6.2. NANOMATERIALS Nanomaterials are corner stones of nanoscience and nanotechnology. Nano science and technology is a broad and interdisciplinary area of research and development activity that has been growing explosively worldwide in the past few years. It is already having a significant commercial impact, which will assuredly increase in the future, : Nanomaterial is defined as a material with at least one dimension less than approximately 1-100 nanometers. Nanomaterials exhibit unique optical, magnetic, electrical, and other properties. Because of these emergent properties, they have great impact in electronics, medicine, cosmetics, textiles, information technology and environmental protection ete. SIunits: 1 nm = 1X10% m (which is 100,000 times smaller than the diameter of human hair.) x 1,00,000 x 1,00,000 ‘Single -walled _ Strand of Hair Carbon Nanotube 100 micrometers 1 Nanometer diameter diameter or example: Carbon nanotube Nanoparticle is an object with all three dimensions at the nanoscale. Example: Naturally occurring nanoparticles are - Volcanic ash, soot from forest fires, and incidental byproducts of welding, diesel engines cte.6.2.1. Classification of Nanomaterials Nanomaterials can be nanoscale in one dimension (eg. surface films), two dimensions (cg. strands or fibres), or three dimensions (eg. particles). They can exist in single, fused, ageregated or agglomerated forms with spherical, tubular, and irregular shapes. Common types of nanomaterials include nanotubes, dendrimers (branched molecules), quantum dots and fullerenes. Nanomaterials have applications in the field of nano technology, and displays different physical chemical characteristics from normal chemicals (i.e., silver nano, carbon nanotube, fullerene, photocatalyst, carbon nano, silica). Nanomaterials are classified as Zero dimensional, one dimensional, two dimensional, three 2s cee 8&5" ba a a a) (a) (b) (c) (d) & Classification of Nanomaterials (2) 0D spheres and clusters, (b) 1D nanofibers, wires, and rods, (c) 2D films, plates, and networks, (d) 3D nanomaterials.6.2.2. Importance of nanomaterials ‘These materials have created a high interest in recent years by virtue of their unusual mechanical, electrical, optical and magnetic properties. Some examples are given below: @ Gi Gin) Gy) ) ow ‘Nanophase ceramics are of particular interest because they are more ductile at elevated temperatures as compared to the coarse-grained ceramics. Nanostructured semiconductors are known to show various non-linear optical properties. Semiconductor Q-particles also show quantum confinement effects which may lead to special properties, fe the luminescence in silicon powders and silicon germanium quantum dots as infrared optoelectronic devices. Nanostructured semiconductors are used as window layers in solar cells. Nanosized metallic powders have been used for the production of gas tight materials, dense parts and porous coatings. Cold welding properties combined with the ductility make them suitable for metal-metal bonding especially in the electronic industry. Single nanosized magnetic particles are mono-domains and one expects that also in magnetic nanophase materials the grains correspond with domains, while boundaries on the contrary to disordered walls. Very small particles have special atomic structures with discrete electronic states, which give rise to special properties in addition to the superparamagnetism behaviour. Magnetic nanocomposites have been used for mechanical force transfer (ferrofluids), for high density information storage and magnetic refrigeration. Nanostructured metal clusters and colloids of mono- or plurimetallic composition have a special impact in catalytic applications. They may serve as precursors for new type of heterogeneous catalysts (Cortex-catalysts) and have been shown to offer substantial advantages concerning act ity, selectivity and lifetime in chemical transformations and electrocatalysis (fuel cells). Enantioselective catalysis was also achieved using chiral modifiers on the surface of nanoscale metal particles. ‘Nanostructured metal-oxide thin films are receiving a growing attention for the realization of gas sensors (NO,, CO, CO,, CH, and aromatic hydrocarbons) withenhanced sensitivity and selectivity. Nanostructured metal-oxide (MnO,) finds application for rechargeable batteries for cars or consumer goods. (vii) Polymer based composites with a high content of inorganic particles leading to a high dielectric constant are interesting materials for photonic band gap structure. 