Zirconolite transformation under reducing conditions

1998 ◽  
Vol 13 (11) ◽  
pp. 3181-3190 ◽  
Author(s):  
B. D. Begg ◽  
E. R. Vance ◽  
B. A. Hunter ◽  
J. V. Hanna
Keyword(s):  
Perovskite Phase ◽  
Charge Compensation ◽  
Fluorite Structure ◽  
Second Phase ◽  
X Ray Diffraction ◽  
Nmr Studies ◽  
Paramagnetic Resonance ◽  
X Ray ◽  
Reducing Conditions ◽  
Quadrupole Resonance

The structural behavior of zirconolite (CaZrTi2O7) under reducing conditions at high temperature has been studied, mainly by scanning electron microscopy (SEM) and x-ray diffraction (XRD), but also with x-ray absorption spectroscopy, thermogravimetry, and electron paramagnetic resonance. The partial reduction of Ti4+ to Ti3+, associated with a reducing atmosphere heat treatment, led to the initial formation of perovskite (CaTiO3) as a second phase. As the concentration of Ti3+ in the zirconolite increased, so did the amount of perovskite until the zirconolite was totally transformed into a fluorite structured phase. Analysis of the reduced zirconolites showed them to be consistently deficient in Ca and enriched in Zr, in proportion to the concentration of Ti3+. To determine how electroneutrality was preserved in these reduced zirconolites, a series of zirconolites were prepared in air using In3+ and Ga3+ as models for Ti3+. These samples were then investigated by neutron and x-ray diffraction, SEM, solid state nuclear magnetic resonance (NMR), and nuclear quadrupole resonance (NQR). 71Ga MAS NMR studies of the Ga substituted zirconolite exhibited a narrow resonance at ˜13 ppm which was attributed to six-coordinate Ga incorporated in a trace perovskite phase. Broadline 71Ga NMR and 69/71Ga NQR were required to characterize the Ga incorporated in the zirconolite. The resultant quadrupolar parameters of CQ = 30.0 ± 0.05 MHz and η = 1.0 ± 0.03 indicate that the Ga site is in a highly distorted environment which would suggest that it is located on the five-coordinate Ti site within the zirconolite lattice. These results were complemented by Rietveld refinement of the neutron diffraction data from the In-doped zirconolite sample, which was optimal when all the In was located on the five-coordinate Ti site with the excess Zr located on the Ca site. It would therefore appear that charge compensation for the presence of Ti3+ in zirconolite is effected via the substitution of an appropriate amount of Zr on the Ca site. The Ti3+-stabilized fluorite structure was readily oxidized back to a single phase zirconolite upon heating in air.

Effect of Synthesis Conditions and Actinide Contents on Phase Composition of Actinide Bearing Ceramics

2003 ◽  
Vol 807 ◽  
Author(s):  
A. G. Ptashkin ◽  
S. V. Stefanovsky ◽  
S. V. Yudintsev ◽  
S. A. Perevalov
Keyword(s):  
Electron Microscopy ◽  
Solid Solution ◽  
Phase Composition ◽  
Fluorite Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Synthesis Conditions ◽  
Reducing Conditions ◽  
Dispersive System ◽  
Scanning Electron

ABSTRACTPu-bearing zirconolite and pyrochlore based ceramics were prepared by melting under oxidizing and reducing conditions at 1550 °C. 239Pu content in the samples ranged between ∼10 and ∼50 wt.%. Phase composition of the ceramics and Pu partitioning were studied using X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive system (SEM/EDS). Major phases in the samples were found to be the target zirconolite and pyrochlore as well as a cubic fluorite structure oxide. Normally the Pu content in the Pu host phases was 10–12 wt.%. This corresponds to the Pu content recommended for matrices for immobilization of excess weapons plutonium. At higher Pu content (up to 50 wt.%) additional phases, such as a PuO2-based cubic fluorite-structured solid solution, perovskite, and rutile were found.

