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At least 217 records · Page 12

Machine-learning and first-principles investigation of lightweight medium-entropy alloys for hydrogen-storage applications

The transition to a low-carbon economy demands efficient and sustainable energy-storage solutions, with hydrogen emerging as a promising clean-energy carrier and with metal hydrides recognized for their hydrogen-storage capacity. Here, we leverage machine learning (ML) to predict hydrogen-to-metal (H/M) ratios and solution energy by incorporating thermodynamic parameters and local lattice distortion (LLD) as key features. Our best-performing ML model provides improvements to H/M ratios and solution energies over a broad class of medium-entripy alloys (easily extendable to multi-principal-element alloys), such as Ti–Nb-X (X = Mo, Cr, Hf, Ta, V, Zr) and Co–Ni-X (X = Al, Mg, V). Ti–Nb–Mo alloys reveal compositional effects in H-storage behavior, in particular Ti, Nb, and V enhance H-storage capacity, while Mo reduces H/M and hydrogen weight percent by 40–50 %. We attributed results in molybdenum-rich alloys to slow hydrogen kinetics, as validated by our pressure-composition-temperature (PCT) isotherm experiments on pure Ti and Ti 5 Mo 95 alloys. Density functional theory (DFT) and molecular dynamics (MD) simulations also confirm that Ti and Nb promote H diffusion, whereas Mo hinders it, highlighting the interplay between electronic structure, lattice distortions, and hydrogen uptake. Notably, our Gradient Boosting Regression model identifies LLD as a critical factor in H/M predictions. Here, to aid material selection, we present two periodic tables illustrating elemental effects on (a) H 2 wt% and (b) solution energy, derived from ML, and provide a reference for identifying alloying elements that enhance hydrogen solubility and storage.

08 HYDROGEN↗

Predictive Simulation of Gas Adsorption in Fixed-Beds and Limitations due to the Ill-Posed Danckwerts Boundary Condition

The 1-D axially dispersed plug flow model is a mathematical model widely used for the simulation of adsorption processes. Lumped mass transfer coefficients such as the Glueckauf linear driving force (LDF) term and the axial dispersion coefficient are generally obtained by fitting simulation results to the experimental breakthrough test data. An approach is introduced where these parameters, along with the only free parameter in the energy balance equations, are individually fit to specific test data that isolates the appropriate physics. It is shown that with this approach this model provides excellent simulation results for the C02 on zeolite SA sorbent/sorbate system; however, for the H20 on zeolite SA system, non-physical deviations from constant pattern behavior occur when fitting dispersive experimental results with a large axial dispersion coefficient. A method has also been developed that determines a priori what values of the LDF and axial dispersion terms will result in non-physical simulation results for a specific sorbent/sorbate system when using the one-dimensional axially dispersed plug flow model. A relationship between the steepness of the adsorption equilibrium isotherm as indicated by the distribution factor, the magnitude of the axial dispersion and mass transfer coefficient, and the resulting non-physical behavior is derived. This relationship is intended to provide a guide for avoiding non-physical behavior by limiting the magnitude of the axial dispersion term on the basis of the mass transfer coefficient and distribution factor.

Knox, James Clinton↗

Pore characterization of the Marcellus Shale by nitrogen adsorption and prediction of its gas storage capacity

In a shale gas reservoir, pore characterization is an important factor used to determine gas storage capacity. However, the nanometer (nm)-scale pore system in shale is difficult to explore by traditional optical, scanning electron microscopy, or even nuclear magnetic resonance well logging. We have investigated the pore structure and storage capacity of the Marcellus Shale through integration of petrophysical analysis from laboratory and well-logging data and nitrogen adsorption. The isotherm of Marcellus Shale is a composite isotherm, which has features of type I, type II, and type IV isotherms with type H4 of the hysteresis loop, suggesting slit-like pores developed in the Marcellus Shale. Quantitative analysis of pore volumes from the nitrogen adsorption indicates that density porosity may be more properly used to approximate the shale porosity and estimate the shale gas volume. In addition, the specific surface area, micropore, and mesopore volumes have a positive relationship with the kerogen volume and total organic content (TOC). By using the Langmuir and Brunauer-Emmet-Teller models, the simulated result indicates that the higher adsorbed quantity of the Marcellus Shale could be the result of the increase of micropore volume contributed, by the increase of kerogen or TOC content. The proposed equations rapidly compute TOC, a key parameter to predict gas storage capacity in overmature shale such as the Marcellus Shale.

