scholarly journals Thermodynamic non-ideality and disorder heterogeneity in actinide silicate solid solutions

2021 ◽  
Vol 5 (1) ◽  
Author(s):  
J. Marcial ◽  
Y. Zhang ◽  
X. Zhao ◽  
H. Xu ◽  
A. Mesbah ◽  
...  
Keyword(s):  
Solid Solutions ◽  
Random Distribution ◽  
Learning Algorithm ◽  
Function Analysis ◽  
Atomic Scale ◽  
Distribution Model ◽  
Nuclear Waste Repository ◽  
Stability Field ◽  
Solid Solution System ◽  
The Stability

AbstractNon-ideal thermodynamics of solid solutions can greatly impact materials degradation behavior. We have investigated an actinide silicate solid solution system (USiO4–ThSiO4), demonstrating that thermodynamic non-ideality follows a distinctive, atomic-scale disordering process, which is usually considered as a random distribution. Neutron total scattering implemented by pair distribution function analysis confirmed a random distribution model for U and Th in first three coordination shells; however, a machine-learning algorithm suggested heterogeneous U and Th clusters at nanoscale (~2 nm). The local disorder and nanosized heterogeneous is an example of the non-ideality of mixing that has an electronic origin. Partial covalency from the U/Th 5f–O 2p hybridization promotes electron transfer during mixing and leads to local polyhedral distortions. The electronic origin accounts for the strong non-ideality in thermodynamic parameters that extends the stability field of the actinide silicates in nature and under typical nuclear waste repository conditions.

scholarly journals Study of silica-undersaturated magmas through the Kalsilite- Nepheline-Diopside-Silica system at 4.0 GPa and dry conditions

2018 ◽  
Vol 18 (2) ◽  
pp. 87-102
Author(s):  
Márcio Roberto Wilbert de Souza ◽  
Rommulo Vieira Conceição ◽  
Daniel Grings Cedeño ◽  
Roberto Vicente Schmitz Quinteiro
Keyword(s):  
High Pressure ◽  
Solid Solutions ◽  
Negative Correlation ◽  
Stability Field ◽  
Thermal Barrier ◽  
High Pressure And Temperature ◽  
Alkaline Magma ◽  
Magma Genesis ◽  
Dry Conditions ◽  
The Stability

This study experimentally investigates the Kalsilite-Nepheline-Diopside-Silica system at high pressure and temperature, with emphasis on silica-undersaturated volume (leucite-nepheline-diopside — Lct-Nph-Di; and kalsilite-nepheline-diopside — Kls + Nph + Di — planes), at 4.0 GPa (~120 km deep), temperatures up to 1,400ºC and dry conditions, to better understand the influence of K2O, Na2O, and CaO in alkali-rich silica-undersaturated magma genesis. In the Lct-Nph-Di plane, we determined the stability fields for kalsilite (Klsss), nepheline (Nphss) and clinopyroxene (Cpxss) solid solutions, wollastonite (Wo) and sanidine (Sa); and three piercing points: (i) pseudo-eutectic Kls + Nph + Di + liquid (Lct62Nph29Di9) at 1,000ºC; (ii) Kls + Sa + (Di + Wo) + liquid (Lct75Nph22Di2) at 1,200ºC; and (iii) pseudo-eutectic Kls + Di + Wo + liquid (Lct74Nph17Di9) at 1,000ºC. Kalsilite stability field represents a thermal barrier between ultrapotassic/potassic vs. sodic compositions. In the plane Kls-Nph-Di, we determined the stability fields for Klsss, Nphss and Cpxss and two aluminous phases in smaller proportions: spinel (Spl) and corundum (Crn). This plane has a piercing point in Kls + Nph + Di(± Spl) + liquid (Kls47Nph43Di10) at 1,100ºC. Our data showed that pressure extends K dissolution in Nph (up to 39 mol%) and Na in Kls (up to 27 mol%), and that these solid solutions, if present, determinate how much enriched in K and Na an alkaline magma will be in an alkaline-enriched metasomatic mantle. Additionally, we noted positive correlation between K2O and SiO2 concentration in experimental melts, negative correlation between CaO and SiO2, and no evident correlation between Na2O and SiO2. 

