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Nucleation: stochastic process strongly dependent on supersaturation (bulk concentration solubility) Growth: deterministic process directly dependent on supersaturation
Microemulsion Technique
A microemulsion can be defined as the thermodynamically stable, optically clear dispersion of two immiscible liquids (water and oil) consisting of nano size domain of one or both liquids in the other that are stabilized by an interfacial film of surfactants molecules.
The water solubilized in the core, forming a waterpool is characterized by R, the water to surfactant molar ratio. (R= [H2O]/[S]). The aqueous core of the w/o microemulsion can be used as a nano reactor to produce nano particles by chemical reactions within the core.
1. Equal volumes of two microemulsions containing two different reactants in their aqueous core are mixed. 2. The Brownian motion of the reverse micelles leads to collision. 3. The surfactant layers open up and coalesce forming transient dimmers. (Fusion). 4. Mixing of reactants during fusion. 5. Reaction between reactants, giving rise to products. 6. Decoalescence to return as reverse micelles (Fission)
Average occupancy number the number of ions/reactant molecules present in the microemulsion droplet. Intermicellar exchange rate. Nature of surfactant molecule Water to surfactant molar ratio (R). Nature of oil phase Additives. Some Nanoparticles synthesized by this method ( CdS, ZnS, Ag, AgCl, TiO2 etc).
1) Post Core Method: A microemulsion of AgNO3 solution was added to the micro emulsion containing CdS nanoparticles, and an excess amount of (NH4)2S, which act as cores. 2) Partial Micro emulsion method : AgNO3 solution was added drop wise directly to the microemulsion containing core CdS nanoparticles with excess (NH4)2S .
The W/O microemulsions can be used as nanoreactors to produce nanoparticles by carrying out chemical reactions in their aqueous core and also the surfactant layer of the microemulsion droplets prevents the aggregation of particles by acting like cage. * This technique does not require any special equipment and extreme conditions of temperature and pressure. 3* It is possible to control the size and morphology of particles formed by controlling the initial parameters. * The nanoparticles can be stored in these W/O microemulsions for a long time without aggregation.
*Therefore the method may turn out to be expensive for commercial applications.
*The separation of particles from the microemulsion droplets is also a challenging task.
The sol-gel processing can control the structure of a material on a nanometer scale from the earliest stages of processing. This technique to material synthesis is based on some organometallic precursors, and the gels may form by network growth from an array of discrete particles or by formation of an interconnected 3-D network by the simultaneous hydrolysis and polycondensation of organometallic precursors.
The size of the sol particles and the crosslinking between the particles depend upon some variable factors such as pH, solution composition, and temperature etc. Thus by controlling the experimental conditions, one can obtain the nanostructured target materials in the form of powder or thin film. Used for prepartion of inorganic oxides such as glasses and ceramics,and organic/inorganic hybrid materials.
Drying
Thermal Decomposition
Sintering
Collapse the gel structure Solidify the gel Enhance further crystallization
Thin films
Dipping factors include viscosity, removal rate of the substrate Spin coating factors include viscosity, surface tension, time to gel, spin speed
Sol-Gel Synthesis
Advantages:
Better control of particle size Homogeneity in particle distribution Potentially higher purity Lower processing temperatures High cost of raw materials Low yield and density of the products Residual carbon
Disadvantages:
Pyrolysis
Pyrolysis is a chemical process in which chemical precursors decompose under suitable thermal treatment into a solid compound and the waste evaporates away. Common precursors used : MCO3, MC2O4, M (CO) x, MNO3, glycolate, citrate and alkoxides. Commonly used protecting agents : Polyvinyl alcohol (PVA) and polyethylene glycol (PEG) Nanoparticles produced : metals, metal oxides, semiconductors, composite materials and carbon nanotubes. The conditions of the reaction which need to be controlled In order to get a uniform nanosized material: * slowing of the reaction rate, * decomposition of precursor in an inert solvent.
Cobalt nanoclusters were synthesized by the thermal decomposition of an organometallic precursor, octacarbonyl dicobalt in an inert atmosphere Stabilizer used polystyrene solvent used - toluene. The reaction condition: The reaction was carried out at 90 C with constant stirring for a period of ten to twelve hours. Kinetics of growth of the nanoclusters was studied in order to understand the role of polymers in the nucleation and
growth process.
The spectrophotometer records the intensity of absorption (A) or optical density (O.D.) as a function of wavelength. The technique gives the preliminary concept of particle size and size distribution. Usually a blue shift (decrease in wavelength ) is associated with a decrease in particle size. This technique has been used to characterize Ag, AgCl , CdS , ZnS , CdS/Ag2 S core shell nano particles.
TEM is a microscopy technique where an image is formed from the interaction of the electrons transmitted through the specimen, which is magnified and focused onto an imaging device. TEM is a powerful analytical technique used for size and morphology charecterization of different materials like metals, semicoductors to polymers and biological specimens. With the addition of energy dispersive x-ray analysis (EDAX) , the TEM can also be used as a tool for identifying the elements in the nano samples. This technique has been used to characterize different types of nanostructured materials like nanoparticles, nanowires, nanotubes as well as core-shell and composite structures.
