An X-ray absorption spectroscopy study of the inversion degree in zinc ferrite nanocrystals dispersed on a highly porous silica aerogel matrix.

The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO(2) aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn(2+) ions are at the tetrahedral sites and trivalent Fe(3+) ions occupy octahedral sites (normal spinel). When particle size decreases, Zn(2+) ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix.

Magnetoresistive phenomena in an Fe-filled carbon nanotube/elastomer composite.

DC magnetoresistive effects were observed in above-percolation-threshold loaded Fe-filled carbon nanotube/polyurethane-urea composite samples. A phenomenological model is derived from interpretation of resistance relaxation for a range of axial strains. The large instantaneous magnetoresistance of + 90% observed at low axial strain was a result of conduction pathway breaking caused by preferential orientation of the conducting nanotubes perpendicular to the axial current flow: a result of the magnetic torque experienced by the ferromagnetic nanotube core. At large strain the observed large instantaneous change in resistance of - 90% resulted from voltage-driven relaxation in the conducting nanotube network. At high axial strain the competition between voltage-driven relaxation and a magnetic torque gave rise to an oscillatory component of resistance relaxation.

Synthesis and microstructure of manganese ferrite colloidal nanocrystals.

The atomic level structure of a series of monodisperse single crystalline nanoparticles with a magnetic core of manganese ferrite was studied using X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) techniques at both the Fe and Mn K-edges, and conventional and high resolution transmission electron microscopy (TEM and HRTEM). In particular, insights on the non-stoichiometry and on the inversion degree of manganese ferrite nanocrystals of different size were obtained by the use of complementary structural and spectroscopic characterization techniques. The inversion degree of the ferrite nanocrystals, i.e. the cation distribution between the octahedral and tetrahedral sites in the spinel structure, was found to be much higher (around 0.6) than the literature values reported for bulk stoichiometric manganese ferrite (around 0.2). The high inversion degree of the nanoparticles is ascribed to the partial oxidation of Mn(2+) to Mn(3+) which was evidenced by XANES, leading to non-stoichiometric manganese ferrite.

The structure of calcium metaphosphate glass obtained from x-ray and neutron diffraction and reverse Monte Carlo modelling.

The short range structure of (CaO)(0.5)(P(2)O(5))(0.5) glass has been studied using x-ray and neutron diffraction and modelled using the reverse Monte Carlo method. Using this combination of techniques has allowed six interatomic correlations to be distinguished and fitted to obtain a set of bond lengths and coordination numbers that describe the structure of the glass. The glass consists of metaphosphate chains of phosphate tetrahedra and each phosphate unit has two non-bridging oxygen atoms available for coordination with Ca. The Ca-O correlation was fitted with two peaks at 2.35 and 2.86 Å, representing a broad distribution of bond lengths. The total Ca-O coordination is 6.9 and is consistent with distorted polyhedral units such as capped octahedra or capped trigonal prisms. It is found that most non-bridging oxygen atoms are bonded to two calcium atoms. All of these observations are consistent with Hoppe's model for phosphate glasses. Furthermore, the medium range order is revealed to consist of phosphate chains intertwined with apparently elongated clusters of Ca ions, and the Ca-O and Ca-P correlations contributed significantly to the first sharp diffraction peak in x-ray diffraction.

Structural origin of light emission in germanium quantum dots.

We used a combination of optically-detected x-ray absorption spectroscopy with molecular dynamics simulations to explore the origins of light emission in small (5 nm to 9 nm) Ge nanoparticles. Two sets of nanoparticles were studied, with oxygen and hydrogen terminated surfaces. We show that optically-detected x-ray absorption spectroscopy shows sufficient sensitivity to reveal the different origins of light emission in these two sets of samples. We found that in oxygen terminated nanoparticles its the oxide-rich regions that are responsible for the light emission. In hydrogen terminated nanoparticles we established that structurally disordered Ge regions contribute to the luminescence. Using a combination of molecular dynamics simulations and optically-detected x-ray absorption spectroscopy we show that these disordered regions correspond to the disordered layer a few Šthick at the surface of the simulated nanoparticle.