Geochemistry & Geophysics↗

Heat Transfer on a Film-Cooled Rotating Blade

A multi-block, three-dimensional Navier-Stokes code has been used to compute heat transfer coefficient on the blade, hub and shroud for a rotating high-pressure turbine blade with 172 film-cooling holes in eight rows. Film cooling effectiveness is also computed on the adiabatic blade. Wilcox's k-omega model is used for modeling the turbulence. Of the eight rows of holes, three are staggered on the shower-head with compound-angled holes. With so many holes on the blade it was somewhat of a challenge to get a good quality grid on and around the blade and in the tip clearance region. The final multi-block grid consists of 4784 elementary blocks which were merged into 276 super blocks. The viscous grid has over 2.2 million cells. Each hole exit, in its true oval shape, has 80 cells within it so that coolant velocity, temperature, k and omega distributions can be specified at these hole exits. It is found that for the given parameters, heat transfer coefficient on the cooled, isothermal blade is highest in the leading edge region and in the tip region. Also, the effectiveness over the cooled, adiabatic blade is the lowest in these regions. Results for an uncooled blade are also shown, providing a direct comparison with those for the cooled blade. Also, the heat transfer coefficient is much higher on the shroud as compared to that on the hub for both the cooled and the uncooled cases.

Garg, Vijay K.↗

Reactor physics benchmark experiments at the JSI TRIGA MARK II reactor - Current status and future outlook

Full text of publication follows. With the development of new high-fidelity computational methods, improvement of nuclear data, and multiphysics modelling, there is an increased need for benchmark experiments to experimentally validate the models, methods and input data. Many of the nuclear facilities designed to perform reactor physics benchmark experiments have been shut down. Therefore, research reactors offer a great opportunity for benchmark experiments, if they are well designed and performed with great care and accuracy. In this presentation we provide an overview of the past and ongoing activities related to benchmark experiments at the Jozef Stefan Institute TRIGA Mark II research reactor. The following experiments have been performed: criticality with fresh fuel, {sup 197}Au(n,γ) and {sup 27}Al(n,α) reaction rates in irradiation channels, absolute and relative {sup 197}Au(n,γ), {sup 235}U(n,f) and {sup 238}U(n,f) reaction rates in the core, burnup, kinetic parameters, control rod worth, isothermal reactivity coefficient, self-shielding, slow and fast (pulse) transients, nuclear heating, delayed and prompt gamma ray production, temperature profiles for multi-physics. Since the existing fleet of research reactors is ageing very rapidly and new experiments are needed, new research reactors should be designed and built to meet the needs of future advanced reactors, education and training, and other technologies in the coming years. We will review planned activities at the JSI TRIGA reactors and plans for the new research reactor in Slovenia. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Interfacial Force Field Characterization in a Constrained Vapor Bubble Thermosyphon

Isothermal profiles of the extended meniscus in a quartz cuvette were measured in the earth's gravitational field using an image-analyzing interferometer that is based on computer-enhanced video microscopy of the naturally occurring interference fringes. These profiles are a function of the stress field. Experimentally, the augmented Young-Laplace equation is an excellent model for the force field at the solid-liquid-vapor interfaces for heptane and pentane menisci on quartz and tetradecane on SFL6. The effects of refractive indices of the solid and liquid on the measurement techniques were demonstrated. Experimentally obtained values of the disjoining pressure and dispersion constants were compared to those predicted from the Dzyaloshinskii - Lifshitz - Pilaevskii theory for an ideal surface and reasonable agreements were obtained. A parameter introduced gives a quantitative measurement of the closeness of the system to equilibrium. The nonequilibrium behavior of this parameter is also presented

