The effect of space-charge formation on the grain-boundary energy of an ionic solid.

Taking the model system of an oxide containing acceptor dopant cations and charge-compensating oxygen vacancies, we calculate at the continuum level the change in the excess grain-boundary energy of an ionic solid upon space-charge formation. Two different cases are considered for the space-charge layers: (i) only vacancies attain electrochemical equilibrium and (ii) both dopants and vacancies attain electrochemical equilibrium. The changes calculated for a specific set of grain boundaries indicate that, depending on dopant concentration, space-charge formation can decrease the excess free energy by up to 15% in the first case and by up to 45% in the second case. The possibility of the excess grain-boundary energy going to zero and the possible effects of an external electric field on the excess grain-boundary energy are also discussed. This article is part of a discussion meeting issue 'Energy materials for a low carbon future'.

Growth of magneto-optically active (Zn,Mn)Se nanowires.

We describe the growth of Zn(1-x)Mn(x)Se nanowires in ultrahigh vacuum seeded by Au nanodroplets. Electron microscopy reveals the formation of single-crystal c-axis wurtzite nanowires (typically 1-3 microm long) with Mn concentrations up to x approximately 0.6, accompanied by a dense horizontal undergrowth of shorter, crooked nanowires. Magnetophotoluminescence measurements show evidence for sp-d exchange effects in a reduced symmetry environment. We find that the optical emission is surprisingly dominated by the undergrowth of crooked nanowires.

Stoichiometry and valence measurements of niobium oxides using electron energy-loss spectroscopy.

Qualitative and quantitative electron energy-loss spectroscopy analyses have been performed on niobium and stable niobium oxides (NbO, NbO(2) and Nb(2)O(5)). At integration windows (Delta) greater than 75 eV, k-factor analysis can be used to distinguish between the stoichiometry of the three oxides within 5.7% error. As seen in other metal oxides, with increasing oxidation state the metal ionization edges shift to higher energies relative to the O-K edge. Normalized M(2,3) white-line intensities show a strong correlation with 4d occupancy for each compound. The data are in correspondence with that observed in the literature for 4d transition metals using normalized L(2,3) white lines. Lastly, a distinctive energy-loss near-edge, structure of the O-K edge was observed for each oxide, which could be used as a fingerprint for analysis of unknowns.

Debundling and dissolution of single-walled carbon nanotubes in amide solvents.

Wet chemical methods involving ultrasound and amide solvents were used to purify and separate large bundles of single-walled carbon nanotubes (SWNTs) into individual nanotubes that could then be transported to silicon or mica substrates. The SWNTs studied were produced by the arc-discharge process. Dry oxidation was used in an initial step to remove amorphous carbon. Subsequently, two acid purification schemes were investigated (HCl- and HNO(3)-reflux) to remove the metal growth catalyst (Ni-Y). Finally, ultrasonic dispersion of isolated tubes into either N,N-dimethylformamide (DMF) or N-methyl-2-pyrrolidone (NMP) was carried out. Raman scattering, atomic force microscopy (AFM), and electron microscopy were used to study the evolution of the products. Raman scattering was used to probe possible wall damage during the chemical processing. We found that both HCl and HNO(3) could be used to successfully remove the Ni-Y below approximately 1 wt %. However, the HNO(3)-reflux produced significant wall damage (that could be reversed by vacuum annealing at 1000 degrees C). In the dispersion step, both amide solvents (DMF and NMP) produced a high degree of isolated tubes in the final product, and no damage during this dispersion step was observed. HNO(3)-refluxed tubes were found to disperse the best into the amide solvents, perhaps because of significant wall functionalization. AFM was used to study the filament diameter and length distributions in the final product, and interesting differences in these distributions were observed, depending on the chemical processing route.

Raman spectroscopy and structure of crystalline gallium phosphide nanowires.

Gallium phosphide nanowires with a most probable diameter of approximately 20.0 nm and more than 10 microns in length have been synthesized by pulsed laser vaporization of a heated GaP/5% Au target. The morphology and microstructure of GaP nanowires have been investigated by scanning electron microscopy and transmission electron microscopy. Twins have been observed along the crystalline nanowires, which have a growth direction of [111]. Raman scattering shows a 4 cm-1 downshift of the longitudinal optical phonon peak in the nanowire with respect to the bulk; the transverse optical phonon frequency and line width are, however, the same as in the bulk. The quantum confinement model first proposed by Richter et al. cannot explain the observed behavior of the Raman modes.

In-situ transmission electron microscopy studies of polymer-carbon nanotube composite deformation.

This paper demonstrates the viability of in-situ transmission electron microscopy for studying the deformation mechanisms of polymer nano-composites. In-situ straining studies are performed on carbon multiwalled nanotube (MWNT)-polystyrene composite films. The experiments show that load transfer across the nanotube-polystyrene interface is operative well into the plastic deformation regime of the composite film. The MWNTs are observed to bridge cracks propagating through the polystyrene, providing closure stresses across the crack wake. Although some MWNTs fracture by either a sword-in-sheath mechanism or transverse shear fracture, most of the MWNTs eventually debond at the MWNT-polymer interface and subsequently pull out of the matrix.

Magnetoelastic sensors in combination with nanometer-scale honeycombed thin film ceramic TiO2 for remote query measurement of humidity.

Ribbonlike magnetoelastic sensors can be considered the magnetic analog of an acoustic bell; in response to an externally applied magnetic field impulse the sensors emit magnetic flux with a characteristic resonant frequency. The magnetic flux can be detected external to the test area using a pick-up coil, enabling query remote monitoring of the sensor. The characteristic resonant frequency of a magnetoelastic sensor changes in response to mass loads. [L.D. Landau and E. M. Lifshitz, Theory of Elasticity, 3rd ed. (Pergamon, New York, 1986). p. 100].Therefore, remote query chemical sensors can be fabricated by combining the magnetoelastic sensors with a mass changing, chemically responsive layer. In this work magnetoelastic sensors are coated with humidity-sensitive thin films of ceramic, nanodimensionally porous TiO2 to make remote query humidity sensors.

Laser pyrolysis fabrication of ferromagnetic gamma'-Fe4N and FeC nanoparticles.

Using the laser pyrolysis method, single phase gamma'-Fe4N nanoparticles were prepared by a two step method involving preparation of nanoscale iron oxide and a subsequent gas-solid nitridation reaction. Single phase Fe3C and Fe7C3 could be prepared by laser pyrolysis from Fe(CO)5 and 3C2H4 directly. Characterization techniques such as XRD, TEM and vibrating sample magnetometer were used to measure phase structure, particle size and magnetic properties of these nanoscale nitride and carbide particles.