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At least 847 records · Page 47

Geologic hydrogen as an emerging fuel: experimental insights, thermodynamics, kinetics, and reactive transport modeling

Geologic hydrogen (GeoH 2 ) is emerging as a viable clean energy source. It is largely produced through serpentinization, a geological process in which ultramafic rocks react with water under suitable temperature and pressure. Here, this review synthesizes the current understanding of H 2 generation by serpentinization, with an emphasis on reaction mechanisms, kinetics, and thermodynamics, as well as on modeling flow and transport of reacting fluids in geological formations. We describe the role of mineral assemblages, such as olivine and pyroxene, fluid-rock interactions, and catalytic surfaces, in influencing GeoH 2 yield and reaction rates. By integrating models of reaction kinetics, subsurface reactive flow and transport, and the serpentinization process, and by accounting for the thermodynamic state of the system, this review aims to guide future GeoH 2 research and to evaluate the potential of natural hydrogen as a sustainable clean energy source.

Moradi, Rasoul [Univ. of Southern California, Los ↗

A probabilistic perspective on thermodynamic parameter uncertainties: Understanding aqueous speciation of mercury

Speciation plays an important role in determining the fate and transport of metals in terrestrial surface and subsurface systems. Equilibrium speciation modeling in aqueous systems relies on thermodynamic constants (log K values) of complexes, which are subject to uncertainties. In this study, using Monte Carlo (MC) simulations with Latin hypercube sampling (LHS) we systematically analyze the propagation of thermodynamic constant uncertainty through speciation modeling of an inorganic mercury-sulfide-chloride-water system. We find that seemingly small variances of the input log K normal distributions can lead to output species concentrations spanning multiple orders of magnitude, with highly skewed probability distributions. When equilibrium with mineral metacinnabar (β-HgS(s)) is neglected, the relative uncertainty of each output species is strongly positively correlated with the skewness of its concentration probability distribution, i.e., the lowest uncertainty occurs when the species concentration probability distribution is the most negatively skewed as its concentration approaches the total element concentration limit. The highest uncertainty in the identity of dominant species is located around species equivalence points. For cases where the mineral equilibrium is included, we derive analytical probability density functions for the log concentrations of all major species in the system. The mineral log K uncertainty is found to be an important contributor to all output concentration uncertainties. The analysis of combined effects of both pH and total sulfide concentration on output concentration uncertainties shows that high concentration uncertainties occur under highly sulfidic alkaline conditions and low uncertainties at low pH and sulfide concentrations. Finally, an analysis as presented here can distinguish between conditions that require a full uncertainty analysis and those for which the classical deterministic speciation modeling suffices.

58 GEOSCIENCES↗

Low temperature heat capacity and thermodynamic functions of anion bearing sodalites Na 8 Al 6 Si 6 O 24 X 2 (X = SO 4 , ReO 4 , Cl, I)

Heat capacities of sulfate, perrhenate, chloride, and iodide sodalites with the ideal formula Na 8 Al 6 Si 6 O 24 X 2 (X = SO 4 , ReO 4 , Cl, I) were measured from 2 K to 300 K using a Quantum Design Physical Property Measurement System (PPMS). From the heat capacity data, the standard thermodynamic functions were determined. All four sodalites undergo a phase transition below room temperature for which thermodynamic parameters were determined. Additionally, the heat capacity of one of the constituent compounds (NaReO 4 ) was measured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and thermodynamic effects of hydration in Na-zeolite A (LTA) from low-temperature heat capacity