DasGupta, Sunando↗

Analytical-based simulation approach for an anion exchange membrane fuel cell

An analytical and empirical-based 1-D, non-isothermal, steady-state model for anion exchange membrane fuel cell capable of capturing two-phase phenomena is presented in this study. Coupled multi-physics including mass and charge transport, electrochemical reactions, heat transfer, and two-phase water transport are considered in the model and the simulated results are compared to experimental data. To better represent actual material properties and localized conditions, the model applies multilayer discretization in the gas diffusion electrode to enhance prediction accuracy. The model successfully predicts the baseline performance at 70 °C, 131 kPa abs., 92% RH with pure H 2 /O 2 gas as well as the limiting current at 10% H 2 . The robust simulation approach allows for simplistic and accurate estimation of cell performance without the complications of applying two-phase parameters and expensive computational need for numerical models. In addition, the results from the sensitivity studies of material properties and operating conditions provide valuable insights on water management strategies and optimal component design for advancing anion exchange membrane fuel cell technology.

1-D model↗

Magnetic structure, excitations and short-range order in honeycomb Na 2 Ni 2 TeO 6

Na 2 Ni 2 TeO 6 has a layered hexagonal structure with a honeycomb lattice constituted by Ni 2+ and a chiral charge distribution of Na + that resides between the Ni layers. In the present work, the antiferromagnetic transition temperature of Na 2 Ni 2 TeO 6 is confirmed at TN˜ 27 K, and further, it is found to be robust up to 8 T magnetic field and 1.2 GPa external pressure; and, without any frequency-dependence. Slight deviations from nominal Na-content (up to 5%) does not seem to influence the magnetic transition temperature, TN. Isothermal magnetization curves remain almost linear up to 13 T. Our analysis of neutron diffraction data shows that the magnetic structure of Na 2 Ni 2 TeO 6 is faithfully described by a model consisting of two phases described by the commensurate wave vectors vec kc, (0.5 0 0) and (0.5 0 0.5), with an additional short-range order component incorporated in to the latter phase. Consequently, a zig-zag long-range ordered magnetic phase of Ni 2+ results in the compound, mixed with a short-range ordered phase, which is supported by our specific heat data. Theoretical computations based on density functional theory (DFT) predict predominantly in-plane magnetic exchange interactions that conform to a J1-J2-J3 model with a strong J3 term. The computationally predicted parameters lead to a reliable estimate for TN and the experimentally observed zig-zag magnetic structure. A spin wave excitation in Na 2 Ni 2 TeO 6 at E ˜ 5 meV at T = 5 K is mapped out through inelastic neutron scattering experiments, which is reproduced by linear spin wave theory calculations using the J values from our computations. Our specific heat data and inelastic neutron scattering data strongly indicate the presence of short-range spin correlations, at T > TN, stemming from incipient antiferromagnetic clusters.

36 MATERIALS SCIENCE↗

Sensitivity analysis for the dynamic response of viscoplastic shells of revolution

A computational procedure is presented for evaluating the sensitivity coefficients of the dynamic axisymmetric response of viscoplastic shells of revolution. The analytical formulation is based on Reissner's large deformation shell theory with the effects of transverse shear deformation, rotatory inertia and moments turning around the normal to the middle surface included. The material model is chosen to be isothermal viscoplasticity, and an associated flow rule is used with a von Mises effective stress. A mixed formulation is used with the fundamental unknowns consisting of six stress resultants, three generalized displacements and three velocity components. Spatial discretization is performed using finite elements, with discontinuous stress resultants across element interfaces. The temporal integration is performed by using an explicit central difference scheme (leap-frog method) with an implicit constitutive update. The sensitivity coefficients are evaluated using a direct differentiation approach. Numerical results are presented for a spherical cap subjected to step loading, and a circular plate subjected to impulsive loading. The sensitivity coefficients are generated by evaluating the derivatives of the response quantities with respect to thickness, mass density, Young's modulus, and two of the material parameters characterizing the viscoplastic response. Time histories of the response and sensitivity coefficients are presented, along with spatial distributions of these quantities at selected times.

