Module 4: Nanomaterials | Nanomaterials: | Prerequisite: Concept of Nano scale, definition of nanoparticles | | | | Types of Nano materials- Fullerenes, Carbon nanotubes, | Properties of nanomaterial ect inomaterials ~optical properties, magnetic properties, electrical | pecan Prope ienetic proper Preparation of Nano materials- Top down and Bottom up approach Synthesis of Nano materials - Chemical vapor deposition (CVD) method and | | Laser Ablation Method | | Application of Nanomaterials 1. What is nanotechnold! Nanotechnology is the toqn given to those areas of science and engineering where ike place Mt dimensions in the nanometre scale are utilised in the roduction and application of materials, structures, devices and tural world there are many examples of structures that exist phenomena thaj MaMbjdls reduced to the nanoscale can suddenly show very different properties compat to what they show on a macroscale. For instance, opaque substances become transparent (copper); inert materials become catalysts (jlatinum); stable materials tum. combustible (aluminiurr); solids turn into liquids at room temperature (gold); insulators become conductors (silicon)Properties of nanomaterials: Optical Properties: effects) On decreasing the size the electron gets confined to the particle (confinement leading to: (increase in bandgap energy and Gi) band levels get quantized (discrete), Y R EB} Atom cluster 2 A Decreasing size wr particle the density of states becomes more quantized and the energies (shorter wavelengths) — the absorption spectrum Bulk Mjs ‘golden’ yellow colour. Nanoparticles of gold (colloidal) can have red, purpie of blue colour. The colour depends on the size (& shape) of the particle.vel ‘freely’ tll they are In nanoscale, two effects become important; si geuantum effects Continuous bands are replaced with discrete energy states 2-Quantum confinement effect: Due to quantum confinement oye te Fective band gap of the material with decreasing crys inerease in the ef Reduction of size of the system plays a major role e.g, chi vibrational energy levels. ‘These effects can lead to altere: ange in glee Mage a «d conductivity in nanomaterial® Magnetic Properties: thas the high suggattio-Whure ratio and different erystal fresttig and considerably different onding bulk materials, Due to finite size effects, su nanoparticles are found to exhit cir cor rend on the surface effect, charge transfer, chemical structure, In most cases, the to 100 nm in size and can display structure Magnetic properties than those found in The properties of magnetic nanop: magnetic interactions, synthes; Magnetic nanoparticles ra superparamagnetic. Nanoscale materials * Fullerepet> Ful potting but an allotrope of carbon wherein its molecules consist of carbon toMy at are connected by single and double bonds. This results in the formation of a closedNgy partially closed cage-like structure (a mesh consisting of fused rings) that al atoms, The fullerene molecule in this form can either have a further Contain seve hollow sphere, be an ellipsoid, tube, ort can also have many other different shapes and sizes. Structure of Fulleren Fullerenes in their natural form tend to be highly symmetrical, Their structure is quite similar to that of graphite and is made up of a sheet of connected hexagonal rings (cageings. They are 4 sometimes heptagonal ring structure), However, they have pentagonal ani ing on their shape ‘ten roferred to as buckyballs and buckytubes depending Model of the C60 fullerene (buckminste In any case, there is an infinite number of fullerenes that Ce Cro, C8, and C9» existing in various forms. Th [Link] present in the molecule, Physical Properties of Fullerene: Q + Its behaviour and structure on the teriperat:.. as the temperature is increased fullerene gets cg IM the Cry Fulllerene structure cay e un Fullerene has an ioy Riggendd largely on the number 0 1 different pressures, py of 7.61 electron volts. B electrons volts but not totally unreactive. tions, fullerene can act as an electrophile lectron-accepting group and is characterized as an oxic when doped or crystallized with alkali or alkaline Ses superconductivity properties, lerene is ferromagnetic. izing agent earth metals it Carbon nanotube (CNT)- A carbon nanotube (CNT) is one of the most important nanomaterials. Before 1991, only two main allotropes of carbon