Zeolite A (Linde Type A; LTA) is an industrially important porous mineral that has recently been shown to exhibit framework flexibility upon changes in hydration level. Here, to investigate the flexibility transition from a thermodynamic perspective, we have performed heat capacity measurements on sodium zeolite A at seven incremental hydration levels ranging from zero to equilibrium with ambient air. Excess low-frequency vibrations beyond the predictions of the Debye model are found in all samples, and the frequency of these vibrations increases as a function of hydration level. This suggests that an increase in hydration causes a decrease in at least one type of framework flexibility for sodium zeolite A. In addition, a subtle excess heat capacity contribution from 150 to 280 K is observed only for low and intermediate hydration levels, which may arise from a transformation tied to framework flexibility previously observed in zeolite A via gas absorption calorimetry. Values of the standard thermodynamic functions C p,m °, Δ 0 T S m °, Δ 0 T H m °, and Φ m ° are also reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidation and Hydrogen Uptake in Zirconium, Zircaloy-2 and Zircaloy-4: Computational Thermodynamics and Ab Initio Calculations

Zirconium-based alloys Zircaloy-2 and Zircaloy-4 are widely used in nuclear industry as cladding materials for BWRs and PWRs, respectively. Over more than 60 years these materials displayed a very good combination of properties such as low neutron absorption, creep behavior, stress-corrosion cracking resistance, reduced hydrogen uptake, corrosion, and/or oxidation, especially in the case of Zircaloy-4. However, over the last couple of years energetic efforts were undertaken to improve their oxidation resistance during off-normal temperature excursions, as well as to further improve upon the already achieved levels of mechanical behavior and reduced hydrogen uptake. In order to facilitate the development of such novel materials, it is very important to achieve not only engineering control, but also scientific understanding of the underlying material degradation mechanisms, both in working conditions and in storage of spent nuclear fuel. This paper strives to contribute to these efforts by constructing the thermodynamic models of both alloys, constructing of the respective phase diagrams, and oxidation mechanisms. A special emphasis was placed upon the role of zirconium suboxides in hydrogen uptake reduction and the atomic mechanisms of oxidation. To that end, computational thermodynamics calculations were conducted concurrently with first-principles atomistic modeling.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermodynamic assessment of the U–La–O system

The CALPHAD methodology was used to develop a thermodynamic assessment of the U-La-O system. The solid solution and liquid phases are described with the compound energy formalism and the partially ionic two-sublattice liquid model respectively. A density functional theory (DFT) calculation for the lattice stability of the fictive lanthanum oxide fluorite structure compound is used to determine the Gibbs energies for the La containing end-members in the CEF model for U 1-y La y O 2+x . Experimental thermodynamic and phase equilibria data were then used in optimizations to develop representations of the phases in the system that can be extended to include other actinide and fission products to develop multi-component models. The models that comprise this assessment very well reproduce experimentally determined oxygen potentials and the observed phase relations for the U-La-O system.

36 MATERIALS SCIENCE↗

The effect of Mn/Ni on thermodynamic properties of critical nucleus in Fe-Cu-Mn (Ni) ternary alloys

The aging- or radiation-induced hardening of Cu/Mn/Ni precipitates in Fe alloys is one of property degradation mechanisms in structural materials in nuclear reactors. Experiments show that aging or radiation leads the formation of Cu-rich precipitates, and the addition of Mn or Ni elements enhances the precipitation kinetics. In this study, the phase-field model coupled with the constrained string method have been applied to investigate the thermodynamic properties of critical nuclei such as the minimum energy path of Cu/Mn/Ni precipitation in Fe-Cu-Mn and Fe-Cu-Ni ternary alloys. The chemical free energies used in the model are taken from CALPHAD. The simulation results show that the formation of Cu/Mn/Ni clusters needs to overcome an energy barrier, and the precipitate has a Core-Shell structure. The thermodynamic properties of the critical nucleus are influenced by temperature and Cu/Mn/Ni overall concentrations, which are in accordance with the simulation results as well as the experimental observations.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Synthesis and thermodynamics of uranium-incorporated α-Fe 2 O 3 nanoparticles