Kulkarni, Makarand↗

Self-regulating galaxy formation. I - H II disk and Lyman-alpha pressure

The nascent interstellar medium and star formation model are incorporated into a scenario for the formation epoch of spiral galaxies. The structure, star formation time scale, and luminosity of a self-gravitating isothermal disk are evaluated as functions of the disk surface density. The importance of radiation pressure, particularly that of Lyman-alpha, in maintaining an inflated disk and halting infall is discussed. The Lyman-alpha pressure also supports a considerable halo of material in the vicinity of the disk. A first-order infall scenario and the time-dependent properties of the system it constructs are presented. Disk properties are evaluated at the epoch at which further material is supportable against infall by Lyman-alpha pressure. The two-dimensional family of disk galaxies whose scales and surface density are expressible in terms of fundamental constants and which arise from the three parameter sets of perturbations in the Hubble flow are determined.

Cox, D. P.↗

Two dimensional topology optimization of heat exchangers with the volume fraction method

We perform a comparison study of two topology optimizations methods applied to the design of a two fluids heat exchanger modeled with a coupled thermal-flow problem. The flow follows an isothermal and incompressible Stokes-Brinkman equation and the heat transfer is governed by a convection-diffusion equation without internal generation and high Peclet number. To keep the two fluid phases separated, we solve two Stokes-Brinkman equations, where the Brinkman term models the other phase as a solid. These two velocity fields are then fed to the heat transfer equation. Our goal is to maximize the enthalpy at the cold outlet while constraining the pressure drop. We first solve the design modeling the solid and fluid phases with a volume fraction variable. A SIMP-like penalization in the Brinkman term drives the optimization to a discrete design. The cost and constraint function derivatives are calculated with the library pyadjoint and the optimization is performed by IPOPT. We present optimized designs in two dimensions and discuss the influence of the parameters.

Beck, VictorA.↗

Modeling glass degradation and release of radionuclides from vitrified waste for performance assessment simulations

The release of radionuclides initially encapsulated in a slowly degrading solid waste form and contained in an eventually corroding canister defines the source term for numerical simulations for the assessment of a geologic repository for high-level radioactive waste. While the details of waste degradation, canister corrosion, and dissolution and mobilization of the radionuclides in pore water include complex chemical reaction and transport processes that are coupled to the thermal, hydrological, microbiological, and mechanical conditions in the repository, the source-term model suitable for use in a numerical performance assessment model should be a defensible abstraction of these mechanisms. We developed a radiological source-term model and implemented it into a non-isothermal flow and transport simulator. While the proposed source-term model is applicable to various waste forms, canister systems, and disposal concepts, we specifically considered radionuclide releases from vitrified high-level waste placed in a cylindrical canister disposed in a deep vertical borehole repository. In this model, waste degradation is a function of temperature, and it can be adjusted to evaluate the influence of and propagate uncertainties in pH, passivation reactions, and chemical conditions as well as geometrical factors. The time-dependent, congruent release of safety-relevant radionuclides present in the decaying inventory is then calculated. Finally, the radionuclides are mobilized by diffusive and advective transport according to the thermo-hydraulic conditions prevailing in the near field of the repository, from where they migrate through the geosphere to the accessible environment. We examine the influence of the source-term model’s parameters on performance assessment calculations through sensitivity and uncertainty propagation analyses, identifying influential factors and confirming the upper bound of their impact. These considerations align with the overarching goal of repository design, which is to demonstrate that engineered and natural barriers can collectively delay radionuclide migration for timescales far exceeding human planning, thereby providing multiple, redundant barriers against environmental contamination.

iTOUGH2↗

Smaller than Expected Bright-spot Offsets in Spitzer Phase Curves of the Hot Jupiter Qatar-1b

