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Mesbah, Adel

Publications and source records attributed to Mesbah, Adel.

9 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

High-Pressure Structural and Thermodynamic Properties of Cerium Orthosilicates (CeSiO 4 )

Pressure-induced phase transitions from the zircon structure-type (I4 1 /amd) to the scheelite structure type (I4 1 /a) are known for many ternary oxides systems (ABO 4 ). In this work, we present the first high-pressure study on synthetic stetindite (CeSiO 4 ) by a combination of in situ high-pressure synchrotron powder X-ray diffraction up to 36 GPa, implemented with and without dual sided laser heating, and in situ high-pressure Raman spectroscopy up to 43 GPa. Two phase transitions were identified: zircon to a high-pressure low-symmetry (HPLS) phase at 15 GPa and then to a scheelite at 18 GPa. The latter from HPLS scheelite phase was found irreversible; i.e., scheelite is fully quenchable at ambient conditions, as in other zircon-type phases. The bulk moduli (K 0 ) of stetindite, HPLS, and high-pressure scheelite phases were determined, respectively, as 171(5), 105(4), and 221(40) GPa by fitting to a second-order Birch-Murnaghan equation of state. The pressure derivatives of vibrational modes and Gru''neisen parameters of the zircon-structured polymorph are similar to those of other orthosilicate minerals. In conclusion, due to the larger ionic radii of Ce 4+ , with respect to Zr 4+ , stetindite was found to possess a softer bulk modulus and undergo the phase transitions at a lower pressure than zircon (ZrSiO 4 ), such observations are consistent with what were found in coffinite (USiO 4 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Chemical and environmental stability of monazite-cheralite solid solutions Ln 1-2 x Ca x Th x PO 4 (Ln = Pr, Nd; x = 0–0.15): A thermodynamic study

Monazite-cheralite ceramics are a promising waste form for actinides. To elucidate the long-term behavior of this matrix in aqueous solutions, this study measured thermodynamic data for Th-rhabdophanes Ln 1-2 x Ca x Th x PO 4 ·nH 2 O (with Ln = Pr, Nd; x = 0–0.15) and the associated anhydrous monazite-cheralites Ln 1-2 x Ca x Th x PO 4 . Further, solubility experiments at 298K and high temperature oxide melt solution calorimetry were combined for calculation of ΔG$^°_f$, ΔH$^°_f$ and S$^°_m$ of Th-rhabdophanes and associated monazite-cheralites. Standard solubility constants were employed in a geochemical simulation using the PHREEQC software, the results of which confirmed the high chemical stability of the monazite-cheralite phases and supported their use as a specific conditioning matrix for the long-term immobilization of actinides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Understanding the setting and hardening process of wollastonite-based brushite cement. Part 2: Influence of the boron and aluminum concentrations in the mixing solution

The mixing solution of wollastonite-based brushite cement is a phosphoric acid solution containing metallic cations and borax. This work complements a previous study devoted to the influence of the H{sub 3}PO{sub 4} concentration, Ca/P and liquid-to-solid (l/s) ratios on the setting and hardening process of the binder by providing new insight into the role of aluminum and boron. Boron retards the setting and decreases the heat released during the process. It also contributes to reduce the macroporosity of the hardened material but yields to poor compressive strength. With aluminum in the mixing solution, the mechanical properties are greatly improved thanks to the precipitation of an amorphous aluminophosphate which increases the density of the cement matrix. But aluminum alone leads to fast setting. A joint addition of boron and aluminum to the mixing solution makes it possible to get a material with optimized properties both in fresh and hardened states.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The Role of Water and Hydroxyl Groups in the Structures of Stetindite and Coffinite, MSiO 4 (M = Ce, U)