Hematite nanoparticles were synthesized with U(VI) in circumneutral water through a coprecipitation and hydrothermal treatment process. XRD, TEM, and EXAFS analyses reveal that uranium may aggregate along grain boundaries and occupy Fe sites within hematite. The described synthesis method produces crystalline, single-phase iron oxide nanoparticles absent of surface-bound uranyl complexes. EXAFS data were comparable to spectra from existing studies whose syntheses were more representative of naturally occurring, extended aging processes. Herein this work provides and validates an accelerated method of synthesizing uranium-immobilized iron oxide nanoparticles for further mechanistic studies. High temperature oxide melt solution calorimetry measurements were performed to calculate the thermodynamic stability of uranium-incorporated iron oxide nanoparticles. Increasing uranium content within hematite resulted in more positive formation enthalpies. Standard formation enthalpies of U x Fe 2–2x O 3 were as high as 76.88 ± 2.83 kJ/mol relative to their binary oxides, or -764.04 ± 3.74 kJ/mol relative to their constituent elements, at x = 0.037. Data on the thermodynamic stability of uranium retention pathways may assist in predicting waste uranyl remobilization, as well as in developing more effective methods to retain uranium captured from aqueous environments.

36 MATERIALS SCIENCE↗

Ab initio modeling and thermodynamics of hydrated plutonium oxalates

An ab initio study on the plutonium oxalate hydrates: Pu 2 (C 2 O 4 ) 3 ·10H 2 O and Pu(C 2 O 4 ) 2 ·6H 2 O, using PBE exchange-correlation with D3 dispersion correction and Hubbard correction for the plutonium atoms, was performed and compared to experimental vibrational spectral and thermodynamic property values. Here we demonstrated that this technique can accurately predict the experimental infrared spectra Pu(III) oxalate hydrate, as well as the Raman peak of PuO 2 (used to calculate the thermodynamic properties of the oxalates). For Pu(IV) oxalate hydrate we found that our predicted structure agreed qualitatively with PXRD measurements, the only available experimental determination of the structure. Using this method at standard temperature and pressure, we predicted standard enthalpies of formation of -6,755 kJ mol -1 and -3,923 kJ mol -1 and standard Gibbs free energy of formation of -5,899 kJ mol -1 and -3,386 kJ mol -1 for Pu 2 (C 2 O 4 ) 3 ·10H 2 O and Pu(C 2 O 4 ) 2 ·6H 2 O, respectively.

36 MATERIALS SCIENCE↗

Experimental determination and thermodynamic modeling of the Ni-Re binary system

The phase diagram of the Ni-Re binary system has been partially reinvestigated by chemical, structural and thermal characterization of the arc melted alloys. The experimental results obtained during the present investigation were combined with the literature data and a new phase diagram of the Ni-Re binary system is proposed. In comparison with the Ni-Re phase diagram proposed by Nash et al. in 1985 [1], significant differences in the homogeneity domains, freezing ranges and peritectic reaction temperature were evidenced. On the other hand, thermodynamic modeling of the studied system by using the new experimental information has also been carried out with the help of the CALPHAD method. The calculated Ni-Re phase diagram showed a good agreement with the selected experimental information. - Graphical abstract: Ni-Re phase diagram according to the present study. Highlights: Black-Right-Pointing-Pointer Re-investigation of the Ni-Re phase diagram. Black-Right-Pointing-Pointer Extended phase field of the hcp phase. Black-Right-Pointing-Pointer Different freezing ranges and peritectic reaction temperature. Black-Right-Pointing-Pointer Thermodynamic modeling of the studied system by using the CALPHAD method.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomistic calculations of the thermodynamic properties of mixing for tetravalent metal dioxide solid solutions: (Zr, Th, Ce)O{sub 2}

