Stoichiometric changes in lithium conducting materials based on Li1+xAlxTi2−x(PO4)3: impedance, X-ray and NMR studies

The lithium fast-ion conductor, Li_1+xAl_xTi_2−x(PO₄)₃ (LATP) has been modified via changes in stoichiometry during the processing steps. The resultant changes have been followed using ²⁷Al MAS NMR, X-ray powder diffraction and impedance spectroscopy. The most important changes were those of the form Li_1.3+4yAl_0.3Ti_1.7−y(PO₄)₃. It was possible to remove the AlPO₄ phase (both tridymite and berlinite polymorphs), as monitored by X-ray diffractograms and ²⁷Al NMR spectra. Consequently, these changes appear to result in increased grain boundary conductivity of the LATP material.

Towards elucidating microscopic structural changes in Li-ion conductors Li1+yTi2–yAly[PO4 ]3 and Li1+yTi2–yAly[PO4 ]3–x [MO4 ]x(M=V and Nb) : X-ray and27Al and31P NMR studies

A combination of X-ray powder diffraction (XRD) and nuclear magnetic resonance (NMR) studies has demonstrated that attempted substitutions of Al, V and Nb into the framework of LiTi₂(PO₄)₃ yield several impurity phases in addition to direct substitutions of Al into Ti and V, Nb into P sites. Direct substitutions were confirmed by changes in the unit cell dimensions as indicated by the peak shifts observed in the X-ray diffractographs and by analyses of the ²⁷Al and ³¹P magic angle spinning (MAS) spectra. A major impurity phase was identified as AlPO₄ (found in at least two polymorphs) and the amount present increases with increasing Al additions. The formation of AlPO₄ appeared to be enhanced by further V but suppressed by Nb substitution. These results suggest that the presence of AlPO₄ , together with the non-stoichiometric modified LTP, may be the cause for the observed densification of this material upon sintering and the increased ionic conductivity.

Voltage-composition profile and synchrotron X-ray structural analysis of low and high temperature LixCoO2 host material

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

X-ray diffraction data of tibolone Delta(4) isomer (isotibolone)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Resonant x-ray diffraction as a tool to calculate mixed valence ratios: Application to Prussian Blue materials

An approach is proposed here to calculate mixed valence ratios in molecular compounds. Synchrotron x-ray powder diffraction experiments were conducted to determine the Fe(+3)/Fe(+2) ratio in Prussian Blue compounds, which were elected as an example of the use of this approach. As a result, a resonant x-ray diffraction measurement provided direct evidence that the vacant [Fe(CN)(6)] group was randomly absent from similar to 31% of the structure, which was indicated by structural differences caused by variations in the anomalous dispersion term. These findings are very important for a deeper understanding of the changes occurring in properties during in situ compositional variations. (c) 2008 American Institute of Physics.

Análises estrutural, nanoestrutural, e quantitativa de fases em materiais cerâmicos de interesse tecnológico, utilizando difração de raios X pelo método do pó

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The T-2 phase in the Nb-Si-B system studied by ab initio calculations and synchrotron X-ray diffraction

The solid solution based on Nb5Si3 (Cr5B3 structure type, D8(l), tl32, 14/mcm, No140, a=6.5767 angstrom, c=11.8967 angstrom) in the Nb-Si-B system was studied from the structural and thermodynamic point of view both experimentally and by ab initio calculations. Rietveld refinement of powder X-ray synchrotron data allowed to determine the boron to silicon substitution mechanism and the structural parameters. Ab initio calculations of different ordered compounds and selected disordered alloys allowed to obtain in addition to the enthalpy of formation of the solution, substitution mechanism and structural parameters which are in excellent agreement with the experimental data. The stability of the phase is discussed. (C) 2012 Elsevier Inc. All rights reserved.

X-ray absorption spectroscopy study on La0.6Sr0.4CoO3 and La0.6Sr0.4Co1¡yFeyO3 nanotubes and nanorods for IT-SOFC cathodes.

In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of La0:6Sr0:4CoO3 (LSCO) and La0:6Sr0:4Co1¡yFeyO3 (LSCFO) nanostructured cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 1000oC in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions. For this pur- pose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder dffraction investigations. [1] M.G. Bellino et al, J. Am. Chem. Soc. 129 (2007) 3066 [2] J.G. Sacanell et al., J. Power Sources 195 (2010) 1786

Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.