6.2.3. Examples of Nanomaterials Examples of engineered nanomaterials include: carbon buckeyballs or fullerenes; carbon nanotubes; metal or metal oxide nanoparticles (¢.g., gold, titanium dioxide); quantum dots, among many others. 6.2.4, Synthesis of nanomaterials Nanomaterials deal with very fine structures: a nanometer is a bi nth of a meter. This indeed allows us to think in both the “bottom up’ or the ‘top down’ approaches to synthesize nanomaterials, i.e. cither to assemble atoms together or to dis-assemble (break, or dissociate) bulk solids into finer pieces until they are constituted of only a few atoms. This domain is a pure example of interdisciplinary work encompassing physics, chet medicine. ry, and engineering upto Nanoparticles Bottom u ‘Schematic illustration of the preparative methods of nanoparticles (a) Preparation of Carbon Nanotubes: Different techniques for nanomaterial synthesis and their current status are briefly explained. First, the growth mechanism is explained, as it is almost general for all techniques. However, typical conditions are stated at all the different techniques. Different types of carbon nanotubes and carbon nanostructure materials can be produced in various ways. The most common techniques used are: are discharge, laser ablation, chemical vapour deposition.Are discharge: The carbon arc discharge method, initially used for producing C60 fullerenes, is the most common and perhaps easiest way to produce carbon nanotubes. However, it is a technique that produces a mixture of components and requires separating nanotubes from the soot and the catalytic metals present in the crude product. This method creates nanotubes through arc-vaporisation of two carbon rods placed end to end, separated by approximately Imm, in an enclosure that is usually filled with inert gas (helium, argon) at low pressure (between 50 and 700 mbar). Recent investigations have shown that it is also possible to create nanotubes with the are method in liquid nitrogen. A direct current of 50 to 100 A is driven at high temperature discharge between the two electrodes. The discharge vaporises one of the carbon rods and forms a small rod shaped deposit on the other rod. Producing nanotubes in high yield depends on the uniformity of the plasma are and the temperature of the deposit form on the carbon electrode. Depending on the mixture of helium and argon, different diameter materials have been found. These mixtures have different diffusion coefficients and thermal conductivities. Temperature, carbon and metal catalyst densities affect the diameter distribution of nanotubes. Depending on the exact technique, it is possible to selectively grow SWNTs or MWNTS, which is shown in Figure. Two distinct methods of synthesis can be performed with the are discharge apparatus. anode doped with Ni, Co, .... Hota somoephere, Sombar pure graphite electrodes Multiwall nanotubes 40 mm Experimental set-up of an arc discharge apparatuspoco sai Ase las = =P Fa ‘Schematic Grawings of the electrode sat-ups for (a) the conventional and (@) the new arc discharge elecirodes,Laser Ablatio : Carbon nanotubes can be synthesized by lasers group vaporization. A pulsed or continuous laser is used to vaporise a graphite target in an oven at 1200°C. ‘The main difference between continuous and pulsed laser, is that the pulsed laser demands a much higher light intensity (100 kW/em* compared with 12 kW/em) ‘The oven is filled with helium or argon gas in order to keep the pressure at 500 Torr. A very hot vapour plume forms, then expands and cools rapidly. As the vaporized species cool, small carbon molecules and atoms quickly condense to form larger clusters, possibly including fullerenes. The catalysts also begin to condense, but more slowly at first, and attach to carbon clusters and prevent their closing into cage structures. Catalysts may even open cage structures when they attach to them. From ‘these initial clusters, tubular molecules grow into single-wall carbon nanotubes until the catalyst particles become too large, or until conditions have cooled sufficiently that carbon no longer can diffuse through or over the surface of the catalyst particles. Itis also possible that the particles become that much coated with a carbon layer that they cannot absorb more and the nanotube stops growing. The SWNTs formed in this case are bundled together by vander Waals forces. Schematic drawings of a laser ablation apparatus There are some striking, but not exact similarities, in the comparison of the spectral emission of excited species in laser ablation of a composite graphite target with that of laser-irradiated C60 vapour. This suggests that fullerenes are also produced by laser ablation of catalyst-filled graphite, as in the case when no catalysts are included in the target, However, subsequent laser pulses excite fullerenes to emit C2 that adsorbs on catalyst particles and feeds SWNT growth. However, there is insufficient evidence to conclude this with certainty. Laser ablation is almost similar to are discharge, since the optimum background gas and catalyst mix is the same as in the arc discharge process.