The thermodynamic mixing properties for isometric Th{sub x}Ce{sub 1-x}O{sub 2}, Ce{sub x}Zr{sub 1-x}O{sub 2}, and Th{sub x}Zr{sub 1-x}O{sub 2} were determined using quantum-mechanical calculations and subsequent Monte-Carlo simulations. Although the Th{sub x}Ce{sub 1-x}O{sub 2} binary indicates exsolution below 600 K, the energy gain due to exsolution is small (E{sub exsoln}=1.5 kJ/(mol cations) at 200 K). The energy gain for exsolution is significant for the binaries containing Zr; at 1000 K, E{sub exsoln}=6 kJ/(mol cations) for the Ce{sub x}Zr{sub 1-x}O{sub 2} binary, and E{sub exsoln}=17 kJ/(mol cations) for the Th{sub x}Zr{sub 1-x}O{sub 2} binary. The binaries containing Zr have limited miscibility and cation ordering (at 200 K for x=0.5). At 1673 K, only 4.0 and 0.25 mol% ZrO{sub 2} can be incorporated into CeO{sub 2} and ThO{sub 2}, respectively. Solid-solution calculations for the tetragonal Th{sub x}Zr{sub 1-x}O{sub 2} binary show decreased mixing enthalpy due to the increased end-member stability of tetragonal ZrO{sub 2}. Inclusion of the monoclinic ZrO{sub 2} is predicted to further reduce the mixing enthalpy for binaries containing Zr. - Graphical abstract: Temperature-composition phase diagram showing miscibility gaps for the isometric Th{sub x}Ce{sub 1-x}O{sub 2}, isometric Ce{sub x}Zr{sub 1-x}O{sub 2}, isometric Th{sub x}Zr{sub 1-x}O{sub 2}, and tetragonal Th{sub x}Zr{sub 1-x}O{sub 2} binaries at low composition (0<x<0.025), where the solid solidus is an average of the linear and Margules approximations for the incorporation limit (x{sub inc}), and the dotted solidus lines are the Margules approximation (above the average) and the linear approximation (below the average). Highlights: Black-Right-Pointing-Pointer {Delta}H{sub mix}, {Delta}G{sub mix}, and {Delta}S{sub mix} of Th{sub x}Ce{sub 1-x}O{sub 2}, Th{sub x}Zr{sub 1-x}O{sub 2}, and Ce{sub x}Zr{sub 1-x}O{sub 2} binaries are calculated. Black-Right-Pointing-Pointer Cation ordering is identified at low T for binaries containing ZrO{sub 2}. Black-Right-Pointing-Pointer Phase diagrams are estimated based on DFT and Monte-Carlo calculations. Black-Right-Pointing-Pointer DFT and Monte-Carlo calculations are in agreement with experimental (and previous computational) results, where available. Black-Right-Pointing-Pointer Increased thermodynamic stability of monoclinic and tetragonal ZrO{sub 2} end-member affects solid solution binaries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermodynamic stability of elemental boron allotropes with varying numbers of interstitial atoms

Elemental boron exists in multiple allotropes, each characterized by structures containing icosahedral subunits. These structures have interstitial sites between the icosahedral subunits that are partially occupied. The number of atoms in the unit cell varies depending on the occupancy of these interstitial sites. Here we have investigated the thermodynamic stability of boron allotropes for different numbers of atoms in the unit cell by calculating the free energies, including the contribution of phonons. It has been found that β-rhombohedral boron is most stable with 107 atoms/cell at low temperatures, while it becomes most stable with 105 atoms/cell above 1700 K. This suggests the occurrence of a phase transition at this temperature, which could account for the large variation in the number of atoms in the unit cell for β-rhombohedral boron samples. α-tetragonal boron is consistently most stable with 52 atom/cell and becomes unstable with more than 52 atoms/cell. Similar to β-rhombohedral boron, β-tetragonal boron may undergo a phase transition between 192 and 190 atoms/cell configurations. However, the thermodynamic stability of pure β-tetragonal boron has been questioned in comparison with other allotropes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and characterization of bulk Cu{sub 2}ZnSnX{sub 4} (X: S, Se) via thermodynamically supported mechano-chemical process

