Dept. of Chemistry, SCSVMV University Course: B.E & B.Tech Subject: APPLIED CHEMISTRY Unit: V NANOTECHNOLOGY Dr. K. SIVAKUMAR Dept. of Chemistry, SCSVMV University Syllabus: Introduction - Synthesis of nanomaterials by ball milling, vapour deposition and sol-gel methods.

Introduction: Properties: A nanometre is one billionth of a metre. For comparison, Size (thickness) of a human hair is ~ 80,000nm a red blood cell is ~ 7,000nm a water molecule is ~ 0.3nm Scientists are interested in nanoscale materials with 1nm to 100nm Properties: Properties of materials at nanoscale are different from larger scale Thermodynamics properties are drastically different from nanoparticles Examples: Melting point of gold decreases from 1200K to 800K when the particle size decreases from 300ºA to 20 ºA. In metals if the size is reduced from the bulk the electronic bands become narrower and the value of ionization potential is raised.

In nanophase metals absorbs hydrogen In nanophase metals absorbs hydrogen. This property can be used for hydrogen storage in metals. Fe, Co & Ni are in ferromagnetic in bulk state. But they are changed into supermagnetic in nanophase. Properties…..

1. Top down process: 1. Top down process: (Types of ) Synthesis of Nanomaterials: Bulk materials are broken into nano sized particle (for processing solid- state materials) Example: Ball milling method. 1. Top down process: (Types of ) Synthesis of Nanomaterials: Bulk materials are broken into nano sized particle (for processing solid- state materials) Example: Ball milling method. 1. Top down process:

2. Bottom-up process: (Types of ) Synthesis of Nanomaterials: Nano materials are produced by building of atom by a atom. Example: Chemical Vapour Deposition Method

Synthesis of Nanomaterials: Top down process: [No control over the size and Morphology of particles] Example: Ball Milling Plasma Arcing Laser sputtering Vapour Deposition methods Bottom up process: [Size and Morphology can be controlled] Sol-Gel method Colloidal method Electro deposition Solution phase reductions

Ball Milling Principle: Small hard balls are allowed to rotate inside a container and then it is made to fall on a solid with high force to crush the solid into nano crystal. Construction and Working: Hardened steel or tungsten carbide balls are put in a container along with powder of particles (50m) of a desired material. The container is closed with tight lids.

Ball Milling…. When the container is rotating around the central axis, the material is forced to press against the walls. The milling balls impart energy on collision and produce smaller grain size of nano particle. Ball milling is also known as Mechanical alloying or crushing

Advantages of Ball Milling Few mg to several kgs of nanoparticle can be synthesized in a short time. This technique can be operated at large scale. Applications Ball milling method is useful in preparation of elemental and metal oxide nano crystals like Co, Cr, Al-Fe, Ag-Fe and Fe. Variety of intermetallic compounds of Ni and Al can be formed. Ball milling method is useful in producing new type building materials, fire – proof materials, glass ceramics, etc.

Vapour Deposition Methods: for fabricating thin films & nano tubes Physical Vapour Deposition – involves direct deposition of materials on surface Chemical Vapour Deposition – involves a chemical reaction followed by the deposition

Chemical Vapour Deposition (CVD): Principle: The reactant particles are mixed with carrier gas and allowed to pass on through the hot solid substrate surface. When the reactant particles and substrate comes in contact, the heat energy initiate the chemical reactions and form nano film on the substrate surface. The byproducts of the reactions on the solid surface can be removed by washing.

CVD….. Description and Working: CVD involves the flow of gas with diffused reactants (substances to be deposited in vapour) over a hot substrate surface. The gas that carries the reactants is called the carrier gas. While the gas flows over the hot solid surface, the heat energy increases chemical reactions of the reactants that form film during and after the reactions. The byproduct of reactions are removed to get the thin film of desired composition

Advantages & applications of CVD To produce defect free nanoparticles Scaling up of the CVD system for manufacturing purpose is achieved without any major difficulties

Sol-gel Method: This method involves two types of materials ‘Sol’ and ‘Gel’ Principle: Sol-Gel method involves formation of ‘sols’ in a liquid and then connecting the sol particles to form a network. By drying the liquid, it is possible to obtain powders, thin films etc., Methods for sol-gel formation: Sol can be obtained by, Hydrolysis Condensation and Polymerization of monomers to form particles Agglomeration of particles After the formation of sol, formation of network (gelation) which extends throughout the liquid medium is obtained to form a gel.

Sol-gel Method… Synthesis of sol-gel involves hydrolysis of precursors, condensation followed by polycondensation to form particles, gelation and drying process by various routes (Figure). Precursors (starting chemicals) are to be chosen such that they have a tendency to form gels.

Sol-gel Method… Rate of hydrolysis and condensation reactions are governed by various factors such as pH Temperature Molar ratio Nature Concentration of catalyst Process of drying Finally, at proper conditions spherical nanoparticles are produced.

Sol-gel Method… Applications: Useful in oxide ceramics synthesis

Nanopolymers: Polymer nanocomposites / Nanopolymer is a polymer having dispersed in its nanoparticles. Nanopolymers may be of different shape (e.g., platelets, fibers, spheroids), but at least one dimension must be in the range of 1 to 50 nm. These PNC's belong to the category of multi-phase systems (MPS, viz. blends, composites, and foams) that consume nearly 95% of plastics production.

Properties of Nanopolymers: The nanofilms show considerable reinforcement when subjected to small deformations. Carbon nanotubes can conduct heat and electricity far better than copper, and are already being used in polymers to control or enhance conductivity.

Vapor condensation process: Preparation of Nanopolymers: Vapor condensation process: Involves evaporation of solid metal followed by rapid condensation to form nano-sized clusters. Various approaches to vaporize the metal can be used and variation of the medium in which the vapor is released affects the size of the particles. Inert gases are used to avoid oxygen while creating nanopolymers, where as the reactive oxygen is used to produce metal oxide ceramic products.

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Department of Chemistry Good Luck! The End Dr. K. SIVAKUMAR Department of Chemistry SCSVMV University chemshiva@gmail.com +91 98423 61378