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A new type of Al-rich hydroxylian pseudortuile (HPR), containing 64.6 wt% Ti[O.sub.2], 12.1 wt% [Al.sub.2][O.sub.3], 10.9 wt% [Fe.sub.2][O.sub.3], and 12.4 wt% [H.sub.2]O, has been identified in detrital heavy mineral concentrates from Central Kalimantan, Indonesia. The unusual translucent orange-colored grains have been characterized using electron microprobe analyses, thermal analyses, [sup.27]Al MAS NMR, and synchrotron XRD studies including the use of differential pair distribution function analysis, to determine how the Al is incorporated. The results support a model in which diaspore-form AIOOH is incorporated into nanopores in the solid hydrogel-like mineral. The HPR matrix structure comprises disordered unit-cell scale intergrowths of diaspore-type and rutile-type structure elements, which have a close dimensional match to the diaspore structure, thus providing a suitable template for epitactic nucleation and growth of the diaspore. The average composition of the grains is [Fe[Ti.sub.6][O.sub.10.8][(OH).sub.5.4]] x 1.8A1OOH x [H.sub.2]O, where the formula within the square brackets represents the HPR matrix, and the A1OOH and [H.sub.2]O occupy the intragrain pore volume. Keywords: Hydroxylian pseudorutile, Al-rich pseudorutile, synchrotron XRD study, diaspore-rutile intergrowth structure DOI: 10.2138/am.2010.3330

A preliminary structural investigation of local disorder in fully oxidized La2NiO4+δ was performed by Pair Distribution Function (PDF) analyses of X-ray and neutron powder diffraction data. X-ray diffraction data were recorded in-situ on warming from room temperature up to 450 ∘C.

Transient (non-equilibrium) microstructures in crystals may arise in an order-disorder phase transition that generates lattice strain. A two-phase field can develop if fluctuations of the order parameter lead to nucleation of an ordered phase in a disordered matrix, as we describe here for columbite. Synchrotron X-ray diffraction and transmission electron microscopy show that ordering in columbite involves two discrete phases with different degree of order but the same composition. A highly unusual distribution of ordered rhombic-shaped domains within a disordered matrix establishes on a nanometer scale and remains relatively stable over a prolonged period of annealing. Progressive ordering takes place within the ordered domains and the disordered matrix but the domains maintain more or less constant shape and distribution. We speculate that a new family of such microstructures could develop in other oxide phases with cation ordering transitions that are strongly first order in character. Long-term stability of such microstructures and their dependence on strain could open up the possibility of engineering the properties of crystals containing a percolating disordered matrix with ordered nanodomains of controlled dimensions. [ABSTRACT FROM AUTHOR]

As transport properties of doped ceria electrolytes depend significantly on the nature of the dopant and the defectivity, the design of new materials and devices requires proper understanding of the defect structure. Among lanthanide dopants, Yb shows some peculiar characteristics that call for a possible different defect structure compared to Gd and Sm conventional dopants, which could be linked to its poorer performance. For this purpose, we combine synchrotron and neutron powder diffraction exploiting the Rietveld and Pair distribution Function. By increasing its concentration, Yb produces qualitatively the same structural distortions as other dopants, leading to a domain structure involving the progressive nucleation and growth of nanodomains with a Yb2O3-like (C-type) structure hosted in a fluorite CeO2 matrix. However, when it comes to growing the C-type nanodomains into a long-range phase, the transformation is less pronounced. At the same time, a stronger structural distortion occurs at the local scale, which is consistent with the segregation of a large amount of oxygen vacancies. The strong trapping of VOs by Yb3+ explains the poor performance of Yb-doped ceria with respect to conventional Sm-, Gd-, and Y-doped samples at equal temperature and dopant amount. [ABSTRACT FROM AUTHOR]

A new hierarchical approach is presented for elucidating the structural disorder in Ce1-x Gd x O2-x/2 solid solutions on different scale lengths. The primary goal of this investigation is to shed light on the relations between the short-range and the average structure of these materials via an analysis of disorder on the mesocopic scale. Real-space (pair distribution function) and reciprocal-space (Rietveld refinement and microstructure probing) analysis of X-ray powder diffraction data and electron spin resonance (ESR) investigations were carried out following this approach. On the local scale, Gd- and Ce-rich droplets (i.e. small regions a few ångströms wide) form, exhibiting either a distorted fluorite (CeO2) or a C-type (Gd2O3) structure in the whole compositional range. These droplets can then form C-type nanodomains which, for Gd concentrations x Gd ≤ 0.25, are embedded in the fluorite matrix. At the site percolation threshold p C for a cubic lattice (x Gd = p C ≃ 0.311), C-type nanodomains percolate inside each crystallite and a structural phase transformation is observed. When this occurs, the peak-to-peak ESR line width ΔH pp shows a step-like behaviour, which can be associated with the increase in Gd-Gd dipolar interactions. A general crystallographic rationale is presented to explain the fluorite-to-C-type phase transformation. The approach shown here could be adopted more generally in the analysis of disorder in other highly doped materials.

