Defect induced electronic states and magnetism in ball-milled graphite.

The electronic structure and magnetism of nanocrystalline graphite prepared by ball milling of graphite in an inert atmosphere have been investigated using valence band spectroscopy (VB), core level near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and magnetic measurements as a function of the milling time. The NEXAFS spectroscopy of graphite milled for 30 hours shows simultaneous evolution of new states at ~284.0 eV and at ~290.5 eV superimposed upon the characteristic transitions at 285.4 eV and 291.6 eV, respectively. The modulation of the density of states is explained by evolution of discontinuities within the sheets and along the fracture lines in the milled graphite. The magnetic measurements in the temperature interval 2-300-2 K at constant magnetic field strength show a correlation between magnetic properties and evolution of the new electronic states. With the reduction of the crystallite sizes of the graphite fragments, the milled material progressively changes its magnetic properties from diamagnetic to paramagnetic with contributions from both Pauli and Curie paramagnetism due to the evolution of new states at ~284 and ~290.5 eV, respectively. These results indicate that the magnetic behaviour of ball-milled graphite can be manipulated by changing the milling conditions.

Photoemission and absorption spectroscopy of carbon nanotube interfacial interaction.

Element-specific techniques including near edge X-ray absorption fine structure, extended X-ray absorption fine structure and X-ray photoemission spectroscopy for the characterization of the carbon nanotube interfacial interactions are reviewed. These techniques involve soft and hard X-rays from the laboratory-based and synchrotron radiation facilities. The results provided information of how the nano-particles of catalysts are involved in the initial stage of nanotube growth, the nanotube chemical properties after purification, functionalization, doping and composite formation.

Structural-chemical evolution within exfoliated clays.

The exfoliated (delaminated) structures of lamellar clays offer potential as precursors for the formation of various nanostructured materials. In this article, Lucentite and Laponite phyllosilicate clays, which both have empirical formulas of Na(0.33)[Mg(2.67)Li(0.33)Si4O10(OH)2] but differ in nanodimensions, have been exfoliated. Experiments were carried out for mixtures containing approximately 1 wt % phyllosilicate in a 5% aqueous solution of poly(acrylic acid) at different temperatures. X-ray diffraction and photoemission spectroscopy measurements for the solid products recovered after stirring the mixtures at 20 degrees C showed that the fully extended chains of poly(acrylic acid) were intercalated within the interlayer spaces between the silicate plates of the clays. At 85 degrees C, however, the clays were exfoliated and/or partially exfoliated. Photoemission spectroscopy also indicated that the exfoliated structures primarily consisted of silica nanoplates. 29Si nuclear magnetic resonance and oxygen K-edge near-edge X-ray absorption fine structure indicated that the surfaces of the plates were terminated by high concentrations of the silanol (-SiOH) groups, which created structural branches during intercalation. A model was developed in which intercalation and the removal of ions from the clays after the poly(acrylic acid) interactions reduced the electrostatic van der Waals forces between the plates. It was also shown that the formation of branches created a steric effect that inhibited the stacking of the plates. Together these resulted in exfoliation.

Dispersion of organically modified clays within n-alcohols.

A method for formation of polymer-clay nanocomposites involves dispersion of the nanometer silicate layers of clays into a solvent, followed by dispersion into polymers. The dispersion of layered silicates within solvents affects the structure and properties of the nanocomposites. We report the dispersion of organically modified clays, used for formation of nanocomposites with organic polymers, within a range of alcohol solvents. Experiments involved stirring a mixture containing approximately 1 wt% of alkylammonium-modified clays in n-alcohols with general molecular structure RnOH, where n represents the number of carbons of alkyl chains, varying from 2 to 8. The clays precipitated from the dispersion when RnOH solvents with n<5 were used, however, they formed gels for solvents with n5. The increased dispersion was related to the decrease of polarity and hydrogen bonding force within solvents. X-ray diffraction for the dispersed clays indicated that the interlayer spaces (1.8 nm), formed by regular stacking of the silicate layers, expanded to a maximum of 3.0 nm after treatment with RnOH with n5. The interlayer expansion was due to the intercalation of n-alcohol molecules within the interlayer spaces. It is suggested that the alkyl chains of n-alcohols remain parallel to the silicate surface in the intercalate. Preliminary experiments on the influence of these alcohol solvents on the intercalation of polyol (polyether) are also reported.