Presented By, Dr. S. T.

Mhaske

Is Nanotechnology really new?

During the middle ages, the Muslims who fought crusaders with swords of Damascus steel had a high-tech edge - carbon nanotubes and nanowires in their sabres. Damascus sabres were forged from Indian steel called wootz. It is likely that the sophisticated process of forging and annealing the steel formed the nanotubes and the nanowires, and could explain the amazing mechanical properties of the swords

TEM image of cementite nanowires

Is Nanotechnology really new?

Lycurgus cup,4th century AD (now at the British Museum,London).The colors originates from metal nanoparticles embedded in the glass. At places, where light is transmitted through the glass it appears red, at places where light is scattered near the surface, the scattered light appears greenish.

Suspensions of spherical gold particles with various diameters (150, 100, 80, 60, 40, 20 nm from left to right) in water. The difference in colors is due to different scattering and absorption behaviour of small and large gold particles.

Nanotechnology

Derives from nanometer, which is one-thousandth of a micrometer (micron), or 109 of a meter The study, manipulation and manufacture of ultrasmall structures and machines made of as few as one molecule 100-500nm: Typical polymer latex particle size 250nm: Hiding grade TiO2 particle size.

Nature is Beautiful

Nanostructure diffracts the light, interference eliminate all the colors except orange/black.

Nanomaterials

Nanowires
Nanoparticles Nanomaterials Fullerenes

Nanotubes

Nanofibers

Carbon nanotubes, quantum dots, and other advanced nanomaterials

Proteins, Biological motors, and other nanobiological systems Real and imagined human-made nanomachines

Nanostructure Material
Metals

Ceramics
Polymers

Biomolecular materials

Nanoparticles
e.g. UV absorber in sun screens

Nanostructured Surfaces
e.g. lotus leaf

Nanostructured Materials
e.g. mortars and concrete

Nano-Particles

Fundamental building blocks of nano-

technology

Starting point for bottom-up approaches for preparing nano-structured materials & devices Their synthesis is an important research component

Building Complex Structures with Small Objects

Top-down (i.e. Lithography)

Bottom-up (i.e. Self-assembly)

This slide is adapted from the presentation on An Introduction to Nanotechnology, by Terry Bigioni, posted at http://www.homepages.utoledo.edu/tbigion/BigioniGroup/Outreach_Home.html

Composite fabrication

Nanotube bundles

Mixing large objects with small ones (i.e. nanocomposites)

Carbon matrix

Top-Down Fabrication
Start with a large piece of material Remove sections of material to carve a specific pattern or shape Has been used for centuries to manufacture artwork, tools and devices

Bottom-Up Fabrication
Start with catalyst particles and/or a substrate Expose to a gas or liquid Reaction leads to the growth of a solid nanostructure or nanoscale self-assembled layer Properties such as temperature, pressure, surface quality, composition, catalyst size, etc. influence growth characteristics

Nano-Materials Synthesis Methods

Colloidal processes Liquid-phase synthesis Gas-phase synthesis

Vapor-phase synthesis
Precipitation

Sonication

Nano-Engineered Products

Semiconductor nano-crystallites for use in microelectronics Ceramics for use in demanding environments

Polymers with enhanced functional properties

Transparent coatings with UV/ IR absorption properties, abrasion resistance

Static dissipative/ conductive films

Enhanced heat-transfer fluids Catalysis

Topical personal care (e.g., sunscreen) & pharmaceutical

applications

Ultrafine polishing of e.g., rigid mememory disks, optical lenses, etc.

Functional Polymer Fillers

To improve visco-plastic properties

By addition of inorganic fillers

Glass fiber, talcum, kaolin 20-60% dosage

Disadvantage: increased density of the composite

materials

Late 80s: Toyota developed nano-clays (bentonite)

for automotive applications

Functional polymers are very versatile, even tiny amounts can have dramatic impact

Colloidal Process

Nanoparticles produced directly to required specifications, assembled to perform a specific task Involves use of surface-active agents e.g., CdS 50 nm particles by mixing two solutions containing inverted micelles of sodium bis(2-ethyl hexyl) sulfosuccinate in heptane e.g., antiferromagnetic nanoparticles of Fe2O3 by decomposition of Fe(CO)5 in a mixture of decaline and oleyl sarcosine Coordinating ligands used to produce nanoclusters Surfactants play a major role

Physical Vapor Deposition (PVD)

A schematics illustrating the general steps and physical mechanism for a PVD process.

Liquid-Phase Synthesis
Used widely for preparation of quantum dots (semiconductor nanoparticles) Sol-Gel method used to synthesize glass, ceramic, and glasss-ceramic nanoparticles Dispersion can be stabilized indefinitely by capping particles with appropriate ligands

Sol-Gel Method

Aqueous or alcohol-based Involves use of molecular precursors, mainly alkoxides

Alternatively, metal formates

Mixture stirred until gel forms Gel is dried @ 100 C for 24 hours over a water bath, then ground to a powder Powder heated gradually (5 C/min), calcined in air @ 500 1200 C for 2 hours Allows mixing of precursors at molecular level
better control

High purity Low sintering temperature High degree of homogeneity Particularly suited to production of nano-sized multicomponent ceramic powders

Gas-Phase Synthesis

Reactant gases Precursors/carrier gas

A schematic of a conventional CVD reactor.

