
Medicine:
 nanotechnology finds application in diagnosis, therapeutics, prosthesis materials
and tissue engineering.
 Nanomaterials have dimensions similar to those of biological molecules and hence
they are useful for biomedical applications.
 By attaching different biomolecules to nanomaterials, they can be used in medical
applications for specific functions.
 Nanotechnology is being developed for both therapeutic (using nano-drug delivery
systems) and diagnostic (nano-biosensors) applications.
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Applications of Nano Materials:

 Gold nanoparticles attached to short segments of DNA can be used to detect the
genetic sequence of a sample.
 Bandages embedded with silver nanoparticles are gaining popularity for providing
anti-microbial protection and to aid faster wound healing.
 Nanostructured synthetic skin is being used for several skin graft applications.
 Biocapsules are increasingly being used as substitutes for diabetic insulin, targeted
drug delivery, biosensors, etc.
 Respiration monitors utilizing nanomaterials can be more sensitive than
conventionalmonitors.
 Early detection of a disease always enables quicker and more effective cure and
recovery.
 Nanoparticles have shown potential for detecting viruses, pre-cancerous cells, etc.
 Targeted drug delivery systems can deliver drugs effectively and conveniently with
increased patient compliance, extended product life and reduced healthcare costs

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Applications of Nano Materials:
Nanobots or nano-robots :

 They are devices that can be injected into the bloodstream to cure diseases at specific
locations and their motion is controlled by an external field.
 Drug delivery systems that rely on nanomaterials are used for the targeted delivery of
compounds characterized by low oral bioavailability due to poor water solubility,
permeability and provide for longer sustained and controlled release.
 The overall drug consumption and side effects can be lowered significantly by coating
drugs on nanoparticles.
 This highly selective approach reduces cost and human suffering.
example: Dendrimers and nanoporous materials can transport small molecules of drugs
to the desired location.
 Another application is based on small electromechanical systems: nano-
electromechanical systems (NEMS) are being investigated for the active release of
drugs.
 The use of gold-coated shells for cancer therapy is in an advanced stage of research.
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Applications of Nano Materials:
Renewable energy:
 Greatest challenge for society and humankind is how to meet our ever-increasing
demand for energy security.
 Although the primary source of energy on earth is derived from the sun
 The fundamental steps for energy conversion occur at the nanoscale :

* Transfer of charge * chemical reactions * transformation of molecular structure

 Some of the promising new areas for the use of nanotechnology in this field are:
 use of nanomaterials to extract hydrogen from water
 to harvest energy from the sun and biomass
 to store energy as hydrogen fuel cells, batteries and capacitors.
 Nanomaterials are also being used as advanced catalysts for energy
conversion.

 Nanomaterials will also impact efficient utilization of energy for industries such as
transportation, power generation and utilization, water management and purification
and environmental cleanup.
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Applications of Nano Materials:
Catalysis:
 It is one of the most lucrative areas for a nanotechnologist is catalysis.

 Chemical catalysis benefits significantly from nanoparticles, due to the extremely large
surface-to-volume ratio.

 It is easy to understand from geometrical principles that the surface area to volume
ratio is inversely proportional to the size of a particle.

 A variety of chemical reactions take place on the surface of a catalyst, and hence the
larger the surface area, the more active the catalyst.

 The application potential of nanoparticles in catalysis ranges from fuel cells to

catalytic converters and photocatalytic devices.

 Automobile catalytic converters for the removal of noxious and toxic gases such as
carbon monoxide and nitrogen oxide

 Power generation equipment to prevent environmental pollution arising from

burning gasoline and coal. 39
Applications of Nano Materials:

Filtration:
 Nanochemistry also finds immense use in wastewater treatment and air purification
devices.
 One class of filtration techniques is based on the use of membranes with
appropriately sized pores, through which the liquid is allowed to pass.
 Nanoporous membranes used in nanofiltration have extremely small pores of less
than 10 nm.
 Nanofiltration is used mainly for the removal of ions or the separation of different
fluids.
 Ultrafiltration is used to remove particles with size between 10 nm and 100 nm.