(ii). Chemical vapour deposition: The basic principle of the CVD process is as follows. Synthesis. ‘Chemical vapour deposition (CVD) synthesis is achieved by putting a carbon source in the gas phase and using an energy source, such as plasma or a resistively heated coil, to transfer energy to a gaseous carbon molecule, Commonly used gaseous carbon sources include methane, carbon monoxide and acetylene. The energy source is used to “crack” the molecule into reactive atomic carbon. Then, the carbon diffuses towards the substrate, which is heated and coated with a catalyst (usually a first row transition nanoscopic fine metal particles are formed, carbon nanotubes will be grown on the metal particles ‘on the substrate by glow discharge generated from high frequency power. A carbon containing reaction gas, such as C,H, CH,. C,H,, C,H, CO is supplied to the chamber during the discharge. The catalyst has a strong effect on the nanotube diameter, growth rate, wall thickness, morphology and microstructure. Ni seems to be the most suitable pure-metal catalyst for the growth of aligned multi-walled carbon nanotubes (MWNTS). The diameter of the MWNTs is approximately 15 nm. The highest yield of carbon nanotubes achieved was about 50% and was obtained at relatively low temperatures (below 330° C). RE ee ee + Be f x Je iL Boe i ee oe a a6.2.5. Fullerenes The first fullerene discovered was the bulky ball, called as buckminsterfullerene. In these molecules, 60 carbon atoms (C,,) are arranged in interlocking hexagons and pentagons, like the patches on a soccer ball. It is in spherical cage structure. Carbon nanotubes made of graphite sheets of hexagonal arrays of carbon rolled into tubes, are close cousins in terms of prowaietiaill ‘methods and some of their properties, and can be included in fullerene family if their ends are closed which looks like bulky ball extended into a tube. Structure of fullerenes.Preparation of Fullerene: Fullerenes are in fact produced in small amounts naturally, in fires and lightning strikes. The first fullerene was produced from vaporizing graphite with laser resulting soot. This produce mainly C,, and C,, and can produce higher fullerenes also by having more porous electrodes. Separation with solvents such as toluene can achieve near 100% purity for C,, Methods such as sputtering and electron beam evaporation (with graphite precursor) have been used to produce higher fullerenes, such as C,,, C,,, Cj,, and C,,. Properties of fullerenes: These are extremely strong molecules, able to resist great pressure. 2. As the layers are stick together by weak vander Waals forces they act as lubricant. 3. When incorporated in low amounts in a polymer matrix, they impart some of their strength and low density to the material. 4. Fullerenes and related substances have shown potential as catalysts. Soot produced using arc or combustion methods can be used for hydrogenation/dehydrogenation or aromatics, and for conversion of methane into higher hydrocarbons by pyrolitic processDue to its interesting electrical properties, they can be used in electronics as data storage devices, solar cells, fuel cells, photo detectors for x-rays. 6. Fullerenes alter the electrical behaviour of the nanotubes creating varying semiconducting properties, when fullerenes have been inserted into nanotubes. 7. Fullerenes exhibit a very large non-linear optical response (i.e. change of optical properties with exposure to light). Hence they found application in telecommunications and this property may be enhanced by the addition of one or more metal atoms externally to the fullerene cage. 8. Fullerenes are effective at mopping up free radicals, with damage living tissue. This led to use in cosmetics for skin protection, 9. The size of C,, is similar to many biologically active molecules, including drugs such as Prozac and steroid hormones. These have high physical and chemical affinity on important enzymes for HIV, called HIV protease and block the action of the enzyme. 10. Bulky balls could be made supertonducting at above the temperature of liquid nitrogen, which is an important finding because liquid nitrogen is relatively cheap to produce by attaining lower temperatures are much harder. 