The atomic structure of niobium and tantalum containing borophosphate glasses.

A complete structural study has been carried out on sodium borophosphate glass containing increasing amounts of either niobium or tantalum. A combination of high energy x-ray diffraction, neutron diffraction, extended x-ray absorption fine structure, nuclear magnetic resonance, and infrared and Raman spectroscopy has been used to discern the local atomic structure of each component and the changes with M content, where M is either niobium or tantalum. The glasses are found to consist of tetrahedral borate and phosphate with octahedral MO(6). As expected, B and P play the roles of tetrahedral network formers. At low M content there are isolated MO(6) units with [Formula: see text] and [Formula: see text] linkages that contribute to the glass network. As the M content increases, the number of [Formula: see text] links increases, and at the highest M content each MO(6) unit is connected to several others. The octahedra become significantly distorted as the niobium content increases, an effect that is not seen for tantalum.

Structural characterization study of FeCo alloy nanoparticles in a highly porous aerogel silica matrix.

A series of FeCo-SiO(2) nanocomposite aerogels having different FeCo loadings of 3, 5, and 8 wt % were prepared using a novel urea-assisted sol-gel route. The size of the nanoparticles, which was estimated using Scherrer analysis of the main peak of the x-ray diffraction pattern, varies from 3 to 8 nm. X-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) techniques at both Fe and Co K edges were used to investigate the structure of the FeCo nanoparticles. EXAFS and XANES show that FeCo nanoparticles have the typical bcc structure. Evidence of oxidation was observed in low FeCo content aerogels. Spatially resolved electron energy loss spectroscopy analysis suggests the formation of a passivation layer of predominantly iron oxide.

A molecular dynamics study of densification mechanisms in calcium silicate glasses CaSi2O5 and CaSiO3 at pressures of 5 and 10 GPa.

Molecular dynamics is used to obtain models of (CaO)(x)(SiO(2))(1-x) glasses, with compositions CaSi(2)O(5) (x=0.33) and CaSiO(3) (x=0.50), at pressures of 5 and 10 GPa. At 5 GPa there are increases in Ca and Si coordinations for x=0.33, whereas for x=0.50 there is distortion of CaO(N) polyhedra but no substantial change in coordination. At 10 GPa the Ca coordination increases by approximately 20% for x=0.33 and by approximately 10% for x=0.50. This increase is due to increased Ca bonds to bridging oxygens (O(b)), since nonbridging oxygens (O(nb)) are already highly bonded to Ca, and the proportion of O(nb) is decreasing due to changes in the silica network. At 10 GPa there are approximately 20% of fivefold and a few percent of sixfold coordinated Si. Since the new Si-O bonds involve the conversion of O(nb) to O(b), there is a corresponding increase in the network connectivity. The x=0.50 glass is more resistant to deformation because there is less possibility to convert O(nb) to O(b) due to lower Si content. The changes in Ca-O, Si-Ca, and Ca-Ca correlations are predicted to produce changes in the x-ray diffraction structure factor S(Q), including a shift of the first sharp diffraction peak to higher Q values.

The effects of different heat treatment and atmospheres on the NMR signal and structure of TiO2-ZrO2-SiO2 sol-gel materials.

The effects of different heat treatment schemes (i.e. successively or directly heated to particular temperatures) and atmospheres (air or nitrogen) on the solid-state NMR spectra obtained from (TiO(2))(0.15)(ZrO(2))(0.05)(SiO(2))(0.80) sol-gel materials are investigated. A combination of 1H, 13C, 17O and 29Si NMR is used. 29Si MAS NMR indicates that the extent of condensation of the silica-based network strongly depends on the maximum temperature the sample has experienced, but the condensation is largely independent of the details of the heat treatment scheme and atmosphere used. For sol-gel produced silicate-based materials the results show that the equilibrium structure at each temperature is reached rapidly compared to the time (2h) spent at that temperature. The 17O NMR results confirm that a nitrogen atmosphere does significantly reduce loss of 17O from the structure but care must be taken since there could be differential loss of 17O from the regions having different local structural characteristics.