Laser beam or plasma can be introduced to enhanced the reaction Can fabricate: carbon nanotubes, inorganic oxide nanorods, nanowire etc.

Chemical Vapor Synthesis

Vapor phase precursors brought into a hot-wall reactor under nucleating condition
Vapor phase nucleation of particles favored over film deposition on surfaces CVC reactor (Chemical Vapor Condensation) versus CVD

Very flexible, can produce wide range of materials Can take advantage of huge database of precursor chemistries developed for CVD processes Precursors can be S, L or G under ambient conditions
but delivered to reactor as vapor (using bubbler, sublimator, etc)

Examples:
Oxide-coated Si nanoparticles for high-density nonvolatile memory devices W nanoparticles by decomposition of tungsten hexacarbonyl Cu and CuxOy nanoparticles from copper lacetonate

Allows formation of doped or multi-component nanoparticles by use of multiple precursors

nanocrystalline europium doped yttria from organometallic yttrium & europium

precursors erbium in Si nanoparticles zirconia doped with alumina one material encapsulated within another (e.g., metal in metal halide)

Can prevent agglomeration

Flame Synthesis

Particle synthesis within a flame Heat produced in-situ by combustion reactions Most commercially successful approach Millions of metric tons per year of carbon black and metal oxides produced Complex process, difficult to control Primarily useful for making oxides Recent advances:
g-Fe2O3 nanoparticles Titania, silica sintered agglomerates

Application of DC electric field to flame can influence particle size

Low-Temperature Reactive Synthesis

React

vapor phase precursors directly w/o external addition of heat and w/o significant production of heat e.g.: ZnSe nanoparticles from dimethylzinctrimethylamine and hydrogen selenide
by mixing in a counter-flow jet reactor at RT heat of reaction sufficient to allow particle

crystallization

Sonochemical Nano-Synthesis

Sonochemistry: molecules undergo a chemical reaction due to application of powerful ultrasound (20 kHz 10 MHz)
Acoustic cavitation can break chemical bonds Hot Spot theory: As bubble implodes, very high

temperatures ( 5,000 25,000 K) are realized for a few nanoseconds; this is followed by very rapid cooling (1011 K/s) High cooling rate hinders product crystallization, hence amorphous nanoparticles are formed

Superior process for:

Preparation of amorphous products (cold quenching) Insertion of nano-materials into mesoporous materials
By acoustic streaming

Deposition of nanoparticles on ceramic and polymeric surfaces Formation of proteinacious micro- and nano-spheres
Sonochemical spherization

Very small particles

Sono- Fragmentation (Size Reduction)

Bubble Bubble Collapse due to Implosion

Particle Fragments due to Particles

a) Violent Bubble collapse b) Inter-particle attrition

Fragmented Particle

Template-based Methods

Nanofibers: What are they? Why are they important?

What is a Nanofiber?

A nanofiber is a continuous fiber which has a diameter in the range of nano-meter. The smallest nanofibers made today are between 1.5 and 1.75 nanometers. At the right a human hair (80,000 nanometers) is place on a mat of nanofibers

Nanofibers range in diameter of 2-600 nanometers and are very difficult to see with the naked eye so they are studied using magnification

Electron micrograph of nanofibers used for tissue scaffolds

Spider dragline 3,000 nanometers

Making Nanofibers
Melt Fibers: some nanofibers can be made by melting polymers and spinning or shooting them through very small holes. As the fiber spins out it stretches smaller and smaller...

Cotton candy is made by heating syrup to a high temperature and then the liquid is spun out through tiny holes. As the fiber spins it is pulled thinner and thinner. It cools, hardens and, presto! Cotton Candy!!

Electrospinning to Make Nanofibers

An electric field pulls on a droplet of polymer solution at the tip of the syringe and pulls out a small liquid fiber. It is pulled thinner and thinner as it approaches the collection plate.

Electrospinning Apparatus

Uses of Nanofibers

High surface area: Filtration, Protective clothing.

Nano-Tex fabrics with water, cranberry juice, vegetable oil, and mustard after 30 minutes (left) and wiped off with wet paper towel (right)

Filter applications: Oil droplet coalescing on nanofibers increase the capture rate of the oil fog.

 Light Weight: Produce Solar sails in space, Aircraft wings, Bullet-proof vests.
New breathable bullet-proof vest: Nomex Nanofibers

Image courtesy of Reneker Group The University of Akron, College of Polymer Science

Nanotechnology is ubiquitous and pervasive. It is an emerging field in all areas of science, engineering and technology.

Welcome to NanoWorld!