11. Fullerenes and their derivatives have been shown to be superconducting, but only at very low temperatures. 12. Fullerenes can be used as precursors for other materials, such as diamond coatings or nanotubes. 6.2.6. Properties of Nanomaterials Structural features of nanomaterials are in between those of atoms and the bulk materials. Hence, the properties of materials with nanometer dimensions are significantly different from those of atoms and bulks materials. This is mainly due to the nanometer size of the materials which make them: (i) large fraction of surface atoms, (i) high surface energy; (ii) spatial confinement; (iv) reduced imperfections, which do not exist in the corresponding bulk materials. Mechanical properties: The large amount of grain boundaries in bulk materials made ‘of nanoparticles allows extended grain boundary sliding, leading to high plasticity. 2. Catalytic Properties: Due to their large surface, nanoparticles made of transition element oxides exhibit interesting catalytic properties. In special cases, catalysis may be enhanced and more specific by decorating these particles with gold or platinum clusters.Magnetic Properties: In magnetic nanoparticles, the energy of magnetic anisotropy may be small that the vector of magnetization fluctuates thermally; this is called superparamagnetism. Such a material is free of remanence, and coercitivity. Touching, superparamagnetie particles are loosing this special property by interaction, except, when the particles are kept at distance. Combining particles with high energy of anisotropy with superparamagnetic ones leads to a new class of permanent magnetic materials, Optical Properties: Distributions of non-agglomerated nanoparticles in a polymer are used to tune the index of refraction. Additionally, such a process may produce materials with non-linear optical properties. Gold or CdSe nanoparticles in glass ead to red or orange coloration, Semi-conducting nanoparticles and some oxide- polymer nanocomposites exhibit fluorescence showing blue shift with decreasing, particle size. 6.2.7. Engineering Applications of Nanomaterials properties, they can be used for a wide variety of app! \ce nanomaterials possess unique, beneficial chemical, physical, and mechanical tations. These applications include, but are not limited to, the following: 1; Next-Generation Computer Chips: The microelectronics industry has been ‘emphasizing miniaturisation, whereby the circuits, such as transistors, resistors, and capacitors, are reduced in size. By achieving a significant reduction in their size, the microprocessors, which contain these components, can run much faster, thereby enabling computations at far greater speeds. However, there are several technological2. impediments to these advancements, including lack of the ultrafine precursors to manufacture these components; poor dissipation of tremendous amount of heat generated by these microprocessors due to faster speeds; short mean time to failures (poor reliability), etc. Nanomaterials help the industry break these barriers down by providing the manufacturers with nanocrystalline starting materials, ultra-high purity materials, materials with better thermal conductivity, and longer-lasting, durable interconnections (connections between various components in the microprocessors). Kinetic Energy (KE) Penetrators with Enhanced Lethality: The Department of Defense (DoD) is currently using depleted-uranium (DU) projectiles (penetrators) for its lethality against hardened targets and enemy armoured vehicles. However, DU has residual radioactivity, and hence, it is toxic (carcinogenic), explosive, and lethal to the personnel who use them. However, some of the important reasons for the continued use of DU penetrators are that they possess a unique self-sharpening mechanism on impact with @ target, and the lack of suitable non-explosive, non- hazardous replacement for DU. Nanocrystalline tungsten heavy alloys lend themselves, to such a self-sharpening mechanisms because of their unique deformation characteristics, such as grain-boundary sliding. Hence, nanocrystalline tungsten heavy alloys and composites are being evaluated as potential candidates to replace DU penetrators,Better Insulation Materials: Nanocrystalline materials synthesised by the sol-gel technique result in foam like structures called “aerogels.” These aerogels are porous and extremely lightweight. Aerogels are composed of three-dimensional, continuous networks of particles with air (or any other fluid, such as a gas) trapped at their interstices. Since they are porous and air is trapped at the interstices, aerogels are currently being used for insulation in offices, homes, etc. Phosphors for High-Definition TV: The resolution of a television, or a monitor, depends greatly on the size of the pixel. These pixels are essentially made of materials called “phosphors,” which glow when struck by a stream of electrons inside the cathode ray tube (CRT). The resolution improves with a reduction in the size of the pixel, or the phosphors, Nanocrystalline zinc selenide, zine sulfide, cadmium sulfide,6. 