scholarly journals Phase equilibria in the CeO2–La2O3–Ln2O3 system at 1250 and 1500 °С

Author(s):  
Korniienko O.A ◽  
Bykov O.I ◽  
Sameljuk A.V ◽  
Bataiev Yu.M

Materials based on cerium oxide, stabilized by oxides of rare earth elements, are promising for use in medicine, energy and mechanical engineering due to the uniqueness of their properties. State diagrams of CeO2–La2O3–Ln2O3 systems are the physicochemical basis for the creation of solid electrolytes for fuel cells, oxygen gas sensors, catalyst carriers, protective coatings on alloys, etc. Phase equilibria and structural transformations in CeO2–La2O3–Gd2O3 systems at temperatures  1250 and 1500 °С and in the binary system La2O3–Gd2O3 at temperatures  1100, 1500 and 1600 ° С in the whole range of concentrations were investigated using X-ray phase and microstructural analyzes. It was found that solid solutions based on cubic (F) modification with CeO2 fluorite type, monoclinic (B) and cubic (C) modifications of Gd2O3 and hexagonal (A) modification of La2O3 are formed in the ternary system CeO2–La2O3–Gd2O3. The boundaries of the phase fields and the periods of the crystal lattices of the formed phases are determined. It is established that in the CeO2–La2O3 –Gd2O3 system at 1250 and 1500 °С the phases of cubic symmetry are in equilibrium: on the basis of F–CeО2 with the spatial group Fm3m and C-phase on the basis of Gd2O3 with the spatial group Ia3. As the temperature decreases, there is a narrowing of all areas of homogeneity.

2021 ◽  
Vol 15 (1) ◽  
pp. 32-39
Author(s):  
Olena Andrievskaya ◽  
Oksana Kornienko ◽  
Oleksandr Bykov ◽  
Olga Chudinovich ◽  
Larysa Spasonova

Materials based on CeO2-La2O3-Eu2O3 and La2O3-Eu2O3 systems are promising candidates for a wide range of applications, but the phase relationship has not been studied systematically previously. The phase relations in the CeO2-La2O3-Eu2O3 ternary system at 1500?C and binary La2O3-Eu2O3 system at 1600-1500?C were studied in air by X-ray diffraction (XRD) investigation in the overall concentration range. The isothermal section of the phase diagram for the CeO2-La2O3-Eu2O3 system has been constructed. It was established that in the ternary CeO2-La2O3-Eu2O3 system there exist fields of solid solutions based on hexagonal (A) modification of La2O3, cubic modification of CeO2 with fluorite-type structure (F), cubic (C) and monoclinic (B) modification Eu2O3. It was established that in the binary La2O3-Eu2O3 system there exist fields of solid solutions based on hexagonal (A) modification of La2O3 and monoclinic (B) modification Eu2O3. The phases were separated by two-phase fields (A+B). The refined lattice parameters of the unit cells for solid solutions and microstructures of the definite field of compositions for the systems were determined.


Metals ◽  
2021 ◽  
Vol 11 (12) ◽  
pp. 2014
Author(s):  
Baojun Zhao ◽  
Kun Su ◽  
Xiaodong Ma

The present study investigated phase equilibria in the Na2O-SiO2-WO3 system experimentally using high-temperature equilibration, quenching, and electron probe X-ray microanalysis (EPMA). New thermodynamic information on the Na2O-SiO2-WO3 system was derived based on the newly obtained experimental results and data from the literature. The primary phase fields of sodium metasilicate, sodium disilicate, and tridymite were determined along with the isotherms at 1073, 1173, and 1273 K. The solubilities of WO3 in SiO2, Na2Si2O5, and Na2SiO3, and the solubility of SiO2 in Na2WO4 were accurately measured using EPMA. Comparisons between the existing and newly constructed phase diagram were carried out and the differences are discussed. The phase equilibrium data will be beneficial to the future development of sustainable tungsten industries and thermodynamic modelling in WO3 related systems.