were known, In 1991, a Japanese ph lizima invented CNT (another allotrope of carbon), Let us discuss the cart definition, carbon nanotube is a hollow tube made up of carbon of nan In short, it is represented as CNTs, Carbon nanotubes are \ysicist, Sumio. bon nanotubes ale diameter, also called Bucky tubes,Pres cM atey ius mensional graphite now fads bre structure, Nanos ar hollow fom sie, The diameter ofthe nanotube i round 1-3 nanometers, The length of the carbon nanotube ie much higher than its Properties of Carbon Nanotube: ‘Carbon nanotubes are stiff. They are as stiff as 4, Carbon nanotubes are stronger than steel mechanical properties. Carbon nanotubes are ten times, a diamond (the hardest natura ly, This twenty times Therefore, it does not expat ing like that of steel, idges Yad aircrafts material stronger than ste Therefore carbon nanotubes uses in making 6. In carbon nanotubes, each carbon ato, miikfed by three other carbon atoms through covalent bonds. These on covalent bonds form lattices in the shape of hexagons, 7. The crystalline structure of Mgkoh nanotubes exists in the form of regular hexagons. Carbon nanotubes are€psy Carbon nanotubes ar\gooMgénductors of heat, 10. Carbon nanotubes have good electrical conductivity. a Nanotubes cer tumour destruction: jan Webs are used to destroy breast cancer tumors. They play with an antibody he antibody along with nanotubes is attracted to the proteins by cancer cells in ser beam killing the bacteria of the tumor. body and nanotubes absorb the | 2, Windmill blades: Tubes are also used in the windmill blades because of their low weight. It increases the efficiency of the windmill and helps to produce more electricity at a faster rate.3. Filtration: Carbon naones the We particles of size greater -— se daring filtration through them. They ean aller sized ions from a solution, 4. Carbon nanotubes as Nano cylinders: ery for Vehicles can be safely stored inside the lem of H2 storage hazards can be solved Carbon nanotubes have also been shown to absorb infrared light agd may have Applications in the IR optics industry. x ~ MWCNT multiple layer of graphene Can be produced without catalyst Gas like H2, for energy, bi carbon nanotubes and the pro! Types of Carbon Nanotubes: L. Single-walled Carbon nanotubes 2. Mutti-walled Carbon nanotubes (5) 13). SWCNT (1) Single layer of graphene (2) Catalyst is required for synthesis (3) Bulk synthesis is difficult (4) More defection during functionalization (5) Purity is poor (6) Less accumulation in body (7) Easy characterization and evaluation Bulk synthesis is easy Less defection, but difficult to improve Purity is high More accumulation in body Difficult characterization and evaluation (8) Easily twisted Difficult to twist Preparation of Nanomaterials: Bottom-up and Top-down Approach’ Synthesis of nanosize materials is of great importance, as particles built up from a few hundred atoms possess properties different from bulk. There are two possible Toutes for the synthesis of nanomaterials — “bottom up” and “top down”, In the bottom upmolecules (small to big) -aswembly. p bulk Ranostructures are built up from iydividual atoms or n reorganization and self 8 Approach also uses the principle of molecular Tn the top down approach the na Materials (big to small). In this method a bulk mate structures are built up from breaking al is broken up into nanoparticles using grinder, lasers ete. = Bulk Fragments Meth domiterials synthesis 1, Chemical Vapor Qgpositio )) Method (gas-phase synthesis methods) ods are of increasing interest because they allow elegant The gas-phase synthesis my e, sape and chemical composition controlled nanostructures. In way to produ 3 ‘vapour deposition (CVD) synthesis, gaseous products either are conventighat cht alloy reat’ homogeneously or heterogeneously depending on a particular appMygtion. Most oMthe synthesis routes are based on the production of small clusters ‘that can aggregate to form Nano particles (condensation), Condensation occurs only when the vapour is supersaturated and in these processes homogeneous nucleation in the gas phase is utilized to form particles, This can be achieved both by physical and chemical methods.nanofiber f carbon (multiwall carbon yeecate: production and. MWNT naphthalene, etby! Ni, Fe, Pt etc:) @ This is a very promising method from Jarl (CNF), SWNT (single