1 and lead telluride synthesised by the sol-gel techniques are candidates for improving the resolution of monitors. Low-Cost Flat-Panel Displays: Flat-panel displays represent a huge market in the laptop (portable) computers industry. By synthesising nanocrystalline phosphors, the resolution of these display devices can be greatly enhanced, and the manufacturing costs can be significantly reduced. Also, the flat-panel displays constructed out of nanomaterials possess much higher brightness and contrast than the conventional ones owing to their enhanced electrical and magnetic properties. ‘Tougher and Harder Cutting Tools: Cutting tools made of nanocrystalline materials, such as tungsten carbide, tantalum carbide, and titanium carbide, are much harder, much more wear-resistant, erosion-resistant, and last longer than their conventional (large-grained) counterparts. Since nanocrystalline carbides are much stronger, harder, and wear-resistant, they are currently being used in these microdrills. Elimination of Pollutants: Nanocrystalline materials possess extremely large grain boundaries relative to their grain size, Hence, nanomaterials are very active in terms of their chemical, physical, and mechanical properties. Due to their enhanced chemical activity, nanomaterials can be used as catalysts to react with stich noxious and toxic gases as carbon monoxide and nitrogen oxide in automobile catalytic converters and power generation equipment to prevent environmental pollution arising from burning gasoline and coal.10. High Energy Density Batteries: Conventional and rechargeable batteries are used in almost all applications that require electric power. The storage capacity of these batteries is quite low requiring frequent recharging: The life of conventional and rechargeable batteries is also low. Nanocrystalline materials synthesised by sol-gel techniques are candidates for separator plates in batteries because of their foam-like (acrogel) structure, which can hold considerably more energy than their conventional counterparts. Furthermore, nickel-metal hydride (Ni-MH) batteries made of nanocrystalline nickel and metal hydrides are envisioned to require far less frequent recharging and to last much longer because of their large grain boundary (surface) area and enhanced physical, chemical, and mechanical properties. High-Power Magnets: The strength of a magnet increases with decrease in the grain ize and increase in specific surface area of the grains. It has been shown that magnets made of nanocrystalline yttrium-samarium-cobalt grains possess very unusual magnetic properties due to their extremely large surface area. Typical applications of these high-power rare-earth magnets include quieter submarines, automobile alternators, land-based power generators, motors for ships, ultra-sensitive analytical instruments, and magnetic resonance imaging (MRI) in medical diagnostics, High-Sensitivity Sensors: Sensors are employed to know the changes in various parameters for which they are designed to measure, The measurable parameters include electrical resistivity, chemical activity, magnetic permeability, thermal conductivity, and capacitance. All of thesé parateters depend greatly on the microstructure (grain size) of the materials employed in the sensors. For instance, a ‘carbon monoxide sensor made of zirconium oxide (zireonia) uses its chemical stability to detect the presence of carbon monoxide. In the event of carbon monoxide’s presence, the oxygen atoms in zirconium oxide react with the carbon in carbon ‘monoxide to partially reduce zirconium oxide. This reaction triggers a change in the sensor’s characteristics, such as conductivity (or resistivity) and capacitance. The rate and the extent of this reaction are greatly increased by a decrease in the grain size. Hence, sensors made of nanocrystalline materials are extremely sensitive to the change in their environment. Typical applications for sensors made out of nanocrystalline materials are smoke detectors, ice detectors on aircraft wings, automobile engine performance sensor, etc.ul. Automobiles with Greater Fuel Efficiency: Currently, automobile engines waste considerable amounts of