Author(s):  
A. Leineweber ◽  
M. Löffler ◽  
S. Martin

Abstract Cu6Sn5 intermetallic occurs in the form of differently ordered phases η, η′ and η′′. In solder joints, this intermetallic can undergo changes in composition and the state of order without or while interacting with excess Cu and excess Sn in the system, potentially giving rise to detrimental changes in the mechanical properties of the solder. In order to study such processes in fundamental detail and to get more detailed information about the metastable and stable phase equilibria, model alloys consisting of Cu3Sn + Cu6Sn5 as well as Cu6Sn5 + Sn-rich melt were heat treated. Powder x-ray diffraction and scanning electron microscopy supplemented by electron backscatter diffraction were used to investigate the structural and microstructural changes. It was shown that Sn-poor η can increase its Sn content by Cu3Sn precipitation at grain boundaries or by uptake of Sn from the Sn-rich melt. From the kinetics of the former process at 513 K and the grain size of the η phase, we obtained an interdiffusion coefficient in η of (3 ± 1) × 10−16 m2 s−1. Comparison of this value with literature data implies that this value reflects pure volume (inter)diffusion, while Cu6Sn5 growth at low temperature is typically strongly influenced by grain-boundary diffusion. These investigations also confirm that η′′ forming below a composition-dependent transus temperature gradually enriches in Sn content, confirming that Sn-poor η′′ is metastable against decomposition into Cu3Sn and more Sn-rich η or (at lower temperatures) η′. Graphic Abstract


2003 ◽  
Vol 58 (9) ◽  
pp. 916-921 ◽  
Author(s):  
Amitabha Datta ◽  
Samiran Mitra ◽  
Georgina Rosair

Two new bimetallic complexes [Zn(phen)3][Fe(CN)5(NO)] · 2 H2O · 0.25 MeOH, (1) and [(bipy)2(H2O)Zn(μ-NC)Fe(CN)4(NO)] · 0.5 H2O, (2), have been isolated (where phen = 1,10-phenanthroline and bipy = bipyridyl) and characterised by X-ray crystallography [as the 2 H2O · 0.25 CH3OH solvate for (1) and hemihydrate for (2)] infrared spectroscopy and thermogravimetric analysis. Substitution of phenanthroline for bipyridyl resulted in a cyano-bridged bimetallic species rather than two discrete mononuclear metal complexes. The bond angles of Fe-N-O were shown to be practically linear for both 1 [179.2(7)°] and 2 [178.3(3)°], and the Zn atoms have distorted octahedral geometry. The solvent molecules in both crystal lattices take part in forming hydrogen-bonded networks.


Coatings ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 379
Author(s):  
Domagoj Mudronja ◽  
Frederik Vanmeert ◽  
Stjepko Fazinic ◽  
Koen Janssens ◽  
Darko Tibljas ◽  
...  

Stone monuments and buildings are susceptible to weathering. Carbonate-based stones are especially vulnerable in acidic environments, whereas magmatic acidic stones are more susceptible to chemical weathering in basic environments. To slow down surface corrosion of limestone and marble artworks/buildings, protective coatings which inhibit calcite dissolution have been proposed. In this work, samples from two stone types with different porosity were treated with ammonium oxalate (AmOx) to create a protective layer of calcium oxalate (CaOx) using the previously developed brushing method. Two different synchrotron microscopy experiments were performed to determine its protective capability. X-ray powder diffraction (SR-μ-XRPD) in transmission geometry allowed visualization of the distributions of calcium carbonate and oxalates along the sample depths. In a second step, X-ray fluorescence (SR-μ-XRF) was used to check the efficiency/integrity of the protective surface coating layer. This was done by measuring the sulfur distribution on the stone surface after exposing the protected stones to sulfuric acid. XRPD showed the formation of a protective oxalate layer with a thickness of 5–15 µm on the less porous stone, while a 20–30 µm thick layer formed on the more porous stone. The XRF study showed that the optimal treatment time depends on the stone porosity. Increasing the treatment time from 1 to 3 h resulted in a decreased efficiency of the protective layer for the low porosity stone. We assume that this is due to the formation of vertical channels (cracks) in the protective layer.