We present Spitzer full-orbit thermal phase curves of the hot Jupiter Qatar-1b, a planet with the same equilibrium temperature—and intermediate surface gravity and orbital period—as the well-studied planets HD 209458b and WASP-43b. We measure secondary eclipse depths of 0.21 ± 0.02% at 3.6 μm and 0.30 ± 0.02% at 4.5 μm, corresponding to dayside brightness temperatures of 1542{sub −31}{sup +32} K and 1557{sub −36}{sup +35} K, respectively, consistent with a vertically isothermal dayside. The respective nightside brightness temperatures are 1117{sub −71}{sup +76} and 1167{sub −74}{sup +69} K, in line with a trend that hot Jupiters all have similar nightside temperatures. We infer a Bond albedo of 0.12{sub −0.16}{sup +0.14} and a moderate day–night heat recirculation efficiency, similar to HD 209458b. General circulation models for HD 209458b and WASP-43b predict that their bright spots should be shifted east of the substellar point by tens of degrees, and these predictions were previously confirmed with Spitzer full-orbit phase curve observations. The phase curves of Qatar-1b are likewise expected to exhibit eastward offsets. Instead, the observed phase curves are consistent with no offset: 11° ± 7° at 3.6 μm and −4° ± 7° at 4.5 μm. The discrepancy in circulation patterns between these three otherwise similar planets points to the importance of secondary parameters like rotation rate and surface gravity, and the presence or absence of clouds, in determining atmospheric conditions on hot Jupiters.

79 ASTRONOMY AND ASTROPHYSICS↗

On Study of Air/Space-borne Dual-Wavelength Radar for Estimates of Rain Profiles

In this study, a framework is discussed to apply air/space-borne dual-wavelength radar for the estimation of characteristic parameters of hydrometeors. The focus of our study is on the Global Precipitation Measurements (GPM) precipitation radar, a dual-wavelength radar that operates at Ku (13.8 GHz) and Ka (35 GHz) bands. As the droplet size distributions (DSD) of rain are expressed as the Gamma function, a procedure is described to derive the median volume diameter (D(sub 0)) and particle number concentration (N(sub T)) of rain. The correspondences of an important quantity of dual-wavelength radar, defined as deferential frequency ratio (DFR), to the D(sub 0) in the melting region are given as a function of the distance from the 0 C isotherm. A self-consistent iterative algorithm that shows a promising to account for rain attenuation of radar and infer the DSD without use of surface reference technique (SRT) is examined by applying it to the apparent radar reflectivity profiles simulated from the DSD model and then comparing the estimates with the model (true) results. For light to moderate rain the self-consistent rain profiling approach converges to unique and correct solutions only if the same shape factors of Gamma functions are used both to generate and retrieve the rain profiles, but does not converges to the true solutions if the DSD form is not chosen correctly. To further examine the dual-wavelength techniques, the self-consistent algorithm, along with forward and backward rain profiling algorithms, is then applied to the measurements taken from the 2nd generation Precipitation Radar (PR-2) built by Jet Propulsion Laboratory. It is found that rain profiles estimated from the forward and backward approaches are not sensitive to shape factor of DSD Gamma distribution, but the self-consistent method is.