Phase Equilibria in the System NaAlSi3O8–NaAlSiO4–H2O with Special Emphasis on the Stability of Analcite

1971 ◽  
Vol 8 (3) ◽  
pp. 311-337 ◽  
Author(s):  
Ki-Tae Kim ◽  
B. J. Burley
Keyword(s):  
Solid Solution ◽  
Phase Equilibria ◽  
Phase Diagrams ◽  
Solid Solutions ◽  
Singular Points ◽  
Phase Relations ◽  
The Other ◽  
Stability Field ◽  
Narrow Zone ◽  
The Stability

Phase equilibria were determined in the P–T range of 0.5–10 Kb and 150–900 °C in the system NaAlSi3O8 – NaAlSiO4 – H2O. Two isobaric (2 Kb and 5.15 Kb) T–X phase diagrams (projected to a dry base) were completely determined and show that the stability field of analcite solid solutions has a large distorted pentagonal shape. The phase relations for the transition: nepheline hydrate I [Formula: see text] nepheline + H2O on the composition join NaAlSiO4 – H2O are not binary. It was found that there exists a narrow zone for the transition. The true P–T curve was found and determined in terms of a ternary univariant reaction: nepheline hydrate I + analcite [Formula: see text] nepheline + H2O. In the system NaAlSi3O8 – SiO2 – H2O, albite contains about 5 wt % silica in solid solution at 5.15 Kb and 670 °C.The equilibrium compositions of various univariant phases were determined essentially on the basis of the T–X phase diagrams. Another univariant reaction (zeolite species P = analcite + nepheline – hydrate I + H2O) was found at 2 Kb/215 °C and 5.15 Kb/235 °C and determined on a P–T projection. Three singular points were determined; two of them are located at 0.8 Kb/390 °C and 9.4 Kb/475 °C respectively on a univariant P–T curve for the reaction nepheline hydrate I + analcite = nepheline + H2O; the other one is located at 6 Kb/655 °C on a univariant P–T curve along which nepheline, analcite, liquid, and vapor coexist. The petrogenetic implication of analcite is discussed fully.

A further study of analcime solid solutions in the system NaAlSi3O8-NaAISiO4-H20, with particular note of an analcime phase transformation

1980 ◽  
Vol 43 (332) ◽  
pp. 1035-1045 ◽  
Author(s):  
Ki-Tae Kim ◽  
B. J. Burley
Keyword(s):  
Phase Transition ◽  
Solid Solution ◽  
Phase Transformation ◽  
Solid Solutions ◽  
Total Pressure ◽  
Room Temperature ◽  
Water Pressure ◽  
Stability Field ◽  
Cell Parameters ◽  
The Stability

SummaryThe stability field of analcime solid solutions in the system NaAlSi3O8-NaAlSiO4-H2O has been previously determined by Kim and Burley (1971a). These experiments are re-examined with a view to determining the variations of the room-temperature cell parameters of analcime as a function of temperature of synthesis and composition. It is shown from this evidence that most of the analcime solid solutions in these experiments are equilibrium compositions. The increase in the cell dimension of quenched analcime solid solution is found to be 5 × 10−5 Å/°C. It is suggested that birefringence in analcime is induced by low water-pressure relative to total pressure. A phase transition appears to be observed in quenched analcimes of this study and is thought to be the same as that in the Golden analcime reported by Yoder and Weir (1960).

