7. Nanomaterials Nanomaterials - Preparation - Pulsed laser deposition - Chemical vapour deposition - Applications. Introduction A nanometre (nm) is one billionth ae of a metre. For 10° comparison, thickness of a single human hair is about 80,000 nm (80um), a red blood cell is approximately 7,000 nm (Tum) wide and a water molecule is almost 0.3 nm across. Scientists and engineers are nowadays interested in nanoscale materials which is ranging from 1 nm to 100 nm. At nanoscale, the properties of materials are very different from those at larger scale. Therefore, the nano-world is in between quantum world and macro world. Nanoscience is concerned with the study of phenomena and manipulation of materials at nanometer scales. Nanotechnology is the design, production, characterization and application of structures, devices and systems by controlling shape and size at the nanometre scale. NANOMATERIALS Definition Nano materials are newly developed materials with Brain size at the nanometre range (10° m) i.e. in the order of 1 - 100 nm. The particle size in a nano material 's in the order of nm.re Proywng — aphawe materials In addition to emailer grain #1e, nanomaterials contair, ousands) of atoms In contrast, le vary from a few several billions Special features of nan Jess number (a few ten Uy the grain sizes of conventional materia microns to @ few millimetres and contain of atome Those basic differences make nanomaterials unique and special Nanomaterials contain a very large number of grain boundaries which may be 50% or more of the total volume of the material This unique microstructure makes these materials to exhibit different properties such as tremendous strength, hardness, formability and toughness. For example, nanocrystalline copper is five times more stronger than ordinary copper, Further, the increased grain boundary increases magnetic and chemical properties. Different forms of nanomaterials Nano-structured material ‘The structures whose characteristic variations in design length is at the nanoscale. Nano particles: ‘The particle size is in the order of 10°? m. Nano dots: Nanoparticles which consist of homogencous material, especially Uhey are almost spherical or cubical in shape.anomaterials a Nanorods: Nanostructures which are shaped like long sticks or rods ith diameter in nanoscale and a length very much longer. Nanotubes: The carbon nanotubes are the wires of pure carbon like rolled sheets of graphite or like soda straws, Nanowires: Nanowires are nanorods which especially conduct electricity. Fullerenes: A form of carbon having a large molecule consisting of an empty cage of 60 or more carbon atoms. Nanocomposites: Composite structures whose characteristic dimensions are found at nanoscale. Cluster: A collection of units (atoms or reactive molecules) upto about 50 units. Colloids: __ A stable liquid phase containing particles of size 1-1000 nm range. A number of metals, alloys, intermetallics, ceramics, Polymers as well as composites are synthesized in nano form. Synthesis of Nanomaterials The methods for the synthesis of nanomaterials are broadly classified into two ways (i) Top-down process (ii) Bottom-up process74 Engineering Physics ~ Synthesis nano materials ‘Top-down process Bottom-up process Example Example Ball milling Chemical vapour ; deposition, sol-gel é (a) Top down process In this process, the bulk materials are broken into nano sized particle as shown in fig 7.1 It is an example of solid-state processing of materials oo 2 Fig. 7.1 Synthesis from bulk materials. Example: Mechanical alloying (or) Ball milling (b) Bottom-up process In this process, nano materials are produced by building of atom by an atom as shown in fig 7.2 of on 00 = einai O° @2@0 Fig. 7.2 Synthesis from individual atoms Example: Chemical vapour depositionterial Nenomaterials 75 7.2) PREPARATION OF NANOMATERIALS There are few widely known methods to produce nanomaterials. They are G) Ball milling (ii) Plasma arcing Gii) Chemical vapour deposition (iv) Sol-Gels. (v) Electro-deposition (vi) Laser synthesis (vii) Inert gas condensation techniques it is possible to produce Using the above form of nano-powders, nano-crystals, nano-materials in the nano-films, nano-wires, methods, let us discuss nano-tube, nano-dots, etc. From these the few methods briefly.wlodern Engineering Materials = 5.46.1.1 Milling One nanofabrication technique