Dielectric and Ferroelectric Properties of Bi-Doped BaTiO3 Ceramics

2007 ◽  
Vol 334-335 ◽  
pp. 977-980 ◽  
Author(s):  
Xiang Ping Jiang ◽  
M. Zeng ◽  
K.W. Kowk ◽  
Helen Lai Wah Chan
Keyword(s):  
Perovskite Phase ◽  
Ferroelectric Properties ◽  
Relaxor Ferroelectric ◽  
Second Phase ◽  
X Ray Diffraction ◽  
Pure Perovskite Structure ◽  
Dielectric Relaxation Process ◽  
X Ray ◽  
Dielectric Peak ◽  
A Site

Barium titanate with A-site substituted by various amount of bismuth oxide (Ba1-x BixTiO3, abbreviated as BBT, x=0.05, 0.1, 0.15) were prepared by solid-state reaction. The effect of bismuth substitution on crystallographic phase, dielectric and ferroelectric properties was studied. The X-ray diffraction shows that the samples were crystallized into pure perovskite structure when x=0.05 and 0.1, while for x=0.15 sample, second phase appeared in the dominant perovskite phase. The temperature dependence of dielectric permittivity of the ceramics was investigated and the evolution from normal ferroelectrics to relaxor ferroelectric sates was observed. In the range 0≤x≤0.1, the temperature of dielectric peak Tm is independence of the frequency, indicating the normal ferroelectrics behavior. At x=0.15, dielectric relaxation process with a broadening distribution of the permittivity dielectric is observed.

Lower crystallization temperature of sol-gel PbTiO3 on Ti/Pt-coated substrates

1999 ◽  
Vol 14 (6) ◽  
pp. 2369-2372 ◽  
Author(s):  
R. E. Avila ◽  
T. P. Velilla ◽  
P. J. Retuert
Keyword(s):  
Thin Film ◽  
Thin Films ◽  
Refractive Index ◽  
Sintering Temperature ◽  
Perovskite Phase ◽  
Sol Gel ◽  
Second Phase ◽  
X Ray Diffraction ◽  
Range Analysis ◽  
X Ray

PbTiO3 (PT) thin films have been deposited by sol-gel on Pt/Si, SiO2/Si, Pt/Ti/SiO2/Si, and Ti/Pt/Ti/SiO2/Si and annealed for 45 min in the 400–670 °C range. Analysis by x-ray diffraction (XRD) and spectroscopic ellipsometry shows that the Ti overlayer promotes early crystallization in the tetragonal perovskite phase, reducing the presence of a second phase, tentatively identified as pyrochlore, starting by 450 %C. The refractive index and extinction coefficient (n, k) of the PT film increase rapidly with the sintering temperature in the range of 450–570 °C and saturate by 570 °C to values of n varying from 2.4 to 2.9, and k from 0.03 to 0.3, over the 1.65–2.95 eV range. Most of the increase of n is related to thin film densification.

New Copper Compounds with Antiplatelet Aggregation Activity

2019 ◽  
Vol 15 (8) ◽  
pp. 850-862
Author(s):  
Mirthala Flores-García ◽  
Juan Manuel Fernández-G. ◽  
Cristina Busqueta-Griera ◽  
Elizabeth Gómez ◽  
Simón Hernández-Ortega ◽  
...  
Keyword(s):  
Schiff Base ◽  
Solid State ◽  
Thrombotic Event ◽  
X Ray Diffraction ◽  
Nmr Studies ◽  
Schiff Base Ligands ◽  
X Ray ◽  
Antiplatelet Aggregation ◽  
Aggregation Activity ◽  
L1 And L2

Background: Ischemic heart disease, cerebrovascular accident, and venous thromboembolism have the presence of a thrombotic event in common and represent the most common causes of death within the population. Objective: Since Schiff base copper(II) complexes are able to interact with polyphosphates (PolyP), a procoagulant and potentially prothrombotic platelet agent, we investigated the antiplatelet aggregating properties of two novel tridentate Schiff base ligands and their corresponding copper( II) complexes. Methods: The Schiff base ligands (L1) and (L2), as well as their corresponding copper(II) complexes (C1) and (C2), were synthesized and characterized by chemical analysis, X-ray diffraction, mass spectrometry, and UV-Visible, IR and far IR spectroscopy. In addition, EPR studies were carried out for (C1) and (C2), while (L1) and (L2) were further analyzed by 1H and 13C NMR. Tests for antiplatelet aggregation activities of all of the four compounds were conducted. Results: X-ray diffraction studies show that (L1) and (L2) exist in the enol-imine tautomeric form with a strong intramolecular hydrogen bond. NMR studies show that both ligands are found as enol-imine tautomers in CDCl3 solution. In the solid state, the geometry around the copper(II) ion in both (C1) and (C2) is square planar. EPR spectra suggest that the geometry of the complexes is similar to that observed in the solid state by X-ray crystallography. Compound (C2) exhibited the strongest antiplatelet aggregation activity. Conclusion: Schiff base copper(II) complexes, which are attracting increasing interest, could represent a new approach to treat thrombosis by blocking the activity of PolyP with a potential anticoagulant activity and, most importantly, demonstrating no adverse bleeding events.