Scalable Approach to High Coverages on Oxides via Iterative Training of a Machine-Learning Algorithm

2019 ◽  
Author(s):  
Andrew Medford ◽  
Shengchun Yang ◽  
Fuzhu Liu
Keyword(s):  
Machine Learning ◽  
Chemical Potential ◽  
Learning Algorithm ◽  
Absolute Error ◽  
Low Energy ◽  
Training Data ◽  
High Coverage ◽  
Metal Compounds ◽  
Adsorption Energies ◽  
The Stability

Understanding the interaction of multiple types of adsorbate molecules on solid surfaces is crucial to establishing the stability of catalysts under various chemical environments. Computational studies on the high coverage and mixed coverages of reaction intermediates are still challenging, especially for transition-metal compounds. In this work, we present a framework to predict differential adsorption energies and identify low-energy structures under high- and mixed-adsorbate coverages on oxide materials. The approach uses Gaussian process machine-learning models with quantified uncertainty in conjunction with an iterative training algorithm to actively identify the training set. The framework is demonstrated for the mixed adsorption of CH<sub>x</sub>, NH<sub>x</sub> and OH<sub>x</sub> species on the oxygen vacancy and pristine rutile TiO<sub>2</sub>(110) surface sites. The results indicate that the proposed algorithm is highly efficient at identifying the most valuable training data, and is able to predict differential adsorption energies with a mean absolute error of ~0.3 eV based on <25% of the total DFT data. The algorithm is also used to identify 76% of the low-energy structures based on <30% of the total DFT data, enabling construction of surface phase diagrams that account for high and mixed coverage as a function of the chemical potential of C, H, O, and N. Furthermore, the computational scaling indicates the algorithm scales nearly linearly (N<sup>1.12</sup>) as the number of adsorbates increases. This framework can be directly extended to metals, metal oxides, and other materials, providing a practical route toward the investigation of the behavior of catalysts under high-coverage conditions.

Atomic-Scale Structure of SixGe1-x Solid Solutions

2005 ◽  
Vol 24-25 ◽  
pp. 523-526 ◽  
Author(s):  
Ichiro Yonenaga ◽  
Masaki Sakurai ◽  
Marcel H.F. Sluiter ◽  
Y. Kawazoe
Keyword(s):  
Solid Solutions ◽  
Scale Structure ◽  
Atomic Scale ◽  
Atomic Scale Structure

Eclogite from central Yukon: a record of subduction at the western margin of ancient North America

1983 ◽  
Vol 20 (9) ◽  
pp. 1389-1408 ◽  
Author(s):  
Philippe Erdmer ◽  
Herwart Helmstaedt
Keyword(s):  
North America ◽  
North American ◽  
Stability Field ◽  
Western Margin ◽  
Thrust Sheets ◽  
The Stability ◽  
Basic Igneous Rock ◽  
Inclusion Trails ◽  
Tectonic Boundary ◽  
Host Rocks

Eclogite occurring in central Yukon, at Faro and near Last Peak, as lenses interleaved with muscovite–quartz blastomylonite has the chemical and field characteristics of group C rocks. From sigmoidal inclusion trails in garnet, from geothermometry and geobarometry, and from mineral parageneses, the eclogite is inferred to have a crustal protolith and to have followed a hysteretic, subduction-cycle P–T trajectory. Transformation of basic igneous rock into schist was followed by eclogite metamorphism during which pressure was at least 1000 MPa and temperature was between 600 and 700 °C. Uplifting involved passage through the stability field of glaucophane; the eclogite and its host rocks were then subjected to greenschist fades metamorphism and deformation, with temperature at approximately 400 °C. The rocks were emplaced as thrust sheets against or onto the western North American cratonal margin. The tectonic boundary ranges from nearly vertical, where it is outlined by a zone of steeply dipping mélange, to nearly horizontal beneath klippen of cataclastic rocks that lie on North American miogeoclinal strata. Together with occurrences of eclogite on strike, in Yukon, near Fairbanks (Alaska), and near Pinchi Lake (British Columbia), eclogite at Faro and near Last Peak implies that the Yukon Cataclastic Complex is a deeply eroded collision mélange that borders over 1000 km of the ancient continental margin.

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