The decomposition of Fe-Cr solid solutions during thermal aging is modeled by Atomistic Kinetic Monte Carlo (AKMC) simulations, using a rigid lattice approximation with composition dependant pair interactions that can reproduce the change of sign of the mixing energy with the alloy composition. The interactions are fitted on ab initio mixing energies and on the experimental phase diagram, as well as on the migration barriers in iron and chromium rich phases. Simulated kinetics is compared with 3D atom probe and neutron scattering experiments.
Yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) with different microstructures were elaborated. The isothermal tetragonal to monoclinic transformation was investigated at 134 °C in steam by X-ray diffraction, Atomic Force Microscopy (AFM) and optical interferometry. The aging kinetics were analyzed in terms of nucleation and growth, using the Mehl-Avrami-Johnson (MAJ) formalism. Numerical simulation of the aging of zirconia surfaces was also conducted, and the results were used to better fit the aging kinetics. The simulation shows that the exponent of the MAJ laws is controlled no…
The process of natural aging in pure ternary Al-Mg-Si alloys was studied by positron annihilation lifetime spectroscopy in real time in order to clarify the sequence and kinetics of clustering and precipitation. It was found that natural aging takes place in at least five stages in these alloys, four of which were directly observed. This is interpreted as the result of complex interactions between vacancies and solute atoms or clusters. One of the early stages of positron lifetime evolution coincides with a clustering process observed by differential scanning calorimetry (DSC) and involves the…
Using methods of statistical kinetic theory parametrized with first-principles interatomic interactions that include chemical and strain contributions, we investigated the kinetics of decomposition and microstructure formation in Al-Cu alloys as a function of temperature and alloy concentration. We show that the decomposition of the solid solution forming platelets of copper, known as Guinier-Preston (GP) zones, includes several stages and that the transition from GP1 to GP2 zones is determined mainly by kinetic factors. With increasing temperature, the model predicts a gradual transition from…
The evolution of the aging process of glassy materials quenched from temperatures above their glass transition temperature $T_g$, when plotting the relaxed enthalpy versus the decrease in volume, leads to a slope comparable to the isothermal compressibility close to $T_g$. This empirical result was explained in an earlier publication (V. Katsika-Tsigourakou, G. E. Zardas J. Non-Cryst. Solids 356 (2010) 179-180) by means of a thermodynamical model. Here, we show that the same model enables the explanation of the rare cases of negative defect activation in solids.
Coarse-Grained Molecular Dynamics Simulations of Oxidative Aging and Stabilization in Polymer Melts with Primary Antioxidants: Effects of Antioxidant Concentration and Molecular Architecture
Nagoya University（名古屋大学）；Arts et Metiers Institute of Technology, CNRS Cnam, HESAM Universite（巴黎国立高等工艺学院，法国国家科学研究中心，Cnam，HESAM大学）
The Pauli kinetic energy enhancement factor $α=(τ-τ^W)/τ^{unif}$ is an important density ingredient, used to construct many meta-generalized gradient approximations (meta-GGA) exchange-correlation (XC) energy functionals, including the very successful strongly constrained and appropriately normed (SCAN) semilocal functional. Another meta-GGA functional, known as MGGAC [Phys. Rev. B 100, 155140 (2019)], is also proposed in recent time depending only on the $α$ ingredient and based on the generalization of the Becke-Roussel approach with the cuspless hydrogen exchange hole density. The MGGAC fun…
Kinetic energy (KE) approximations are key elements in orbital-free density functional theory. To date, the use of non-local functionals, possibly employing system dependent parameters, has been considered mandatory in order to obtain satisfactory accuracy for different solid-state systems, whereas semilocal approximations are generally regarded as unfit to this aim. Here, we show that instead properly constructed semilocal approximations, the Pauli-Gaussian (PG) KE functionals, especially at the Laplacian-level of theory, can indeed achieve similar accuracy as non-local functionals and can be…
Solute trapping is an important phenomenon in rapid solidification of alloys, for which the continuous growth model (CGM) is a popular sharp interface theory. Using matched asymptotic analysis, we show how to quantitatively map the sharp interface behavior of a binary alloy phase field model onto the CGM kinetics of Aziz et al. [1], with a controllable partition coefficient k(V ). We demonstrate the parameterizations that allow the phase field model to map onto the corresponding CGM or classical sharp interface models. We also demonstrate that the mapping is convergent for different interface …
The rapid solidification of a binary mixture in the region of the interface velocities $V$ close to the diffusion speed in the bulk of the liquid phase $V_D$ is considered within the framework of the local nonequilibrium approach. In this high-speed region the derivation of the analytical expression for the response function "temperature-velocity" representing kinetic phase diagram is given without using the concept of the equilibrium phase diagram. The modes of movement of the interface both without and with the drag effect are analyzed. It is shown that the drag effect can be accompanied by …