scholarly journals Electrospun Nanosystems Based on PHBV and ZnO for Ecological Food Packaging

Polymers ◽  
2021 ◽  
Vol 13 (13) ◽  
pp. 2123
Author(s):  
Maria Râpă ◽  
Maria Stefan ◽  
Paula Popa ◽  
Dana Toloman ◽  
Cristian Leostean ◽  
...  
Keyword(s):  
Food Packaging ◽  
Spin Trapping ◽  
X Ray Diffraction ◽  
Paramagnetic Resonance ◽  
Hno3 Solution ◽  
X Ray ◽  
Trapping Method ◽  
Ft Ir ◽  
Doped Zno ◽  
Electron Paramagnetic

The electrospun nanosystems containing poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and 1 wt% Fe doped ZnO nanoparticles (NPs) (with the content of dopant in the range of 0–1 wt% Fe) deposited onto polylactic acid (PLA) film were prepared for food packaging application. They were investigated by scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), antimicrobial analysis, and X-ray photoelectron spectrometry (XPS) techniques. Migration studies conducted in acetic acid 3% (wt/wt) and ethanol 10% (v/v) food simulants as well as by the use of treated ashes with 3% HNO3 solution reveal that the migration of Zn and Fe falls into the specific limits imposed by the legislation in force. Results indicated that the PLA/PHBV/ZnO:Fex electrospun nanosystems exhibit excellent antibacterial activity against the Pseudomonas aeruginosa (ATCC-27853) due to the generation of a larger amount of perhydroxyl (˙OOH) radicals as assessed using electron paramagnetic resonance (EPR) spectroscopy coupled with a spin trapping method.

Nanostructured TiO2-Based Composites for Light Absorption

2014 ◽  
Vol 975 ◽  
pp. 207-212
Author(s):  
Dayse I. dos Santos ◽  
Olayr Modesto Jr. ◽  
Luis Vicente A. Scalvi ◽  
Americo S. Tabata
Keyword(s):  
Metal Oxide ◽  
Light Absorption ◽  
Structural Characteristics ◽  
Sol Gel ◽  
Second Phase ◽  
X Ray Diffraction ◽  
Two Phase ◽  
X Ray ◽  
Oxide Powders

Metal oxide nanocomposites were prepared by two different routes: polyol and sol-gel. Characterization by X ray diffraction showed that the first process produces directly a two-phase material, while the sol-gel powder never showed second phase below 600°C. Light spectroscopy of the treated powders indicated similarities for the processed materials. Although the overall material compositions are about the same, different structural characteristics are found for each processing. With the exception of Ti-Zn materials, all the double metal oxide powders showed higher absorbance than either TiO2 powder.

Mixed Metal Oxide Interfaces: An Experimental and Theoretical Assessment of Secondary Metal Influences in Metal Impregnated Aluminas

1994 ◽  
Vol 368 ◽  
Author(s):  
M. Malaty ◽  
D. Singh ◽  
R. Schaeffer ◽  
S. Jansen ◽  
S. Lawrence
Keyword(s):  
Photoelectron Spectroscopy ◽  
Theoretical Calculations ◽  
Mixed Metal Oxide ◽  
X Ray Diffraction ◽  
Paramagnetic Resonance ◽  
X Ray ◽  
Mixed Metal ◽  
Metal Interactions ◽  
Metal Metal ◽  
Bimetallic System