Orthosilicates adopt the zircon structure types ( I 4 1 /amd ), consisting of isolated SiO 4 tetrahedra joined by A-site metal cations, such as Ce and U. They are of significant interest in the fields of geochemistry, mineralogy, nuclear waste form development, and material science. Stetindite (CeSiO 4 ) and coffinite (USiO 4 ) can be formed under hydrothermal conditions despite both being thermodynamically metastable. Water has been hypothesized to play a significant role in stabilizing and forming these orthosilicate phases, though little experimental evidence exists. To understand the effects of hydration or hydroxylation on these orthosilicates, in situ high-temperature synchrotron and laboratory-based X-ray diffraction was conducted from 25 to ~850 °C. Stetindite maintains its I 4 1 /amd symmetry with increasing temperature but exhibits a discontinuous expansion along the a- axis during heating, presumably due to the removal of water confined in the [001] channels, which shrink against thermal expansion along the a -axis. Furthermore, additional in situ high-temperature Raman and Fourier transform infrared spectroscopy also confirmed the presence of the confined water. Coffinite was also found to expand nonlinearly up to 600 °C and then thermally decompose into a mixture of UO 2 and SiO 2 . A combination of dehydration and dehydroxylation is proposed for explaining the thermal behavior of coffinite synthesized hydrothermally. Additionally, we investigated high-temperature structures of two coffinite-thorite solid solutions, uranothorite (U x Th 1– x SiO 4 ), which displayed complex variations in composition during heating that was attributed to the negative enthalpy of mixing. Lastly, for the first time, the coefficients of thermal expansion of CeSiO 4 , USiO 4 , U 0.46 Th 0.54 SiO 4 , and U 0.9 Th 0.1 SiO 4 were determined to be α V = 14.49 × 10 –6 , 14.29 × 10 –6 , 17.21 × 10 –6 , and 17.23 × 10 –6 °C –1 , respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2020

High-Temperature Thermodynamics of Cerium Silicates, A-Ce 2 Si 2 O 7 , and Ce 4.67 (SiO 4 ) 3 O

Lanthanide disilicates and oxyapatites have potential roles in high temperature applications as thermal (TBC) and environmental barrier coatings (EBC), or possible alteration phases in geological nuclear waste repositories. However, those Ce 3+ -bearing silicates have only been limitedly studied. In this work, we performed detailed structural and thermodynamic investigations on A-Ce 2 Si 2 O 7 (tetragonal, P4 1 ) and Ce 4.67 (SiO 4 ) 3 O (hexagonal, P6 3 /m). The high temperature structural behaviors and coefficients of thermal expansion were determined by in situ high temperature synchrotron X-ray diffraction (HT-XRD) implemented with Rietveld analysis and thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC). A-Ce 2 Si 2 O 7 was found to be stable in N 2 and air up to ~1483 K with anisotropic thermal expansion along the a and c axes (α a = 12.3 × 10 -6 K -1 and α c = 12.4 × 10 -6 K -1 ). Ce 4.67 (SiO 4 ) 3 O had a slow partial oxidation between 533 K and 873 K to a new nonstoichiometric phase Ce 3+ 1.67- xCe4 + x Ce 3+ 3 (SiO 4 ) 3 O 1+0.5x , followed by a thermal decomposition to CeO 2 and SiO 2 at ~1000 K in air. By using high temperature oxide melt solution calorimetry at 973 K with lead borate as the solvent, the standard enthalpy of formation was determined for A-Ce 2 Si 2 O 7 (-3825.1 ± 6.0 kJ/mol) and Ce 4.67 (SiO 4 ) 3 O (-7391.3 ± 9.5 kJ/mol). Finally, these thermodynamic parameters were compared with those of CeO 2 , CeSiO 4 , and other silicate oxyapatites for examining their chemical stability in high temperature environments relevant for aeronautical applications, mineral formation, and nuclear fuel cycle.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Thermodynamics of CeSiO 4 : Implications for Actinide Orthosilicates

Zircon (ZrSiO 4 : I4 1 /amd) can accommodate actinides, such as thorium, uranium, and plutonium. The zircon structure has been determined for several of the end member compositions of other actinides, such as plutonium and neptunium. However, the thermodynamic properties of these actinide zircon structure-types are largely unknown due to the difficulties in synthesizing these materials and handling transuranium actinides. Thus, we have completed a thermodynamic study of cerium orthosilicate, stetindite (CeSiO 4 ), a surrogate of PuSiO 4 . For the first time, the standard enthalpy of formation of CeSiO 4 was obtained by high temperature oxide melt solution calorimetry to be -1971.9 ± 3.6 kJ/mol. Stetindite is energetically metastable with respect to CeO 2 and SiO 2 by 27.5 ± 3.1 kJ/mol. The metastability explains the rarity of the natural occurrence of stetindite and the difficulty of its synthesis. Applying the obtained enthalpy of formation of CeSiO 4 from this work, along with those previously reported for USiO 4 and ThSiO 4 , we developed an empirical energetic relation for actinide orthosilicates. Here, the predicted enthalpies of formation of AnSiO 4 are then made with a discussion of future strategies to efficiently immobilize Pu or minor actinides in the zircon structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