Liao, Liang↗

Characterization of shale using Helium and Argon at high pressures

In order to estimate the shale gas in place and the eventual recovery during shale gas operations, one of the key requirements is to accurately characterize the shale’s petrophysical and transport properties such as porosity, permeability, diffusivity, and storage capacity. Despite the many efforts reported in the technical literature aiming to provide an improved understanding of the complex pore structures and the associated fluid flow in gas shales, complete characterization of organic-rich shale samples still poses a big challenge. Here, we have characterized mass transfer and sorption in shale at different length scales using Helium (He) and Argon (Ar) as probe gases. Thermogravimetric analysis (TGA) with a shale cube of ~1 cm 3 in size and gas expansion experiments with a full-diameter core (3.5” in diameter) were used to measure sorption kinetics/isotherms and mass transfer, respectively. Both samples are from the same depth/location in the Marcellus shale formation. The TGA steady-state technique was initially used to generate excess sorption isotherms for Ar, while dynamic TGA experiments were used to study its sorption kinetics. The TGA experiments demonstrate that Ar, which has a similar sorption potential as Methane, but is generally assumed to be inert, adsorbs onto the surfaces of the mesoporous and microporous regions of the shale samples according to a Langmuir-type behavior. Helium expansion experiments, on the full-diameter core, were used to measure the overall porosity, on the basis that He is a non-sorbing and inert gas as compared to Ar. The He expansion experiments, furthermore, allow us to delineate the mass transfer of gas across the inherent hierarchy of pore sizes, including macropores (macro- and microcracks), mesopores and micropores. Similar expansion experiments were also performed with Ar to study the combined impact of mass transfer and sorption. A triple-porosity model (TPM) was utilized to interpret the He expansion experiments with the shale core and to extract (estimate) relevant transport parameters. We report and compare here the diffusivities and permeabilities of the whole core for both He and Ar, as calculated from the modeling and fitting of the experimental data. On the premise that the shale cube is representative of the matrix region of the core, the Ar sorption kinetics from the cube experiments were subsequently combined with the transport parameters extracted from the He experiments to predict the behavior of the Ar expansion test with the full-diameter core. An excellent agreement is observed between the model predictions and the experimental data. The experimental observations and their interpretation indicate that one must be cautious when using Ar to estimate the true porosity and permeability of shales. In addition, we demonstrate that He and Ar probe gases, when used in tandem, can be employed effectively as a tool to characterize shales in terms of mass transfer and sorption dynamics across scales.

04 OIL SHALES AND TAR SANDS↗

A Deployable 4 Meter 180 to 680 GHz Antenna for the Scanning Microwave Limb Sounder

The Scanning Microwave Limb Sounder (SMLS) is a space-borne heterodyne radiometer which will measure pressure, temperature and atmospheric constituents from thermal emission between 180 and 680 GHz. SMLS, planned for the Global Atmospheric Composition Mission of the NRC Decadal Survey, uses a novel toric Cassegrain antenna to perform both elevation and azimuth scanning. These provide better horizontal and temporal resolution and coverage than were possible with elevation-only scanning at typical Low-Earth orbit spacing in the two previous MLS satellite instruments. Development of the SMLS antenna was the focus of a 2006 Small Business Innovative Research (SBIR) program whose phase II culminated in the fabrication and thermal stability testing of a composite demonstration model of the SMLS primary reflector. This reflector has the full 4m height and 1/3 the width planned for flight. An Instrument Incubator Program (IIP) titled "A deployable 4 Meter 180 to 680 GHz antenna for the Scanning Microwave Limb Sounder" continues development of the SMLS antenna with the study of 5 topics: 1) detailed mathematical modeling of the antenna patterns from which we simulate geophysical parameter retrievals in order to establish FOV performance requirements; 2) thorough correlation of finite element model predictions with measurements made on the SBIR reflector. We will again measure deformations of this reflector, under more flight-like thermal gradients, using higher precision metrology techniques available in a new large-aperture facility at JPL; 3) fabrication of a full-width primary reflector whose asbuilt surface figure will better meet the figure requirements of SMLS than did the SBIR reflector; 4) integration of the primary with other reflectors, and with residual front ends built in a 2007 IIP, in a breadboard antenna; and finally 5) RF testing of the breadboard on a Near Field Range at JPL. We report on significant progress in 3 areas of the current IIP: development of the mathematical model to predict SMLS antenna patterns and their application in a preliminary set of geophysical retrievals; the correlation between surface deformation predicted by finite element models and measurement in the 2009 isothermal stability tests of the SBIR, with implications for the thermal gradient testing to be performed at JPL; and aspects of the conceptual design of the full-width primary reflector to be fabricated and tested in the 2nd and 3rd years of the IIP.