wall carbon nanotubes) ie nanotubes), Hydrocarbons (e.g. methane, benzene, acetylene, " hexane ete) are allowed to decompose over metal eatalysts (e.8- Cr pproximately 30% produce CNT, Typical yields for CVD are During CVD, a substrate is prepared with a layer of metal catalyst commonly nickel, cobalt, iron, or a combination, The metal nanopart) gases are fed into the reactor: a process gas or can or hydrogen) and a carbon-containing gas (such as methane). Nanotubes grow at the sites of the metal is broken apart atthe surface of the catalyst p edges of the particle, where it forms the qanot fanz C,H, N, quar Schematics of experimental setup for CVD process Thdeechanism is still being studied. The catalyst particles can stay at the tips of the growinManotube during the growth process, or remain at the nanotube base, depending on the adhesion between the catalyst particle and the “ubstrate. Thermal catalytic decomposition of hydrocarbon hzs become an active area of research and can be a promising route for the bulk production of CNTs,Ablation Method (Wet chemical synthesis of nanomaterials) icles and KF ablation has been extensively used for the preparation of nanoparti Particulate films. In this method, vaporization ofthe material is effected usin high vacuum system pulses of Taser beam of high power. The setup is a ultra-high vacuum oF : equipped with inert or reactive gas introduction facility, laser beam, solid tart and cooled substrate, Usually laser giving UV wavelength such as excimer laser is BECES#35Y because other wavelengths like IR or visible are often reflected by some MQ the 7 Surface. A powerfull beam of laser evaporates the atoms from a it Byfoms rs, They collide with inert gas atoms (or reactive gases) and cool on thei forkgin condense on the cooled substrate. The method is often xr ablation. Gas pressure is very critical in determining the particle size, ution. Laser Ablation Method for synthesis of Rasy janotubes a In 1995, Smalley and co-workers produced carbon nanotubes using laser ablation technique. Both MWNTs and SWNT can be produced with this method. This tion of awe graphite targets inside a fmigspheRAfor generating MWNT. Tube growth takes arbon species at the edge of adjacent growing technique involves high power furnace at 1200°C, under Ay, place by the attachment results in a multilayered tube. A laser beam (typically graphene tubules and Nd-YAG or CO; laser) is Mygroduced through the window and focused into the target located in thaGenj ae furnace. The target (pure graphite) is vapourised at 1200°C in flowig Bt Myo order to gencrate SWNTs, metal particles as catalysts must be added to the graphite targets. A 50-50 catalyst mixture of Co and Ni is used. Argon gas carries the vapors from the high temperature chamber into a cooled eollector positioned Bee tie furnace, The vee Of two suecenive InaR phe es icin aaa of C deposited as soot, The second laser pulse break up the larger particles ablated by the first one and feds them to growing NT structure, The nanotubes will self-assemble from carbon vapors and condense on the walls of the flow tube, The diameter distribution of SWNTs from this method varies about 1.0 - 1.6 nm,Drawbacks Br dost oye ty seco ee VY 1 The laser technique is not economically advanta 2) This method involves evaporating the carbon the production to industrial level; usis je approaches. 3) Laser method can prepare small dhantitie phigh quality CNT’s. +) CNT’s produced are om A * Applications of Nanomaterials: posites are being used in various consumer products ‘indows, automobiles, etc. 1. Nano coatings and nanocom such as sports equipment, wi s from sunlight, glass bottles are being 2. To protect the damage caused to beverage: 1¢ UV rays. coated with nano coating which blocks th Using nano-clay composites longer-lasting tennis balls are being manufactured. 4. Nanoscale silica is used as a filler in dental fillings. The optical properties of the nanomaterials are used to form optical detectors, sensors, lasers, displays, solar cells. This property is also used in To increase the sun protection factor (SPF) in the sunscreens nano-Ti02 is used. To provide highly active surface to the sensors, engineered nanolayers are used. Fullerenes are used in cancer to treat cancer cells such as melanoma, These have also found use as light-activated antimicrobial agents,