of major industrial importance is high energy ball milling. > This technique is also known as mechanical alloying \ or mechanical attrition. It is a solid state process [ | used for the manufacture of a wide range of nanopowders. High energy ball milling can induce structural changes and chemical reactions at room temperature. Fig. 5.19 Rolling ball mill The method consists of placing materials in the form of powder into a stainless steel rotating drum with hard steel or tungsten carbide balls inside it as shown in Fig. 5.19. The container is purged and argon is introduced to prevent unwanted reaction such as oxidation. The milling is carried out at room temperature for upto 150 hours. As shown in Fig. 5.20 the Development of laminar structure ; and grain size refinement powder materials are crushed < Powders in the rotating drum ! mechanically i by the hard balls. This repeated deformation ca” cause large ns in grain size in the reductio The size of the particles. ru ctured grains induced in ee wor particles i8 determined the pow istry of the powder Hard steel or Repeated fracture by the chem! ae A tee WC balls and cold welding articles milling an eal Fig. 5.20 Mechanical alloying process P + conditions. tr ee grocess steps in the formation of nanoparticles by milling i shown in5.22 Reaction product is heat Ball mill acts as a Chemical reactions : low temperature occur at nanoscale. treated. Solid phase chemistry chemical reactor, Low temperature prevents particles from reaction process enables controlled agglomeration. results from local nano particle heat and pressure formation. at contact surface. Fig. 5.21 Schematic representation of proce: High energy ball milling is used for the production of nanocrystalline materials ss steps in the nanoparticle formation is milling nanoparticles nanocomposites a. b. c. d. nanotubes e. nanorods and f. nanowiresSa\-get cauthod . This % @ vergolile industrial approoch Sabricating Manoenalenials: TH » a solution Phase symbhetic owe do poo highly pure MoterialeGelence well as densities. This method affords easy control over the stoichiometry and homogeneity that conventional methods lack. This technique allows us to change the composition and structure of materials on the nanometer scale. Its benifits include the convenience of low-temperature preparation using general and inexpensive laboratory equipment. One of the important features of the technique is its ability to produce materials in different forms, such as powders, films, fibres of nanosize and free standing pieces of materials called monoliths. Scientists have used this technique to produce the world’s lightest materials and some of the toughest ceramics. The sol-gel method is based on the phase transformation of a sol obtained from metallic alkoxides or organometallic precursors. This sol, which is a solution containing particles in suspension is polymerised at low temperature to form a wet gel. The wet gel is then densified through thermal annealing to get the products like a glass, polycrystals or a dry gel. Typically this involves a hydrolysis reaction followed by condensation and polymerisation. For example ‘Tetraethylorthosilicate (TEOS) (Si(OC,H,),) + ethanol (C,H,OH) —“t*#2_, SiO, + other products The polymer gel so formed is a three dimensional skelton surrounding interconnected pores and this can be dried and shrunk to form a rigid solid form. The transformation to a gel is achieved by changing the pH or the concentration of the solution. The entire sol-gel process is summarised in the scheme shown in Fig. 5.36, The method starts with a solution consisting of metal compounds such as metal alkoxides and acetylacetonates as source of oxides, water as hydrolysis agent, alcohol as solvent and acid or base catalyst as shown in the first beaker. A sol like that shown in the second beaker can be formed through the hydrolysis and condensation of dissolved molecular precursors. This produces nanometer sized particles to form a colloidal suspension or sol. The colloidal nanoparticles are then linked with one another in a 8D, liquid filled solid network called Gel as shown in the third beaker. The transformation to a Gel network isModern Engineering Materials | achieved by changing pH of the solution, solvent, the temperature and concentrations of reactions, The super critical drying process removes the liquid phase from the