Quil A-lipid powder formulations releasing ISCOMs and related colloidal stuctures upon hydration

The aim of the present study was to prepare solid Quil A-cholesterol-phospholid formulations (as powder mixtures or compressed to pellets) by physical mixing or by freeze-drying of aqueous dispersions of these components in ratios that allow spontaneous formation of ISCOMs and other colloidal stuctures upon hydration. The effect of addition of excess cholesterol to the lipid mixtures on the release of a model antigen (PE-FITC-OVA) from the pellets was also investigated. Physical properties were evaluated by X-ray powder diffractometry (XPRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and polarized light microscopy (PLM). Characterization of aqueous colloidal dispersions was performed by negative staining transmission electron microscopy (TEM). Physically mixed powders (with or without PE-FITC-OVA) and pellets prepared from the same powders did not spontaneously form ISCOM matrices and related colloidal structures such as worm-like micelles, ring-like micelles, lipidic/layered structures and lamellae (hexagonal array of ring-like micelles) upon hydration as expected from the pseudo-temary diagram for aqueous mixtures of Quil A, cholesterol and phospholipid. In contrast, spontaneous formation of the expected colloids was demonstrated for the freeze-dried lipid mixtures. Pellets prepared by compression of freeze-dried powders released PE-FITC-OVA slower than those prepared from physically mixed powders. TEM investigations revealed that the antigen was released in the form of colloidal particles (ISCOMs) from pellets prepared by compression of freeze-dried powders. The addition of excess cholesterol slowed down the release of antigen. The findings obtained in this study are important for the formulation of solid Quil A-containing lipid articles as controlled particulate adjuvant containing antigen delivery systems. (c) 2004 Elsevier B.V. All rights reserved.

Novel inclusion complex of ibuprofen tromethamine with cyclodextrins: Physico-chemical characterization

Guest-host interactions of ibuprofen tromethamine salt (Ibu.T) with native and modified cyclodextrins (CyDs) have been investigated using several techniques, namely phase solubility diagrams (PSDs), proton nuclear magnetic resonance (H-1 NMR), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffractometry (XRPD). scanning-electron microscopy (SEM) and molecular mechanics (MM). From the analysis of PSD data (A(L)-type) it is concluded that the anionic tromethamine salt of ibuprofen (pK(a) = 4.55) forms 1: 1 soluble complexes with all CyDs investigated in buffered water at pH 7.0, while the neutral form of Ibu forms an insoluble complex with beta-CyD (B-S-type) in buffered water at pH 2.0. Ibu.T has a lower tendency to complex with beta-CyD (K-11 = 58 M-1 at pH 7.0) compared with the neutral Ibu (K-11 = 4200 M (1)) in water. Complex formation of Ibu.T with beta-CyD (Delta G degrees = -20.4 kJ/mol) is enthalpy driven (Delta H degrees = -22.9 kJ/mol) and is accompanied by a small unfavorable entropy (Delta S degrees = -8.4 J/mol K) change. H-1 NMR studies and MM computations revealed that, on complexation, the hydrophobic central benzene ring of lbu.T and part of the isobutyl group reside within the beta-CyD cavity leaving the peripheral groups (carboxylate, tromethamine and methyl groups) located near the hydroxyl group networks at either rim of beta-CyD. PSD, H-1 NMR, DSC, FT-IR, XRPD, SEM and MM studies confirmed the formation of Ibu.T/beta-CyD inclusion complex in solution and the solid state. (C) 2009 Elsevier B.V. All rights reserved.

Disorder and dissolution enhancement: Deposition of ibuprofen on to insoluble polymers

Microcrystalline cellulose (MCC) and cross-linked polyvinylpyrrolidone (PVP-CL) were examined as polymeric carriers to support amorphous ibuprofen (IB). Drug/cartier systems were prepared as physical mixes, and drug was loaded onto the polymers by hot mix and solvent deposition methods. The systems were examined using differential scanning calorimetry (DSC), X-ray powder diffractometry (XRD) and by dissolution testing. PVP-CL reduced drug crystallinity more than MCC and, surprisingly, even very simple mixing of ibuprofen with PVP-CL induced disordering of the drug. Increased ibuprofen dissolution rates were achieved with both polymers, in the order of solvent deposition > hot mixes > physical mixes. The increased dissolution rates could be attributed to a combination of faster dissolution from amorphous ibuprofen, microcrystalline drug deposition on carrier surfaces and polymer swelling. However, no clear relationship was observed between ibuprofen dissolution rates (using first order, Higuchi or Hixson-Crowell relationships) and drug crystallinity. (C) 2005 Elsevier B.V. All rights reserved.

Polymer-mediated disruption of drug crystallinity

Ibuprofen (IB), a BCS Class II compound, is a highly crystalline substance with poor solubility properties. Here we report on the disruption of this crystalline structure upon intimate contact with the polymeric carrier cross-linked polyvinylpyrrolidone (PVP-CL) facilitated by low energy simple mixing. Whilst strong molecular interactions between APIs and carriers within delivery systems would be expected on melting or through solvent depositions, this is not the case with less energetic mixing. Simple mixing of the two compounds resulted in a significant decrease in the differential scanning calorimetry (DSC) melting enthalpy for IB, indicating that approximately 30% of the crystalline content was disordered. This structural change was confirmed by broadening and intensity diminution of characteristic IB X-ray powder diffractometry (PXRD) peaks. Unexpectedly, the crystalline content of the drug continued to decrease upon storage under ambient conditions. The molecular environment of the mixture was further investigated using Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) spectroscopy. These data suggest that the primary interaction between these components of the physical mix is hydrogen bonding, with a secondary mechanism involving electrostatic/hydrophobic interactions through the IB benzene ring. Such interactions and subsequent loss of crystallinity could confer a dissolution rate advantage for IB. (C) 2006 Elsevier B.V. All rights reserved.