The crystal structures of eight mono-methyl alkanes have been determined from single-crystal or high-resolution powder X-ray diffraction using synchrotron radiation. Mono-methyl alkanes can be found on the cuticles of insects and are believed to act as recognition pheromones in some social species, e.g. ants, wasps etc. The molecules were synthesized as pure S enantiomers and are (S)-9-methylpentacosane, C26H54; (S)-9-methylheptacosane and (S)-11-methylheptacosane, C28H58; (S)-7-methylnonacosane, (S)-9-methylnonacosane, (S)-11-methylnonacosane and (S)-13-methylnonacosane, C30H62; and (S)-9-methylhentriacontane, C32H66. All crystallize in space group P21. Depending on the position of the methyl group on the carbon chain, two packing schemes are observed, in which the molecules pack together hexagonally as linear rods with terminal and side methyl groups clustering to form distinct motifs. Carbon-chain torsion angles deviate by less than 10° from the fully extended conformation, but with one packing form showing greater curvature than the other near the position of the methyl side group. The crystal structures are optimized by dispersion-corrected DFT calculations, because of the difficulties in refining accurate structural parameters from powder diffraction data from relatively poorly crystalline materials.

The (S)-4-alkoxo-2-azetidinecarboxylic acids are optically active beta-lactam derivatives of aspartic acid, which are used as precursors of carbapenem-type antibiotics and poly-beta-aspartates. The crystal structures of three (S)-4-alkoxo-2-azetidinecarboxylic acids with alkyl chains with 10, 12 and 16 C atoms were solved using parallel tempering and refined against the X-ray powder diffraction data using the Rietveld method. The azetidinone rings in the three compounds display a pattern of asymmetrical bond distances and an almost planar conformation; these characteristics are compared with periodic solid-state, gas-phase density-functional theory (DFT) calculations and MOGUL average bond distances and angles from the CSD. The compounds pack along [001] as corrugated sheets separated by approximately 4.40 A and connected by hydrogen bonds of the type N-H...O.

The molecular and crystalline structure of ethyl 1',2',3',4',4a',5',6',7'-octahydrodispiro[cyclohexane-1,2'-quinazoline-4',1''-cyclohexane]-8'-carbodithioate (I) was solved and refined from powder synchrotron X-ray diffraction data. The initial model for the structural solution in direct space using the simulated annealing algorithm implemented in DASH [David et al. (2006). J. Appl. Cryst. 39, 910-915] was obtained performing a conformational study on the fused six-membered rings of the octahydroquinazoline system and the two spiran cyclohexane rings of (I). The best model was chosen using experimental evidence from 1H and 13C NMR [Contreras et al. (2001). J. Heterocycl. Chem. 38, 1223-1225] in combination with semi-empirical AM1 calculations. In the refined structure the two spiran rings have the chair conformation, while both of the fused rings in the octahydroquinazoline system have half-chair conformations compared with in-vacuum density-functional theory (DFT) B3LYP/6-311G*, DFTB (density-functional tight-binding) theoretical calculations in the solid state and other related structures from X-ray diffraction data. Compound (I) presents weak intramolecular hydrogen bonds of the type N-H...S and C-H...S, which produce delocalization of the electron density in the generated rings described by graph symbols S(6) and S(5). Packing of the molecules is dominated by van der Waals interactions.

The crystal structure of the nanocrystalline alpha phase of Pigment Yellow 213 (P.Y. 213) was solved by a combination of single-crystal electron diffraction and X-ray powder diffraction, despite the poor crystallinity of the material. The molecules form an efficient dense packing, which explains the observed insolubility and weather fastness of the pigment. The pair-distribution function (PDF) of the alpha phase is consistent with the determined crystal structure. The beta phase of P.Y. 213 shows even lower crystal quality, so extracting any structural information directly from the diffraction data is not possible. PDF analysis indicates the beta phase to have a columnar structure with a similar local structure as the alpha phase and a domain size in column direction of approximately 4 nm.