Materials with the general formula, Cu{sub 2}ZnSnX{sub 4} (CZTX; X: Group 16 elements), with X being S/Se, have been receiving considerable attention due to their utility as an absorber layer in solar photovoltaics (PV). This paper reports on the synthesis of CZTSe and CZTS nanocrystalline powders at low temperatures, starting from elemental metal and chalcogen powders, via the low cost, scalable technique of ball milling. The prepared samples were well characterized using the different characterization tools. XRD, Raman, SEM and TEM studies confirm the formation of single-phase, stoichiometric, nano-crystalline kesterite CZTS and CZTSe powders. The low temperature phase selection of the complex quaternary compound in this system is seen as a direct consequence of the thermodynamic facilitation, coupled with the capability of mechano-chemical synthesis to aid in overcoming kinetic constraints. The optical bandgap of the various samples of CZTS was observed in the range of 1.4–1.6 eV and corresponding values for CZTSe was observed to be in the range of 1.08–1.18 eV. Our work provides a pathway for developing cheap, scalable, and ink-based techniques for low cost solar PV. - Graphical abstract: Display Omitted - Highlights: • A scalable route for synthesis of near phase pure CZTS/Se nano-crystals has been demonstrated. • Stoichiometric CZTS and CZTSe were synthesized via mechano-chemical synthesis route. • Synthesis at near room temperature is supported by thermodynamic calculations.

36 MATERIALS SCIENCE↗

Thermodynamic constitutive model for load-biased thermal cycling test of shape memory alloy

Graphical abstract: - Highlights: • Thermodynamic calculation model for martensitic transformation of shape memory alloy was proposed. • Evolution of the self-accommodation was considered independently by a rate-dependent kinetic equation. • Finite element calculation was conducted for B2–B19′ transformation of Ti–44.5Ni–5Cu–0.5 V (at.%). • Three-dimensional numerical results predict the macroscopic strain under bias loading accurately. - Abstract: This paper presents a three-dimensional calculation model for martensitic phase transformation of shape memory alloy. Constitutive model based on thermodynamic theory was provided. The average behavior was accounted for by considering the volume fraction of each martensitic variant in the material. Evolution of the volume fraction of each variant was determined by a rate-dependent kinetic equation. We assumed that nucleation rate is faster for the self-accommodation than for the stress-induced variants. Three-dimensional finite element analysis was conducted and the results were compared with the experimental data of Ti–44.5Ni–5Cu–0.5 V (at.%) alloy under bias loading.

36 MATERIALS SCIENCE↗

Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: Thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance

Graphical abstract: In this research nanostructured CeAPSO-34 was synthesized to explore the effect of TEAOH and morpholine on its physiochemical properties and MTO performance. Prepared catalysts were characterized with XRD, FESEM, BET, FTIR and NH3-TPD techniques. The results indicated that the nature of the template determines the physiochemical properties of CeAPSO-34 due to different rate of crystal growth. The catalyst obtained by using morpholine showed longer life time as well as sustaining light olefins selectivity at higher values. Furthermore, a comprehensive thermodynamic analysis of overall reactions network was carried out to address the major channels of methanol to olefins conversion. - Highlights: • Introduction of Ce into SAPO-34 framework. • Comparison of CeAPSO-34 synthesized using morpholine and TEAOH. • The nature of the template determines the physiochemical properties of CeAPSO-34. • Morpholine enhances catalyst lifetime in MTO process. • Presenting a complete reaction network for MTO process. - Abstract: TEAOH and morpholine were employed in synthesis of nanostructured CeAPSO-34 molecular sieve and used in methanol to olefins conversion. Prepared samples were characterized by XRD, FESEM, EDX, BET, FTIR and NH{sub 3}-TPD techniques. XRD patterns reflected the higher crystallinity of the catalyst synthesized with morpholine. The FESEM results indicated that the nature of the template determines the morphology of nanostructured CeAPSO-34 due to different rate of crystal growth. There was a meaningful difference in the strength of both strong and weak acid sites for CeAPSO-34 catalysts synthesized with TEAOH and morpholine templates. The catalyst synthesized with morpholine showed higher desorption temperature of both weak and strong acid sites evidenced by NH{sub 3}-TPD characterization. The catalyst obtained using morpholine template had the longer lifetime and sustained desired light olefins at higher values. A comprehensive thermodynamic analysis of overall reactions network was carried out to address the major channels of methanol to olefins conversion.

