Thermodynamics of Materials in Extreme Environments: On-Demand: Thermodynamics and Stabilities of Alloys and Ceramics
Sponsored by: ACerS Basic Science Division, ACerS Energy Materials and Systems Division
Program Organizers: Xiaofeng Guo, Washington State University; Kristina Lilova, Arizona State University; Kyle Brinkman, Clemson University; Alexandra Navrotsky, Arizona State University; Jake Amoroso, Savannah River National Laboratory; Xingbo Liu, West Virginia University; Gustavo Costa, NASA Glenn Research Center
Friday 8:00 AM
October 22, 2021
Room: On-Demand Room 9
Location: MS&T On Demand
Session Chair: Kristina Lilova, Arizona State University; Gustavo Costa, NASA Glenn Research Center
Invited
Thermodynamics in the Design and Performance of Glass: Joseph Ryan1; 1Pacific Northwest National Laboratory
Glasses, in a way, operate in a more loose relationship with thermodynamics than many materials. They scoff at the notion of melting points, with supercooling a key part of their formation. When solidification happens, the glass transition can fluctuate widely with cooling rate and is not even a fixed point in temperature. Even during their dissolution, amorphous silicate phases precipitate on their surfaces with no consideration to the thermodynamically stable crystalline end points. Thermodynamics influences all materials, however – even ones as favorable to metastable states as glasses. This talk will explore how improved understanding of thermodynamics in glass systems can help to enable smart materials development and improved models for performance.
Invited
In-situ Hydrothermal Synthesis Calorimetry on Nonclassical Pathways of Nickel–aluminum Layered Double Hydroxide (NiAl-LDH) Formation: Xianghui Zhang1; Cody Cockreham1; Esra Mertsoy1; Hui Sun2; Xiaofeng Guo1; Hongwu Xu3; Di Wu1; 1Washington State University; 2East China University of Science and Technology; 3Los Alamos National Laboratory
Nickel–Aluminum layered double hydroxides (NiAl-LDHs) demonstrate competitive energy storage performance as capacitive electrode materials. Our earlier studies elucidated the energetics-structure-performance relationships of NiAl-LDHs with different Ni/Al ratios, from 2 to 4. Here, coupling in situ hydrothermal synthesis calorimetry, ex situ XRD, DRIFTS, SEM and TEM we further reveal the energetic pathways of formation of NiAl-LDHs modulated with different molecular modifiers (urea, hexamethylenetetramine and NaOH) under hydrothermal conditions within autoclaves in real-time. Our results highlight that subtle variations in type and concentration of molecular modifiers lead to rerouted formation pathways, clearly evidenced by the in situ calorimetric data.
Strength, Deformation, and Equation of State of Tungsten Carbide to 66 GPa: Benjamin Brugman1; Feng Lin2; Mingda Lv3; Curtis Kenney-Benson4; Dmitry Popov4; Lowell Miyagi2; Susannah Dorfman3; 1Arizona State University; 2University of Utah; 3Michigan State University; 4HPCAT, Argonne National Lab
Tungsten carbide exhibits remarkable physical properties including high strength and incompressibility, making it useful for industrial applications. Yet the bulk modulus of WC is discrepant by 120 GPa and its quasi-static strength and deformation mechanisms have not been studied at high pressure. We used synchrotron X-ray diffraction at the Advanced Photon Source Sector 16 to study bulk and nano-grain WC compressed to 66 GPa in the diamond anvil cell. Bulk WC is stiffer than nano WC, with respective bulk moduli of K0 = 397 ± 7 and 377 ± 7 GPa and K0’ = 3.3 ± 0.3 and 3.8 ± 0.3. Strength and plasticity were determined from lattice strain and preferred orientation. Slip mechanisms were determined by Elasto-viscoplastic self-consistent simulations of experimental strain and texture. Yielding at ~30 GPa is accommodated by prismatic slip, at which pressure WC sustains 12-16 GPa differential stress, with pyramidal slip activated at ~40 GPa.
Incorporation of Thorium and Uranium in the Monazite Structure by Wet Chemistry Route: Synthesis, Sintering and Long-term Behavior: Nicolas Dacheux1; Danwen Qin2; Alison Roche1; Adel Mesbah3; Nicolas Clavier3; Stephanie Szenknect4; Renaud Podor3; 1University of Montpellier; 2ENSCM; 3CNRS; 4CEA
From long, several phosphate-based ceramics, including monazites, have been considered to manage the specific conditioning of actinides or plutonium. In this field, monazite ceramics were reported as promising candidates based on their easy way of elaboration, structural flexibility, sintering capability and good resistance to radiation damage and to weathering conditions.New recent advances allowed preparing, by wet chemistry routes, some single phase and homogeneous samples containing tetravalent thorium or uranium. Optimized sintering conditions were fixed with the help of sintering maps to prepare well densified pellets, which were submitted to multiparametric leaching tests. From a kinetic point of view, the high chemical durability of the ceramics was confirmed. Moreover, several low-soluble neoformed phases formed rapidly at the solid/solution interface when saturation conditions were reached in the solution. Associated thermodynamic data, including solubility constants confirmed the very good properties of monazites in terms of long-term behavior.