The scanning electron microscope (SEM) is a type of electron microscope that images the sample surface by scanning it with a highenergy beam of electrons across a rectangular area of the specimen. The signals result from the interactions of the electron beam with atoms at or near the surface of the sample. Generally, the image resolution of an SEM is about an order of magnitude poorer than that of a TEM. SEM image relies on surface processes rather than transmission , so it has a much greater depth of view, and so can produce images that are a good representation of the 3D structure of the sample.
An SEM image of trigonal tellurium nano tubes
( B. Mayers, Y. Xia, Adv. Mat. 2002, 14, 279)
The X-ray photoemission technique (XPS) is an analytical technique generally used for the surface analysis of materials. XPS is used to obtain information about elements and their chemical bonds, enabling identifications of the different chemical compounds on the surface. The XPS technique is surface specific due to the short range of the photoelectrons that are excited from the solid.
The basic process is the interaction of a photon (x-ray) of energy h , with an electron of biding energy BE in the material. BE is the direct measure of the energy required to remove an electron from its initial level to vacuum level. The kinetic energy of the photoelectron in the vacuum level is given by KE = h BE. The energy of the photoelectron thus leaving the surface is determined, and this gives a spectrum of intensity as a function of binding energy. The binding energies of the peaks are characteristics of each element. The peak areas can be used to determine the composition of material surface. XPS is not sensitive to hydrogen or helium, but can detect all other elements.This technique has been used to characterize nanoparticles as well as nano composites like CdS, Ag2S , CeO2-ZrO2.
XPS spectra of Cd 3d core level (a) CdS nanoparticles;and (b) CdSAg2S (post-core method) core-shell nanoparticles. (Hota etal, colloids and surfaces A, 293, 5-12, 2007)
Applications of Nanoparticles
Engineering Applications
Catalysis: The catalytic properties of nanoparticles are enhanced due to presence of large fraction of reactive atoms that reside on the surface. Ni nanoparticles embedded in silica Paints, pigments, coatings: Silver nano particles have been used in paints for refrigerators and washing machines for their antimicrobial properties. Zinc nanoparticles dispersed in industrial coatings can be used to protect wood, plastic and textiles from exposure to UV rays. Superhydrophobic coatings; lotus spray
Application of Nanoparticles(contd.)
Optical and electronic devices Semiconductor nanoparticles can be used for preparation of laser diode, transducer, photo emitter and computer chips. Polymer materials with high content of inorganic nanoparticles leading to a high dielectric constant are interesting materials for photonic band gap structures.
Applications of Nanoparticles(contd.)
Nanoelectronics
Nanoelectronic devices are likely to use nanoparticles for a variety of purposes spanning from using it as component device to using it as in connecting and supporting features. Nanoparticles can be used in improving display screens on electronics devices by reducing power consumption while decreasing the weight and thickness of the screens and increasing the density of memory chips. Researchers are also currently developing a type of memory chip with a projected density of one terabyte of memory per square inch or greater.
Applications of Nanoparticles(contd.)
Healthcare Products
Nanocrystalline silver is used as an antimicrobial agent in the
treatment of wounds. Q-Dots are being developed that identify the location of cancer cells in the body. Drug delivery directly to cancer cells to minimize damage to healthy cells. Nanoshells have been developed that concentrate the heat from infrared light to destroy cancer cells with minimal damage to surrounding healthy cells. Nanotubes have been used in broken bones to provide a structure for new bone material to grow.
Applications of Nanoparticles(contd.)
Energy
Nanotechnology in fuel cells
Reduce the cost of catalysts used in fuel cells to produce hydrogen ions from
fuel such as methanol. Improve the efficiency of membranes used in fuel cells to separate hydrogen ions from other gases such as oxygen.
Researchers at the University of San Diego have shown how to use nanowires
to improve efficiency of thin film solar cells. Researchers at Georgia Research Institute demonstrate nanotube based solar cells that absorb much higher percentage of light than ordinary solar cells. Companies have developed nanotech solar cells that can be manufactured at significantly lower cost than conventional solar cells.
Application of Nanoparticles(contd.)
Nanotechnology in Batteries Battery using nanomaterials will be as good as new
after sitting on the shelf for decades. Another battery can be recharged significantly faster than conventional batteries.
Applications of Nanoparticles(contd.)
Environment Nanoparticles are used for reducing the amount of platinum used in catalytic converters in automobiles and industries. Reducing emissions from power plants by converting carbon dioxide to carbon nanotubes. Iron nanoparticles can be used to cleanup carbon tetrachloride pollution in ground water. Nanoparticles that can absorb radioactive particles polluting ground water are used to remove radioactive waste. Gold tipped carbon nanotubes have been used to trap oil drops polluting water.
Applications of Nanoparticles(contd.)
Personal Care Products
Titanium dioxide nanoparticles and zinc oxide coated titanium
dioxide nanoparticles have potential application in developing transparent sunscreen lotions and creams. Sunglasses using antireflective ultra thin polymer coatings are available in the market. The use of engineered nanofibers already makes clothes waterand stain-repellent or wrinkle-free. A nanocomposite coating process could improve food packaging by placing anti-microbial agents directly on the surface of the coated
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