 Renal dialysis is an important application of ultrafiltration.

 Magnetic nanoparticles offer an effective and reliable method to remove heavy
metal contaminants from wastewater by the use of magnetic separation techniques.
 Nanoscale particles increase the efficiency to adsorb contaminants.
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Applications of Nano Materials:
Pollutants:
Elimination of pollutants Nanoscale materials can be used effectively in soil/sediment and
water remediation.

For sites where refractory organic contamination has penetrated deeply into the soil, it
would be cost effective to develop remediation technologies that do not require
excavation.

The use of zero-valent iron particles has been shown to be effective in penetrating the
required distances, and oxidizing selected organic contaminants.

Sensors:
Sensors made of nanocrystalline materials are extremely sensitive to a change in their
environment.
Some of the applications for sensors made of nanocrystalline materials are
• smoke detectors,
• ice detectors on aircraft wings and
• automobile engine performance sensors.
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Applications of Nano Materials:
Food :
 Food packaging can be improved by placing anti-microbial agents directly on the surface
of the coated nanocomposite film.
 The incorporation of nanoscale clay particles in a polymer matrix can result in lower
oxygen and water permeation with better recyclability.
 This can protect food from drying and spoilage (incurred by oxygen access).
 Silver has been used as an anti-microbial agent for centuries.
 Nanoscale silver has introduced in antimicrobial containers to keep food fresh for longer.
Consumer :
 Nanotechnology provides consumer products with novel functions ranging from easy-to-
clean to scratch-resistant coatings.

 The most prominent application of nanotechnology in the household is self-cleaning or

‘easy-to clean’ ceramic or glass surfaces.
 Nano-ceramic particles have improved the smoothness and heat resistance of common
household equipment such as the flat iron and cooking pans.
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Applications of Nano Materials:
Sports:
Nanotechnology is promising to enhance life and performance of sports gadgets.
Nanotechnology has been employed to produce tennis balls that last longer, rackets
that are stronger and bowling balls that are harder.
Nano-ski wax is easier to apply and more effective than standard wax.
Nanotechnology enhanced golf balls can correct their own flight path so that they fly
straighter than conventional balls.
Textiles :
There are several applications of nanotechnology in textiles and fabrics, ranging from anti-
microbial, hydrophobic and self-cleaning applications.
When the fabric is mixed with a hydrophobic material, it repels water and is also stain
resistant.
Nanoparticles have been incorporated into products such as nylon, polypropylene and
other polymers to impart long-term anti-microbial characteristics even under harsh
environmental conditions or after extensive thermal cycling.
Nano-socks with nano-silver dispersions are odourless and also possess
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properties.
NATURE: THE BEST NANOTECHNOLOGIST :
 Nature is perhaps the foremost inspiration for nanoscientists and nanotechnologists.

Fig: Biological features such as DNA, cells and membranes are of nanoscale.
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NATURE: THE BEST NANOTECHNOLOGIST :

Fig: Spider’s web: It is not only aesthetically pleasing but is also a biological wonder
as the fibres of the web are the strongest known fibres—until the carbon nanotubes
were discovered. 45
NATURE: THE BEST NANOTECHNOLOGIST :

Fig: Water striders: Nano-grooves on microhairs are responsible for their

ability to move on water without getting wet.
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CHALLENGES AND FUTURE PROSPECTS :

Engines of Creation: The Coming Era of Nanotechnology, book published in 1986,

Drexler imagined sophisticated nanoscale machines that could operate with atomic
precision.
Hard materials like diamond to fabricate complex nanoscale structures by moving reactive
molecular fragments into position.
His approach was essentially mechanical, whereby tiny gears and bearings are integrated to
make tiny robot factories, probes and vehicles.
The beauty of nanotechnology is that it is truly multidisciplinary, re-unifying the common
threads between science, engineering and technology.
It is so vivid, with possibilities left only to the constraint of perhaps human imagination.

The effect of nanoparticles on biological and ecological systems in large is a subject to be

studied with the highest priority.
It is important to qualify the application of nanomaterials for industrial and large-scale
societal applications, not only based on their properties but also based on their possible
long-term side effects.
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