heterodyne radiometer↗

Kinetic Model for the Reduction of Cu II Sites by NO + NH 3 and Reoxidation of NH 3 -Solvated Cu I Sites by O 2 and NO in Cu-SSZ-13

In this work, a kinetic model is developed for the reduction of Cu II sites by NO + NH 3 and the reoxidation of NH 3 -solvated Cu I sites by O 2 and NO in Cu-SSZ-13. Fourier transform infrared (FTIR) spectroscopy and spatially resolved capillary inlet mass spectrometry (SpaciMS) measurements during transient reactor experiments are utilized to identify the rate parameters associated with NO + NH 3 RHC (reduction half-cycle), proposed to occur via two distinct pathways involving adsorbed NH 3 and gas-phase NH 3 . The resulting NO + NH 3 RHC model is validated using spatiotemporal N 2 measurements covering a wide range of temperatures (200–450 °C) and space velocities (53,000–640,000 h –1 ). N 2 O formation is observed and modeled during NO + NH 3 RHC, with quantitative validation under standard selective catalytic reduction (SCR) conditions. Experimentally measured enthalpic and entropic changes associated with O 2 adsorption on NH 3 -solvated Cu I (ZCu(NH 3 ) 2 ) complexes [ Kamasamudram, K. Catal. Today 2010 , 151 (3–4), 212-222], along with activation energies estimated computationally for the intercage diffusion of ZCu(NH 3 ) 2 complexes [ Paolucci, C. Science 2017 , 357 (6 354), 898-903], are incorporated into a mean field kinetic model for the low-temperature oxidation half-cycle (OHC). Significant NH 3 release is observed during the isothermal oxidation of Cu I sites, attributed to desorption of NH 3 ligands from NH 3 -solvated Cu II dimers (Z 2 Cu 2 (NH 3 ) 4 O 2 ). Reduction of these dimeric complexes leads to the consumption of one NO/Cu II , contradicting the expected reduction stoichiometry. Inclusion of a global Arrhenius rate for the NO titration of Z 2 Cu 2 (NH 3 ) 4 O 2 complexes provides accurate representations of standard SCR on reduced and oxidized catalysts, predicting transient NO and NH 3 consumption between 150 and 250 °C as a function of hydrothermal aging. Deactivation of low-temperature standard SCR by NH 3 is observed at high NH 3 pressures, modeled via the formation of superoxo amino (ZCu(NH 3 ) 3 OO*) complexes during NH 3 titration of Z 2 Cu 2 (NH 3 ) 4 O 2 complexes [ Negri, C. J. Am. Chem. Soc. 2020 , 142 (37), 15884-15896]. The redox kinetic model presented here provides a foundational description of active site redox during low-temperature standard SCR, combining the recent kinetic, spectroscopic, and computational findings on the mechanism of standard SCR over Cu-SSZ-13.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A differential CDM model for fatigue of unidirectional metal matrix composites

A multiaxial, isothermal, continuum damage mechanics (CDM) model for fatigue of a unidirectional metal matrix composite volume element is presented. The model is phenomenological, stress based, and assumes a single scalar internal damage variable, the evolution of which is anisotropic. The development of the fatigue damage model, (i.e., evolutionary law) is based on the definition of an initially transversely isotropic fatigue limit surface, a static fracture surface, and a normalized stress amplitude function. The anisotropy of these surfaces and function, and therefore the model, is defined through physically meaningful invariants reflecting the local stress and material orientation. This transversely isotropic model is shown, when taken to it's isotropic limit, to directly simplify to a previously developed and validated isotropic fatigue continuum damage model. Results of a nondimensional parametric study illustrate (1) the flexibility of the present formulation in attempting to characterize a class of composite materials, and (2) the capability of the formulation in predicting anticipated qualitative trends in the fatigue behavior of unidirectional metal matrix composites. Also, specific material parameters representing an initial characterization of the composite system SiC/Ti 15-3 and the matrix material (Ti 15-3) are reported.

Arnold, S. M.↗