gasoline, thereby contributing to environmental pollution by not completely combusting the fuel. A conventional spark plug is not designed to burn the gasoline completely and efficiently. This problem is compounded by defective, or worn-out, spark plug electrodes. Since nanomaterials are stronger, harder, and much more wear-resistant and erosion-resistant, they are presently being envisioned to be used as spark plugs. These electrodes render the spark plugs longer- lasting and combust fuel far more efficiently and completely. Hence, conventional materials erode and corrode too soon and quite frequently to be of any practical use in automobiles. Also, automobiles waste significant amounts of energy by losing the thermal energy generated by the engine. This is especially true in the case of diesel engines. Hence, the engine cylinders (liners) are currently being envisioned to be12. 13. 14. coated with nanocrystalline ceramics, such as zirconia and-alumina, so that they retain heat much more efficiently and result in complete and efficient combustion of the fuel. ‘Aerospace Components with Enhanced Performance Characteristies: One of the key properties required for the aircraft components is the fatigue strength, which decreases with the component's age. The fatigue strength increases with a reduction in the grain size of the material. Nanomaterials provide such a significant reduction in the grain size over conventional materials that the fatigue life is inereased by an average of 200-300%. Furthermore, components made of nanomaterials are stronger and can operate at higher temperatures, aircrafts can fly faster and more efficiently (for the same amount of aviation fuel). Longer-Lasting Medical Implants: Currently, medical implants, such as orthopaedic implants and heart valves, are made of titanium and stainless steel alloys. Since these materials arerelatively impervious, human tissue does not penetrate the implants, thereby reducing their effectiveness. Furthermofe, these metal alloys necessitate frequent very expensive surgeries. However, nanocrystalline zirconia (zirconium oxide) ceramic is hard, wear-resistant, corrosion-resistant (biological fluids are corrosive), and biocompatible, Nanoceramics can also be made porous into aerogels (aerogels can withstand up to 100 times their weight), if they are synthesized by sol gel techniques. This results in far less frequent implant surgeries. Nanocrystalline silicon carbide (SiC) is a material for artificial heart valves primarily due to its low weight, high strength, extreme hardness, wear resistance, inertness (SiC does not react with biological fluids), and corrosion resistance. Large Electrochromic Display Devices: An electrochromic device consists of materials in which an optical absorption band can be introduced, or an existing band can be altered by the passage of current through the materials, or by the application of an electric field. Nanocrystalline materials, such as tungstic oxide (WO,-xH,O) gel, are used in very large electrochromic display devices. Electrochromic devices are similar to liquid-crystal displays (LCD) commonly used in calculators and watches. However, electrochromic devices display information by changing colour when a voltages applied. When the polarity is reversed, the colour is bleached, The resolution, Trighlness and coulest ofthese device) greally depend on tie tagestc aca elt grain size. Hence, nanomaterials are being explored for this purpose.Pack MethodFurnace Nitriding Method Cyanding Method Flame HardeningOrifices for pressure spraying of heated surface Quench medium intet Inductor to set up magnetic field at desired area High frequency magnetic field ‘Area inductively heated by hysteresis and eddy currents Parts to be locally surface hardened Induction Hardening Fr Age Hardening Treatment of All Solid Solution Treatment > This method Is used to Increase the strength of malleable materials, magnesium, titanium, nickel, aluminum alloys and in certain stainless steels Solubility > Solubility is the property of solid, liquid or gaseous solute to dissolve in solid, liquid or gaseous solvent to form a homogeneous solution of them Solid Solution Treatment‘Solid Solution Treatment > Age or precipitation hardening is @ two step process, involving solution heat treatment and precipitation heat treatment steps, respectively > In the solution heat treatment step, the alloy is heated to high temperature T, where it forms a solution At this stage, the salute atoms uniformly spread across the host lattice and ensure there Is no scope for distortion in the lattice structure Solaion heat ‘Temperature TTT Diagram