Fundamental and Technological Aspects of Actinide Oxide Pyrochlores: Relevance For Immobilization Matrices

1999 ◽  
Vol 556 ◽  
Author(s):  
P. E. Raison ◽  
R. G. Haire ◽  
T. Sato ◽  
T. Ogawa

AbstractPolycrystalline pyrochlore oxides consisting of selected f elements (lanthanides and actinides) and Zr and Hf have been prepared and characterized. Characterization to date has been primarily by X-ray diffraction, both at room and at elevated temperatures. Initial studies concentrated on selected lanthanides and the Np, Pu and Am analogs (reported here) but have been extended to the other actinide elements through Cf. Data from these studies have been used to establish a systematic correlation regarding the fundamental materials science of these particular pyrochlores and structurally related fluorite-type dioxides. In addition to pursuing their materials science, we have addressed some potential technological applications for these materials. Some of the latter concern: (1) immobilization matrices; (2) materials for transmutation concepts; and (3) special nuclear fuel forms that can minimize the generation of nuclear wastes. For f elements that display both a III and IV oxidation state in oxide matrices, the synthetic path required for producing the desired pyrochlore oxide is dictated by their pseudo-oxidation potential the stability of the compound towards oxygen uptake. For the f elements that display an oxidationreduction cycle for pyrochlore-dioxide solid solution, X-ray diffraction can be used to identify the composition in the oxidation-reduction cycle, the oxygen stoichiometry and/or the composition. This paper concentrates on the Np, Pu and Am systems, and addresses the above aspects, the role of the crystal matrix in controlling the ceramic products as well as discussingsome custom-tailored materials.

2017 ◽  
Vol 19 (29) ◽  
pp. 19243-19251 ◽  
Author(s):  
Konrad Świerczek ◽  
Alicja Klimkowicz ◽  
Kengo Nishihara ◽  
Shuntaro Kobayashi ◽  
Akito Takasaki ◽  
...  

Structural and oxygen content changes of hexagonal HoMnO3+δ manganite at the stability boundary in the perovskite phase have been studied by X-ray diffraction and thermogravimetry using in situ oxidation and reduction processes at elevated temperatures in oxygen and air.


1999 ◽  
Vol 576 ◽  
Author(s):  
H. P. Oliveira ◽  
C. L. P. S. Zanta ◽  
A. C. Galina ◽  
C. F. O. Graeff

ABSTRACTIn this work, intercalated material was prepared consisting of a regular interchange of organic/inorganic layers. The products were obtained by reacting 3,4-dihidroxi-fenilalanina (DL-DOPA) in a solution with V2O5.nH2O gel, which suffered an oxidative polymerization/intercalation process, forming a film with a dark blue metallic color. The films were characterized using UV\Vis transmission spectroscopy, FTLR, ESR, X-ray diffraction, dc conductivity, and cyclic voltammetry. The X-ray diffractograms indicate that the lamellar structure of the V2O5 is preserved but the inter-planar space increase from 1.18 nm to 1.38 nm. The FTIR and ESR spectra confirms that the V2O5 structure is preserved, however the presence of melanin induces the reduction of Vv ions to Viv. The increase in the inter-planar spacing is observed to increase the stability and reproducibility of the electrochemical insertion/de-insertion of Li+. This increase in stability is also observed in the electrochromic properties of the film, which are fully reproducible even after more than 60 oxidation-reduction cycles. The melanin affects also the activation energy of the dc conductivity which changes from 0.35 eV to 0.20 eV.


Author(s):  
Douglas L. Dorset

A variety of linear chain materials exist as polydisperse systems which are difficultly purified. The stability of continuous binary solid solutions assume that the Gibbs free energy of the solution is lower than that of either crystal component, a condition which includes such factors as relative molecular sizes and shapes and perhaps the symmetry of the pure component crystal structures.Although extensive studies of n-alkane miscibility have been carried out via powder X-ray diffraction of bulk samples we have begun to examine binary systems as single crystals, taking advantage of the well-known enhanced scattering cross section of matter for electrons and also the favorable projection of a paraffin crystal structure posited by epitaxial crystallization of such samples on organic substrates such as benzoic acid.