ABSTRACTStudies of the mixed-metal interface in metal impregnated alumina have indicated the possibility of much metal-metal and metal-substrate interaction. Studies were carried out on NiCu/Al2O3 system which was evaluated to develop a better understanding of the forces that drive modification of the catalytic selectivity of Ni in the presence of Cu. Electron Paramagnetic Resonance (EPR), Powder X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD) and theoretical calculations were carried out on this bimetallic system, using Ni,Ag/Al2O3 as a reference as Ni shows negligible electron perturbation on co-adsorbance with Ag onto alumina. XRD results indicate that gross modification of the electronic fields of Ni and Cu are due to direct coupling and intercalation into the alumina matrix. As a result of this phenomena, these materials may form a good base for the development of novel ceramics based on mixed-metal interactions where the intermetallic perturbations are driven by the substrate effects.

X-ray Diffraction and NMR Studies on a Series of Binap-Based Ru(II) Hydroxyphosphine π-Arene Complexes

2004 ◽  
Vol 43 (6) ◽  
pp. 1920-1928 ◽  
Author(s):  
Tilmann J. Geldbach ◽  
Frank Breher ◽  
Volker Gramlich ◽  
P. G. Anil Kumar ◽  
Paul S. Pregosin
Keyword(s):  
Arene Complexes ◽  
X Ray Diffraction ◽  
Nmr Studies ◽  
X Ray

The Kinetics of Ordering in Gadolinium Zirconate: an Unusual Oxygen Ion Conductor

1995 ◽  
Vol 398 ◽  
Author(s):  
Sossina M. Haile ◽  
Scott Meilicke
Keyword(s):  
Impedance Spectroscopy ◽  
Pyrochlore Structure ◽  
Fluorite Structure ◽  
Transformation Kinetics ◽  
X Ray Diffraction ◽  
Ion Conductor ◽  
Gadolinium Zirconate ◽  
X Ray ◽  
Oxygen Ion ◽  
Kinetics Of

ABSTRACTGadolinium zirconate, Gd2Zr2O7, undergoes an order-disorder transition at ∼1550°C, transforming from a defect fluorite structure (Fm3m) to a pyrochlore structure (Fd3m). Both cations and anions are ordered in the low-temperature, pyrochlore structure. In order to understand the interplay between anion and cation order parameters and ordering rates, the transformation kinetics of Gd2Zr2O7 have been examined via X-ray diffraction. Gadolinium zirconate is of particular interest because the oxygen ion conductivity of the ordered phase is significantly greatly than that of the disordered phase, in contrast to virtually every other known solid electrolyte. This difference in conductivity has provided a second technique for characterizing the transformation kinetics: in situ A.C. impedance spectroscopy. Results of the X-ray diffraction showed the growth of superstructure peak intensity to follow an apparent (time)½ dependence, rather than that expected from a nucleation and growth model. The impedance spectroscopy measurements, on the other hand, showed the conductivity to increase linearly with time. These results suggest the transition is second order in nature.

scholarly journals Charge Compensation in Europium-Doped Hafnia Nanoparticles: Solvothermal Synthesis and Colloidal Dispersion

Crystals ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 1042
Author(s):  
Xavier H. Guichard ◽  
Francesco Bernasconi ◽  
Alessandro Lauria
Keyword(s):  
Low Temperature ◽  
Hafnium Oxide ◽  
Aqueous Media ◽  
Charge Compensation ◽  
Colloidal Dispersion ◽  
X Ray Diffraction ◽  
X Ray ◽  
Wide Range ◽  
Direct Formation ◽  
Enhanced Luminescence

Effective charge compensation of europium in hafnium oxide nanoparticles was achieved at low temperature, allowing high doping incorporation (up to 6 at.%) and enhanced luminescence. The efficiency of the incorporation and charge compensation was confirmed by scanning electron microscope energy dispersive X-ray spectroscopy and powder X-ray diffraction measurements. Despite the known polymorphism of hafnium oxide, when doped to a concentration above 3 at.%, only the pure monoclinic phase was observed up to 6 at.% of europium. Furthermore, the low-temperature solvothermal route allowed the direct formation of stable dispersions of the synthesized material over a wide range of concentrations in aqueous media. The dispersions were studied by diffuse light scattering (DLS) to evaluate their quality and by photoluminescence to investigate the incorporation of the dopants into the lattice.

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