Geometry of α-Cr2O3(0001) as a Function of H2O Partial Pressure.

Surface X-ray diffraction has been employed to elucidate the surface structure of α-Cr2O3(0001) as a function of water partial pressure at room temperature. In ultra high vacuum, following exposure to ∼2000 Langmuir of H2O, the surface is found to be terminated by a partially occupied double layer of chromium atoms. No evidence of adsorbed OH/H2O is found, which is likely due to either adsorption at minority sites, or X-ray induced desorption. At a water partial pressure of ∼30 mbar, a single OH/H2O species is found to be bound atop each surface Cr atom. This adsorption geometry does not agree with that predicted by ab initio calculations, which may be a result of some differences between the experimental conditions and those modeled.

Controlled cobalt doping in biogenic magnetite nanoparticles.

Cobalt-doped magnetite (CoxFe3 -xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe(2+) site with Co(2+), with up to 17 per cent Co substituted into tetrahedral sites.

Surface characterization of precious alloys treated with thione metal primers.

OBJECTIVES: To characterize the effect of two thione metal primers with phosphate groups on the surface morphology and composition of two noble prosthodontic alloys. METHODS: Cast specimens from Argen 81(Au-Pd) and Argipal (Hi-Pd) alloys which were ground, polished and ultrasonicated in water, were divided in two groups (2 x 3) and treated with single layers of Alloy Primer (AP) and Metal Primer II (MP) primers respectively. The treated alloy surfaces were washed off with acetone and then examined by polarized light microscopy (PLM), reflection FTIR microspectroscopy (FTIRM) and X-ray photoelectron spectroscopy (XPS). RESULTS: After AP treatment, PLM revealed a crystalline phase (VBATDT) dispersed in an amorphous phase (MDP plus soluble VBATDT) on both the alloys tested. MP demonstrated a fibrial arrangement with the most dense structure found on the Hi-Pd alloy. FTIRM failed to clearly resolve the presence of SH peaks on alloy surfaces. Moreover, NH and PS peaks were identified denoting the presence of original thione tautomers. In both primers, phosphates were detected in a dissociative state (-PO(3)(2-)). FTIR molecular mapping confirmed separation of VBATDT from MDP and MEPS from residual MMA. XPS showed that on alloy surfaces approximately 50% of sulphur was in the sulphide state, the rest being organic sulphur. AP showed higher sulphide percentage than MP on both alloys and higher sulphide percentage on the Au-Pd alloy (p<0.05). CLINICAL SIGNIFICANCE: Phase separation of the primer components on alloy surfaces may adversely affect their clinical performance. Sulphide formation on alloy surfaces was confirmed only by XPS under ultra-high vacuum and not by environmental techniques like FTIR; this poses serious questions on the chemical bonding capacity of these primers with the noble alloys tested under environmental conditions.

Performance of the VUV beamline 4.1 at the SRS, Daresbury Laboratory.

The performance of a recently commissioned beamline, designated BL4.1, at the SRS, Daresbury Laboratory, is described. This beamline covers the energy range 15 >/= hupsilon >/= 200 eV, using a spherical grating monochromator, and is equipped with a UHV surface-science endstation containing a Scienta SES200 and an HA54 angle-resolving electron-energy analyser. Design parameters and optical specifications are tabulated. Monochromator resolution has been determined by measuring the Fermi edge of a Pt foil cooled to 40 K and these values are compared with the calculated resolution. The flux delivered to the endstation has been measured directly using a calibrated photodiode. The performance of the beamline is further illustrated by reference to a study of the angular distribution of photoemitted intensity from a band-gap state on a TiO(2)(110) 1 x 2 surface.

Resonant photoemission from complex cuprates and nickelates.

Synchrotron-excited resonant-photoemission measurements at rare-earth 4d --> 4f and transition-metal 3p --> 3d thresholds have been carried out using a variety of complex cuprates and nickelates on stations 6.1 (grazing-incidence monochromator) and 6.2 (toroidal-grating monochromator) at the SRS CLRC Daresbury Laboratory. The systems studied are Nd(2)Ni(1 - x)Cu(x)O(4), La(2 - x)Sr(x)Ni(1- y)Fe(y)O(4 + delta) and Bi(2)Sr(2)Ca(1 - x)Y(x)Cu(2)O(8 + delta). A combination of EDC and constant-initial-state data is used to examine the 4f and 3d contributions to the valence-band density of states and their binding-energy positions relative to the Fermi energy. This allows the study of the valence states of the transition-metal ions and their modulation on doping. For La(2 - x)Sr(x)Ni(1 - y)Fe(y)O(4 + delta), this approach is used to infer a valence state of >/= 3.0 for Fe. In the case of Bi(2)Sr(2)Ca(1 - x)Y(x)Cu(2)O(8 + delta), the effect of Cu valence modulation on the 3p resonance is observed as x is varied. This is discussed in the light of controversy surrounding shifts in core-level photoemission with doping for this system.