gel and produces a low-density 3D porus material called aerogel. Aerogels densities are typically between 1 - 20% that of the bulk material when the gel is dried slowly in a fluid evaporation process, the gels original network collapses, which creates a high density material known as a Xerogel. Xerogel densities can be between 30 - 80% that of the bulk. = = Concensation _ 4 go Solution of precursors aN Spray, dip. oF spin coat“ te ve Soddoe oSoddow oPEDISP, Coated substrate Dense ceramic Pow Fig. 5.36 Process steps of sol-gel processing nanoparticles and the possible final products of the method The sol-gel method allows the straightforward preparation of monoliths or powders. Fibres can be drawn from the viscous sol having proper composition. Coating of films can be made by spin or dip coating of the sol. Bulk bodies can be made by casting the gelling sol into a mold. Membranes are prepared by pouring the sol on the porous oxide with coarse pores. Fig. 5.37 is a schematic representation of such a sol-gel derived nanocomposite.nornaterials Ne 7.13 ) APPLICATIONS OF NANQPHASE MATERIALS Nanoparticles are “the small particles with a bi future”. Because of their extremely small particle size, they have extremely large specific surface area. Hence, they eh chemically very active. They are stronger and more ductile. Their electronic states are quite different from those of bulk. Some of the detailed applications of nanomaterials are given below. 4, Materials Technology thesis harder metals having hardness 5 times « We can syni articles. higher than normal metals using nanop: resistant, tougher and flame hesized with nanoparticles as acement of body parts and Stronger, lighter, wear retardant polymers are syntl fillers. They are used in repl. metals (bio-materials). unusual colour paints using e We can produce nanoparticles exhibit entirely nanoparticles since different optical properties. are used in nanoelectronic devices ceramic capacitors for energy bilisers. The special features d reduced power Nanophase materials such as nanotransistors, storage, nois of these devi losses- e filters and stal ices include smaller sizes ant rs are used in thermal-protection and 7nO_ thermisto: current-controlling devices. 2, Information Technology 5 Nanoparticles are used for data storage. Quantum electronic conventional devices. devices have started replacing bulkEngineering Physics - 7.14 o produce very tiny permanent used t | Hence, they are used orgy produc ording. « Nano materials are magnets of high ¢ y h-density magnetic rec u-Fe alloy are used in RAM, in hig « Magnetic devices made of C READ/WRITE heads and sensors. quantum wells and quantum wires are semiconductor nanomaterials, in computer storage (memory) * Quantum dots, mainly produced from Hence, they are used devices. 3. Biomedicals itive nanoparticles are used for tagging of DNA * Biosens and DNA chips. « Controlled drug delivery is possible —_ using nanotechnology. Diffusion of medicine through nanoporous polymer reservoir as per the requirement is very useful in controlling the disease. * Nanostructured ceramics readily interact with bone cells and hence finds applications as an implant material. 4. Energy storage * Since the hydrogen absorbing capability increases with decrease of size of nanoparticles, nanoparticles of Ni, Pd and Pt are useful in hydrogen storage devices. * Metal nanoparticles are very useful in fabrication of ionic batteries. 5. Optical devices + Nanomaterials are i : used in z fe semiconductor laser and CD's. making _ efficie + Nanoparticulate zine oxide : iste effective Sunacreons, is used to manufacture * Nanoparticles are used in the to protect from scratch or breal coatings for eye glass kage.somaterials Nanomal 716 6. Transmission lines Nanophase materials are used in the fabrication of signal processing elements such as filters, delay lines, switches o| 7, Nanomicro-Electro Mechanical Systems (Nano MEMS) have direct implications on in pressure sensors and mass sensors, , optical switches, 8. Molecular Nano-Technology (MNT) is aimed to develop robotic machines, called assemblers on a molecular scale, molecular-size power sources and batteries. 9. Underwater nanosensor networks arc used to detect the movement of ships in an efficient manner with faster response. They can also detect chemical, biological or radiological materials in cargo containe a