Elastic properties of nanoparticle chain aggregates of TiO2, Al2O3, and Fe2O3 generated by laser ablation

Previous studies have shown that nanoparticle chain aggregates (NCA) of titania are elastic [S. K. Friedlander, H. D. Jang and K. H. Ryu, Appl. Phys. Lett. 72, 1 (1998)]. The NCA were a few tenths of a micron long and composed of (approximately) 7 nm primary particles. They were produced by thermal decomposition of titanium tetraisopropoxide vapor in nitrogen. The goal of this study was to see whether the elastic behavior depends on (a) the material properties, (b) primary particle size, and (c) method of NCA formation. For this purpose, titania, alumina, and iron oxide NCA were generated by laser ablation. Rotating metal foil targets were mounted in a small cylindrical chamber and exposed to an excimer laser beam. The resulting aerosol was swept out by an oxygen stream. The generator was operated to produce NCA with similar mobility diameter and primary particle size. The NCA were deposited on the carbon or formvar films of an electron micrograph grid. Under the electron beam a hole develops in the carbon film in the neighborhood of the deposited NCA. The NCA then stretch and contract as described in our earlier study [S. K. Friedlander, H. D. Jang and K. H. Ryu, Appl. Phys. Lett. 72, 1 (1998)]. The titania, alumina, and iron oxide NCA generated by laser ablation all showed elastic behavior for primary particles smaller than about 10 nm. However, titania NCA composed of 36 nm primary particles did not exhibit elastic behavior indicating that very small primary nanoparticles are needed for this phenomenon to occur. The small scale stretching and contraction of chain segments were studied by measuring changes in the bond angles between adjoining particles and in the lengths of the segments studied. The elastic behavior is probably associated with local folding of chain segments due to van der Waals forces. Under tension, folded chains straighten but when the tension is relaxed, folds tend to reform but not reversibly. Rotation and sliding probably occur at the boundaries between particles during stretching. We hypothesize that elastic behavior is a general property of NCA composed of transition metal oxides with primary particles smaller than 10-15 nm; the phenomenon has now been observed for NCA produced in two ways, thermal decomposition and laser ablation. These phenomena may play a role in the action of nanoparticle additives such as fumed silica and carbon black used to improve the properties of rubber. NCA elasticity may also contribute to the ductile properties of nanoparticle compacts. (C) 2000 American Institute of Physics. [S0021-8979(00)06701-3].