A recent study of Mejia-Rodriguez and Trickey [Phys. Rev. A 96, 052512 (2017)] showed that the deorbitalization procedure (replacing the exact Kohn-Sham kinetic-energy density by an approximate orbital-free expression) applied to exchange-correlation functionals of the meta-generalized gradient approximation (MGGA) can lead to important changes in the results for molecular properties. For the present work, the deorbitalization of MGGA functionals is further investigated by considering various properties of solids. It is shown that depending on the MGGA, common orbital-free approximations to th…
Local decomposition at the ferroelectric-antiferroelectric interphase boundaries and formation of mesoscopic structures in lead lanthanum titanate-zirconate solid solutions
The integrity of irradiated zirconium based nuclear fuel cladding is related to the precipitation of hydrides which is closely connected with the solubility of hydrogen. A review on the development of measurement technologies is given and the resulting terminal solid solubilities are reflected with respect to the established model of hydrogen solubility in zirconium alloys. The results often allow for a different interpretation than the established model. An alternative qualitative approach is proposed in which the fixed TSSp for the precipitation of zirconium hydrides is replaced by a kinetic…
Terahertz time domain spectroscopy (THz TDS) is used to measure the melting kinetics of fructose molecular crystals. Combining single crystal anisotropy measurements with density functional calculations we assign the phonon frequencies and interrogate how specific phonons behave with melting. While nearly all the low frequency phonons continuously red shift with heating and melting, the lowest energy phonon polarized along the c-axis blue shifts at the melting temperature, suggesting an initial structural change immediately before melting. We find that the kinetics follow a 3D growth model wit…
Here we study the kinetics of liquefaction and solidification of thin bismuth films grown on the insulating substrate by the pulsed laser deposited (PLD) and molecular beam epitaxy (MBE) and investigated by in situ electron and X-ray diffraction. By PLD, we can grow films similar to those obtained using MBE, studied by ex-situ AFM, KPFM, XRR, and XRD. The liquefaction-solidification transition is monitored in real-time by RHEED and synchrotron XRD, resulting in a dewetting phenomenon and the formation of spherical droplets which size depends on the initial film thickness. Studying this phase t…
Diffusion of atoms in solids is one of the most fundamental kinetic processes that ultimately governs many materials properties. Here, we report on a combined first-principles and kinetic Monte Carlo study of macroscopic diffusion properties of disordered Ti-Ta alloys over the entire composition range. Using simple cluster expansion model Hamiltonians parametrized on density functional theory data, we compute transport properties explicitly including local interactions between the two atomic species and compare them with the non-interacting diffusion model for disordered, random alloys. Surpri…
In this brief review we discuss the transient processes in solids under irradiation with femtosecond X-ray free-electron-laser (FEL) pulses and swift-heavy ions (SHI). Both kinds of irradiation produce highly excited electrons in a target on extremely short timescales. Transfer of the excess electronic energy into the lattice may lead to observable target modifications such as phase transitions and damage formation. Transient kinetics of material excitation and relaxation under FEL or SHI irradiation are comparatively discussed. The same origin for the electronic and atomic relaxation in both …
We present a kinetic model for solid state phase transformation (alpha<-->beta) of common zirconium alloys used as fuel cladding material in light water reactors. The model computes the relative amounts of beta or alpha phase fraction as a function of time or temperature in the alloys. The model accounts for the influence of excess oxygen (due to oxidation) and hydrogen concentration (due to hydrogen pickup) on phase transformation kinetics. Two variants of the model denoted by A and B are presented. Model A is suitable for simulation of laboratory experiments in which the heating/cooling rate…
Kinetic equations and level-set approach for simulating solid-state microstructure evolutions at the mesoscopic scale: state of the art, limitations, and prospects
Detailed understanding of solid-solid interface structure-function relations is critical for the improvement and wide deployment of all solid-state batteries. The interfaces between lithium phosphorous oxynitride ("LiPON") solid electrolyte material and lithium metal anode, between LiPON and Li(x)CoO(2) cathode surfaces, have been reported to generate solid electrolyte interphase ("SEI")-like products and/or disordered regions. Using electronic structure calculations and crystalline LiPON models with atomic-layer-deposition-like stoichiometry, we predict LiPON models with purely P-N-P backbone…