36 MATERIALS SCIENCE↗

Thermodynamic origin of nonvolatility in resistive memory

Electronic switches based on the migration of high-density point defects, or memristors, are poised to revolutionize post-digital electronics. Despite significant research, key mechanisms for filament formation and oxygen transport remain unresolved, hindering our ability to predict and design device properties. For example, experiments have achieved 10 orders of magnitude longer retention times than predicted by current models. Here, using electrical measurements, scanning probe microscopy, and first-principles calculations on tantalum oxide memristors, we reveal that the formation and stability of conductive filaments crucially depend on the thermodynamic stability of the amorphous oxygen-rich and oxygen-poor compounds, which undergo composition phase separation. Including the previously neglected effects of this amorphous phase separation reconciles unexplained discrepancies in retention and enables predictive design of key performance indicators such as retention stability. Furthermore, this result emphasizes non-ideal thermodynamic interactions as key design criteria in post-digital devices with defect densities substantially exceeding those of today’s covalent semiconductors.

36 MATERIALS SCIENCE↗

Influence of concentration polarization and thermodynamic non-ideality on salt transport in reverse osmosis membranes

The classic Merten and Lonsdale transport model for reverse osmosis membranes was reformulated to explicitly demonstrate the effects of concentration polarization and solution phase thermodynamic non-idealities on salt transport. A framework presented here accounts for the concentration dependence of ion activity coefficients in salt solutions, which was not explicitly included in the classic model. This approach was applied to four salt solutions, NaCl, MgCl 2 , CaCl 2 , and Na 2 SO 4 , tested in cross-flow conditions for a commercial RO membrane, Dow Filmtec™ BW30XFR. Salt transport coefficients corrected for concentration polarization and non-ideal thermodynamic effects, B a , were calculated as a function of permeate flux and compared with apparent salt transport coefficients, B . Finally, these corrections were significant, resulting in B a values greater than B values by a factor of 1.3–2.1 for 2:1 and 1:2 salts (i.e., MgCl 2 , CaCl 2 , and Na 2 SO 4 ). B a values for NaCl (a 1:1 salt), however, were similar to or somewhat smaller than B values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermodynamic investigation of the NaCl-KCl salt system from 25 to 950 °C

NaCl-KCl molten salt system has been proposed as a primary component of several promising heat transfer eutectics and fuel host for Generation IV molten salt reactors (MSR). In this work, several key thermodynamic parameters, including high temperature enthalpies, isobaric heat capacities (C p ) and molar enthalpies of mixing (ΔH mix ), of the NaCl -KCl system (NaCl, 75mol% NaCl – 25mol% KCl, 51mol% NaCl – 49mol% KCl, 25mol% NaCl – 75mol% KCl, and KCl) were measured by high temperature drop calorimetry (HTDC) utilizing laser sealed nickel and aluminum crucibles. Salts were checked for phase purity by X-ray diffraction (XRD), and water content by Karl Fischer coulometric titrimetry and thermogravimetric analysis (TGA). Thermo-mechanical analysis (TMA) utilizing custom-built boron nitride (BN) crucibles was employed to determine temperatures of phase transitions (solid $\rightarrow$ liquid) for the salts and plotted against the pseudobinary phase diagram for the NaCl-KCl system. Small deviations (3-10 %) were found among C p values obtained from HTDC, differential scanning calorimetry (DSC), and NIST, comparable to the average uncertainty based on two standard deviations of measured data that are ~6% for DSC and ~3% for HTDC. Additionally, the measured enthalpies and C p values of mixed NaCl-KCl salts (e.g., 51mol% NaCl – 49mol% KCl eutectic) were shown to behave as statistical mixtures of its pure endmembers, consistent with ΔH mix = ~ 0 kJ/mol at 800 °C, and a regular interaction parameter of Ω = 1.20 ± 0.76 kJ/mol. In conclusion, this study represents a step towards improved accuracy and precision in determinations of thermodynamic parameters of molten salts by using DSC, TMA, and HTDC, in completion of the Molten Salt Thermal Properties Database (MSTDB).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