2010 ◽  
Vol 660-661 ◽  
pp. 983-988 ◽  
Author(s):  
Alexander Rodrigo Arakaki ◽  
Walter Kenji Yoshito ◽  
Valter Ussui ◽  
Dolores Ribeiro Ricci Lazar

Zirconia stabilized with 8.5 mol% yttria (YSZ) were synthesized by coprecipitation and resulting gels were hydrothermallly treated at 200°C and 220 PSI for 4, 8 and 16 hours. Products were oven dried at 70°C for 24 hours, isostatically pressed as pellets and sintered at 1500 °C for 1 hour. Powders were characterized for surface area with N2 gas adsorption, X-ray diffraction, laser diffraction granulometric analysis and scanning and transmission electronic microscopy. Density of ceramics was measured by an immersion method based on the Archimedes principle. Results showed that powders dried at 70°C are amorphous and after treatment has tetragonal/cubic symmetry. Surface area of powders presented a significant reduction after hydrothermal treatment. Ceramics prepared from hydrothermally treated powders have higher green density but sintered pellets are less dense when compared to that made with powders calcined at 800°C for 1 hour due to the agglomerate state of powders. Solvothermal treatment is a promising procedure to enhance density.


1997 ◽  
Vol 504 ◽  
Author(s):  
S. C. Choi ◽  
K. H. Kim ◽  
H-J. Jung ◽  
C. N. Whang ◽  
S. K. Koha

ABSTRACTPolyimide films are modified by ion assisted reaction method using various ion beams in various gases environments. Amount of ion and blown gases rate were changed from 5 × 1014 to 1 × 1017 and from 0 to 8 sccm, respectively. Wetting angles between water and polyimide films modified by Ar+ ion without oxygen blowing decrease from 67° to 400° and surface free energies increase from 46 to 64 dyne/cm2. Wetting angle of polyimide films modified by Ar+ ion in an oxygen environment decreases to 12° and surface free energy increases to 72 dyne/cm2. The lowest wetting angle was obtained by oxygen ion irradiation in the oxygen gas environment and its value was 7°. In the case of polyimide film modified by Ar+ ions in an oxygen environment, the wetting angle increases up to 65° when it kept in air and that increases up to 46° when it kept in water after 5 day. In the case of polyimide film modified by O2+ ion in oxygen environment, however, the wetting angle of polyimide film dose not increase. X-ray photoelectron analysis shows that the chemical bonds between polyimide components are severed by ion irradiation and hydrophilic groups such as CO and C=O are formed by the reaction between newly formed radicals and blown oxygen. It was found that adhesion between Cu and polyimide modified by ion assisted reaction was improved. The main reason of the enhanced adhesion is due to the reaction between Cu and C-O or C=O groups formed by ion assisted reaction on the polyimide surface.


1992 ◽  
Vol 45 (9) ◽  
pp. 1375 ◽  
Author(s):  
RL Withers ◽  
JG Thompson ◽  
PJ Barlow ◽  
JC Barry

A detailed transmission electron microscope and X-ray powder diffraction study has been made of the so-called 'defect fluorite' phase field in the ZrO2-PrO1.5 system and of its close relationship to the pyrochlore solid solution field in the same system. Even for the lowest possible PrO1.5 content within the 'defect fluorite' phase field, it is clear that the sharp Bragg reflections characteristic of the underlying fluorite average structure are accompanied by some of the 'satellite reflections' characteristic of the pyrochlore solid solution field. As the PrO1.5 content increases, these satellite reflections increase systematically in intensity as well as sharpening very considerably. It is shown that this 'defect fluorite' phase field cannot be adequately described either in terms of random point defects within an average fluorite-type matrix or in terms of a diphasic texture of pyrochlore domains embedded coherently into a fluorite matrix, but must be regarded as enuinely intermediate between these two end-member structures and of commensurately modulated fluorite type. A group theoretical approach is used to propose a model for the structural deviation from the underlying fluorite average structure.


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.


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