Thermodynamic Properties of Special Alloys of the Ti-Al System Formed under SHS Conditions: Borys Sereda1; Dmytro Sereda1; Dmytro Kruglyak2; Yuriy Belokon2; 1Dneprovsky State Technical University; 2Zaporizhzhya National University
The results of a thermodynamic analysis of the reactions that are possible in the preparation of titanium-aluminum alloy intermetallic compounds under conditions of self-propagating high-temperature synthesis (SHS) are presented. Thermodynamic analysis showed that the adiabatic combustion temperature for the titanium-aluminum system is lower than the melting temperature of the final product, which is an insufficient condition for the SHS reaction to occur under normal conditions. To carry out the synthesis reaction, coarse heating of the system to the a-TiAl temperature of alloys of 400 ... 600 K is necessary. A sequence of SHS reactions is also established, leading to the formation, which helps to elucidate the mechanism of obtaining special alloys of the Ti-Al system formed under SHS conditions.
Thermal and Microstructural Evolutions in Kerogen-rich Marcellus Shale: Cody Cockreham1; Xianghui Zhang1; Miu Lun Lau2; Min Long2; Xiaofeng Guo1; Hongwu Xu3; Di Wu1; 1Washington State University; 2Boise State University; 3Los Alamos National Laboratory
To develop hydrocarbon recovery with heating methods, it is essential to understand the nature of the thermal and microstructural behaviors of shale in both oxidative and reductive atmospheres. Here, we report our recent studies on the thermal and microstructural properties of a shale sample from the Marcellus Formation, Pennsylvania. Employing in situ XRD, in situ DRIFTS, small-angle neutron scattering (SANS), integrated TG-DSC-MS, and TEM, we were able to correlate the naturally heterogeneous and complex chemistry of the Marcellus shale with its mineralogical and thermal stability up to 900 °C in both air and inert gas. The thermal decomposition of organic and inorganic phases led to systematic evolutions in the shale characteristics. The decompositions of kerogen and minerals resulted in microscopic cracks and accessible channels/pores within the shale, which were probed and elucidated with SANS. This study enables insights into the thermal pyrolysis process of shale for enhanced hydrocarbon recovery.
High-temperature Structure and Thermodynamics of Cerium Silicates, A-Ce2Si2O7, and Ce4.67(SiO4)3O: Andrew Strzelecki1; Kyle Kriegsman2; Paul Estevenon3; Vitaliy Goncharov2; Jianming Bai4; Stephanie Szenknect3; Adel Mesbah3; Di Wu2; John McCloy5; Nicolas Dacheux3; Xiaofeng Guo2; 1Washington State University; 2Alexandra Navrotsky Institute for Experimental Thermodynamics, Washington State University; 3ICSM, Univ Montpellier, CNRS, CEA, ENSCM, Site de Marcoule; 4National Synchrotron Light Source II, Brookhaven National Laboratory; 5Mechanical and Materials Engineering, Washington State University
Lanthanide disilicates and oxyapatites have potential roles in high temperature applications as thermal (TBC) and environmental barrier coatings (EBC). In this work, structural and thermodynamic investigations on A-Ce2Si2O7 (tetragonal, P41) and Ce4.67(SiO4)3O (hexagonal, P63/m) were performed. The high temperature structural behaviors and coefficients of thermal expansion were determined by in situ high temperature synchrotron XRD and TGA-DSC. A-Ce2Si2O7 was found to be stable in N2 and air up to ~1483 K with an isotropic thermal expansion. Ce4.67(SiO4)3O had a slow partial oxidation between 533 K and 873 K, followed by a thermal decomposition to CeO2 and SiO2 at ~1000 K in air. By using high temperature oxide melt solution calorimetry, the standard enthalpy of formation was determined for A-Ce2Si2O7 (-3825.1 ± 6.0 kJ/mol) and Ce4.67(SiO4)3O (-7391.3 ± 9.5 kJ/mol). These thermodynamic parameters were used in examining each phases chemical stability in high temperature environments relevant to aeronautical applications.
Determination of the Activation Energy of the Formation of Intermetallic Compounds in the Ni-Al and Ti-Al System upon Receipt of Special Alloys: Borys Sereda1; Dmytro Sereda1; Yuriy Belokon2; 1Dneprovsky State Technical University; 2Zaporizhzhya National University
In work the two methods for activation energy determination at the intermetallics formation are considered: theoretical calculation method based on the results of thermodynamic analysis during SHS-reactions and experimental method based on the study of the kinetics formation in intermetallic phases. It is established that the activation energies for the Ni-Al and Ti-Al systems are ~45 and ~82 kJ/mol respectively. It is shown that the difference between the values of activation energies obtained by two different methods does not exceed 5 %. The obtained results can be used for further calculations of reactions in the physicochemical model in intermetallide systems upon receipt of special alloys of the Ni-Al and Ti-Al systems formed under non-stationary temperature conditions.