Small particles and clusters nanomaterials

There is a distinct region of small aggregates or clusters which falls between the atomic (or molecular) domain and that of condensed matter. These small particles and clusters possess unique properties and have several technological applications. The formation of these particles involves a vapour-solid, a liquid-solid, a solid-solid or a vapour-liquid-solid type of phase change governed by nucleation and it is important that the size of the growing nucleus is controlled (Multani, 1981 Hadjipanyas Siegel, 1994). 

Transmission and scanning electron microscopy are employed for a direct study of microclusters while the distribution of sizes (or average diameter) is provided by sedimentation and other techniques. The average particle diameter is obtained by the Brunauer-Emmett-Teller (BET) surface-area method and by X-ray line broadening. 

Microcrystals exhibit properties distinctly different from those of bulk solids. The fractional change in lattice spacing has been found to increase with decreasing particle size in FejOj. Magnetic hyperfine fields in a-FejOj and FejO are lower in the microcrystalline phase compared to those of the bulk crystalline phases. The tetra-gonality (i.e. the departure of the axial ratio from unity) of ferroelectric BaTiOj decreases with decrease in particle size in PZT, the low-frequency dielectric constant decreases and the Curie temperature increases with decreasing particle size. The small particle size in microcrystals cannot apparently sustain low-frequency lattice vibrations. 

The various methods of preparation employed to prepare nanoscale clusters include evaporation in inert-gas atmosphere, laser pyrolysis, sputtering techniques, mechanical grinding, plasma techniques and chemical methods (Hadjipanyas Siegel, 1994). In Table 3.5, we list typical materials prepared by inert-gas evaporation, sputtering and chemical methods. Nanoparticles of oxide materials can be prepared by the oxidation of fine metal particles, by spray techniques, by precipitation methods (involving the adjustment of reaction conditions, pH etc) or by the sol-gel method. Nanomaterials based on carbon nanotubes (see Chapter 1) have been prepared. For example, nanorods of metal carbides can be made by the reaction of volatile oxides or halides with the nanotubes (Dai et al., 1995). 

Nanophase materials are prepared by compacting the nanosized clusters generally under high vacuum. Synthesis of such nanomaterials has been reported in a few systems. The average grain sizes in these materials range from 5 to 25 nm. 

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