Author(s):  
G.E. Ice

The increasing availability of synchrotron x-ray sources has stimulated the development of advanced hard x-ray (E≥5 keV) microprobes. With new x-ray optics these microprobes can achieve micron and submicron spatial resolutions. The inherent elemental and crystallographic sensitivity of an x-ray microprobe and its inherently nondestructive and penetrating nature will have important applications to materials science. For example, x-ray fluorescent microanalysis of materials can reveal elemental distributions with greater sensitivity than alternative nondestructive probes. In materials, segregation and nonuniform distributions are the rule rather than the exception. Common interfaces to whichsegregation occurs are surfaces, grain and precipitate boundaries, dislocations, and surfaces formed by defects such as vacancy and interstitial configurations. In addition to chemical information, an x-ray diffraction microprobe can reveal the local structure of a material by detecting its phase, crystallographic orientation and strain.Demonstration experiments have already exploited the penetrating nature of an x-ray microprobe and its inherent elemental sensitivity to provide new information about elemental distributions in novel materials.


1961 ◽  
Vol 5 ◽  
pp. 276-284
Author(s):  
E. L. Moore ◽  
J. S. Metcalf

AbstractHigh-temperature X-ray diffraction techniques were employed to study the condensation reactions which occur when sodium orthophosphates are heated to 380°C. Crystalline Na4P2O7 and an amorphous phase were formed first from an equimolar mixture of Na2HPO4·NaH2PO4 and Na2HPO4 at temperatures above 150°C. Further heating resulted in the formation of Na5P3O10-I (high-temperature form) at the expense of the crystalline Na4P4O7 and amorphous phase. Crystalline Na5P3O10-II (low-temperature form) appears after Na5P3O10-I.Conditions which affect the yield of crystalline Na4P2O7 and amorphous phase as intermediates and their effect on the yield of Na5P3O10 are also presented.


Catalysts ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 346
Author(s):  
Sonam Goyal ◽  
Maizatul Shima Shaharun ◽  
Ganaga Suriya Jayabal ◽  
Chong Fai Kait ◽  
Bawadi Abdullah ◽  
...  

A set of novel photocatalysts, i.e., copper-zirconia imidazolate (CuZrIm) frameworks, were synthesized using different zirconia molar ratios (i.e., 0.5, 1, and 1.5 mmol). The photoreduction process of CO2 to methanol in a continuous-flow stirred photoreactor at pressure and temperature of 1 atm and 25 °C, respectively, was studied. The physicochemical properties of the synthesized catalysts were studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy. The highest methanol activity of 818.59 µmol/L.g was recorded when the CuZrIm1 catalyst with Cu/Zr/Im/NH4OH molar ratio of 2:1:4:2 (mmol/mmol/mmol/M) was employed. The enhanced yield is attributed to the presence of Cu2+ oxidation state and the uniformly dispersed active metals. The response surface methodology (RSM) was used to optimize the reaction parameters. The predicted results agreed well with the experimental ones with the correlation coefficient (R2) of 0.99. The optimization results showed that the highest methanol activity of 1054 µmol/L.g was recorded when the optimum parameters were employed, i.e., stirring rate (540 rpm), intensity of light (275 W/m2) and photocatalyst loading (1.3 g/L). The redox potential value for the CuZrIm1 shows that the reduction potential is −1.70 V and the oxidation potential is +1.28 V for the photoreduction of CO2 to methanol. The current work has established the potential utilization of the imidazolate framework as catalyst support for the photoreduction of CO2 to methanol.


Nanomaterials ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 1885
Author(s):  
Xinyu Wu ◽  
Feng Yang ◽  
Jian Gan ◽  
Zhangqian Kong ◽  
Yan Wu

The silver particles were grown in situ on the surface of wood by the silver mirror method and modified with stearic acid to acquire a surface with superhydrophobic and antibacterial properties. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and X-ray energy spectroscopy (XPS) were used to analyze the reaction mechanism of the modification process. Scanning electron microscopy (SEM) and contact angle tests were used to characterize the wettability and surface morphology. A coating with a micro rough structure was successfully constructed by the modification of stearic acid, which imparted superhydrophobicity and antibacterial activity to poplar wood. The stability tests were performed to discuss the stability of its hydrophobic performance. The results showed that it has good mechanical properties, acid and alkali resistance, and UV stability. The durability tests demonstrated that the coating has the function of water resistance and fouling resistance and can maintain the stability of its hydrophobic properties under different temperatures of heat treatment.


Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1321
Author(s):  
Yasunobu Asawa ◽  
Aleksandra V. Arsent’eva ◽  
Sergey A. Anufriev ◽  
Alexei A. Anisimov ◽  
Kyrill Yu. Suponitsky ◽  
...  

Bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) were prepared by the reactions of the corresponding carboranyl acyl chlorides with ethylenediamine. Crystal molecular structure of 1,1′-μ-(CH2NH(O)C-1,2-C2B10H11)2 was determined by single crystal X-ray diffraction. Treatment of bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 with ammonium or cesium fluoride results in partial deboronation of the ortho-carborane cages to the nido-carborane ones with formation of [7,7′(8′)-μ-(CH2NH(O)C(CH2)n-7,8-C2B9H11)2]2−. The attempted reaction of [7,7′(8′)-μ-(CH2NH(O)CCH2-7,8-C2B9H11)2]2− with GdCl3 in 1,2-dimethoxy- ethane did not give the expected metallacarborane. The stability of different conformations of Gd-containing metallacarboranes has been estimated by quantum-chemical calculations using [3,3-μ-DME-3,3′-Gd(1,2-C2B9H11)2]− as a model. It was found that in the most stable conformation the CH groups of the dicarbollide ligands are in anti,anti-orientation with respect to the DME ligand, while any rotation of the dicarbollide ligand reduces the stability of the system. This makes it possible to rationalize the design of carborane ligands for the synthesis of gadolinium metallacarboranes on their base.


Nanomaterials ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 1141
Author(s):  
Georgia Basina ◽  
Hafsa Khurshid ◽  
Nikolaos Tzitzios ◽  
George Hadjipanayis ◽  
Vasileios Tzitzios

Fe-based colloids with a core/shell structure consisting of metallic iron and iron oxide were synthesized by a facile hot injection reaction of iron pentacarbonyl in a multi-surfactant mixture. The size of the colloidal particles was affected by the reaction temperature and the results demonstrated that their stability against complete oxidation related to their size. The crystal structure and the morphology were identified by powder X-ray diffraction and transmission electron microscopy, while the magnetic properties were studied at room temperature with a vibrating sample magnetometer. The injection temperature plays a very crucial role and higher temperatures enhance the stability and the resistance against oxidation. For the case of injection at 315 °C, the nanoparticles had around a 10 nm mean diameter and revealed 132 emu/g. Remarkably, a stable dispersion was created due to the colloids’ surface functionalization in a nonpolar solvent.


Crystals ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 753
Author(s):  
Dmitriy Shlimas ◽  
Artem L. Kozlovskiy ◽  
Maxim Zdorovets

The interest in lithium-containing ceramics is due to their huge potential as blanket materials for thermonuclear reactors for the accumulation of tritium. However, an important factor in their use is the preservation of the stability of their strength and structural properties when under the influence of external factors that determine the time frame of their operation. This paper presents the results of a study that investigated the influence of the LiTiO2 phase on the increasing resistance to degradation and corrosion of Li2TiO3 ceramic when exposed to aggressive acidic media. Using the X-ray diffraction method, it was found that an increase in the concentration of LiClO4·3H2O during synthesis leads to the formation of a cubic LiTiO2 phase in the structure as a result of thermal sintering of the samples. During corrosion tests, it was found that the presence of the LiTiO2 phase leads to a decrease in the degradation rate in acidic media by 20–70%, depending on the concentration of the phase. At the same time, and in contrast to the samples of Li2TiO3 ceramics, for which the mechanisms of degradation during a long stay in aggressive media are accompanied by large mass losses, for the samples containing the LiTiO2 phase, the main degradation mechanism is pitting corrosion with the formation of pitting inclusions.


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