Understanding long-time vacancy aggregation in iron: a kinetic activation-relaxation technique study

Vacancy diffusion and clustering processes in body-centered-cubic (bcc) Fe are studied using the kinetic activation-relaxation technique (k-ART), an off-lattice kinetic Monte Carlo method with on-the-fly catalog building capabilities. For monovacancies and divacancies, k-ART recovers previously published results while clustering in a 50-vacancy simulation box agrees with experimental estimates. Applying k-ART to the study of clustering pathways for systems containing from one to six vacancies, we find a rich set of diffusion mechanisms. In particular, we show that the path followed to reach a hexavacancy cluster influences greatly the associated mean-square displacement. Aggregation in a 50-vacancy box also shows a notable dispersion in relaxation time associated with effective barriers varying from 0.84 to 1.1 eV depending on the exact pathway selected. We isolate the effects of long-range elastic interactions between defects by comparing to simulations where those effects are deliberately suppressed. This allows us to demonstrate that in bcc Fe, suppressing long-range interactions mainly influences kinetics in the first 0.3 ms, slowing down quick energy release cascades seen more frequently in full simulations, whereas long-term behavior and final state are not significantly affected.Comment: 11 pages, 12 figures. Updated to post-review manuscrip

Experimental determination of the growth rate of Richtmyer-Meshkov induced turbulent mixing after reshock

The time evolution of the width of the turbulent mixing zone arising from the late development of Richtmyer-Meshkov instability is investigated in this work. This is achieved by means of the analysis of time-resolved Schlieren images obtained with a given set of shock-tube experiments. The post-reshock growth rate of the mixing zone width is found to be nearly insensitive to the development state of the mixing at the time of reshock

Study of the turbulent mixing zone induced by the Richtmyer-Meshkov instability using Laser Doppler Velocimetry and Schlieren visualizations

An experimental study of the compressible mixing generated by the Richtmyer-Meshkov instability (RMI) is carried out in a vertical shock tube by means of two-components Laser Doppler Velocimetry (2C-LDV) measurements and Time-resolved Schlieren visualizations. An attempt is made to quantify the RMI-induced air/sulphurhexafluoride (SF6) mixing by measuring turbulence levels inside the mixing zone at a given stage of its development and by extracting the growth rate of the mixing zone from the Schlieren images

É́tude sur la cinétique des défauts structuraux dans le silicium amorphe

Cette thèse présente à la fois des résultats de simulations numériques en plus de ré- sultats expérimentaux obtenus en laboratoire sur le rôle joué par les défauts de structure dans le silicium amorphe. Nos travaux de simulation numérique furent réalisés avec une nouvelle méthode de simulation Monte-Carlo cinétique pour décrire l’évolution tempo- relle de modèles de silicium amorphe endommagés sur plusieurs échelles de temps jus- qu’à une seconde à la température pièce. Ces simulations montrent que les lacunes dans le silicium amorphe sont instables et ne diffusent pas sans être détruites. Nous montrons également que l’évolution d’un modèle de silicium amorphe endommagé par une colli- sion ionique lors d’un recuit peut être divisée en deux phases : la première est dominée exclusivement par la diffusion et la création/destruction de défauts de liaison, alors que la deuxième voit les créations/destructions de liens remplacées par des échanges de liens entre atomes parfaitement coordonnés. Les défauts ont aussi un effet sur la viscosité du silicium amorphe. Afin d’approfondir cette question, nous avons mesuré la viscosité du silicium amorphe et du silicium amorphe hydrogéné sous l’effet d’un faisceau d’ions. Nous montrons que la variation de la viscosité dans les deux matériaux est différente : le silicium amorphe hydrogéné a une viscosité constante en fonction de la fluence des ions alors que le silicium amorphe pur a une viscosité qui augmente de façon linéaire. Pour de faibles fluences, la viscosité du silicium hydrogéné est plus grande que la viscosité sans hydrogène. La présence d’hydrogène diminue également l’amplitude de la variation logarithmique de la contrainte observée lors de la relaxation à la température de la pièce.This thesis presents the results of both computational and experimental studies on the role of structural defects in amorphous silicon. The computational work was done using a novel kinetic Monte-Carlo method to simulate the time evolution of defective models of amorphous silicon over timescales reaching one second at room temperature. These simulations show that the vacancy in amorphous silicon is unstable and does not diffuse without being annihilated. We also show that the annealing behavior of an ion-damaged model of amorphous silicon can be divided in two phases: the initial one being dom- inated exclusively by the diffusion and rapid creation/annihilation of bond defects, the other one with bond defect creation/annihilation being progressively replaced by bond exchanges from perfectly coordinated atoms. Defects also have an effect on the viscosity amorphous silicon. To explore this further we mesure the radiation-enhanced viscosity of pure and hydrogenated amorphous silicon under the effect an ion-beam. We show the change in viscosity is different, the hydrogenated samples having a constant density while the pure amorphous silicon samples having a viscosity that increases linearly with ion fluence. At low fluence, the viscosity of hydrogenated amorphous silicon is higher than the viscosity of pure amorphous silicon. The presence of hydrogen also reduces the amplitude of the logarithmic stress change observed during annealing at room tempera- ture

Synthesis of Macromolecules Containing Phenylalanine and Aliphatic Building Blocks

Aiming at developing efficient interfacial agents for fiber‐reinforced composite materials, macromolecules are designed to have different components able to stick to the fiber and be compatible with the polymer matrix, respectively. Herein, macromolecules are prepared by solid‐phase synthesis considering phenylalanine residues to promote adsorption of the macromolecule on aramid fibers and aliphatic building blocks to interact with a hydrophobic polymer matrix. Using phenylalanine as building block for the preparation of macromolecules by iterative synthesis has been shown to be challenging. Thus, the screening of various parameters for the optimization of the synthesis of these macromolecules is discussed in this communication. A preliminary thermal study by thermal gravimetric analysis is conducted to evaluate their thermal stability

African monsoon teleconnections with tropical SSTs: validation and evolution in a set of IPCC4 simulations

A set of 12 state-of-the-art coupled oceanatmosphere general circulation models (OAGCMs) is explored to assess their ability to simulate the main teleconnections between the West African monsoon (WAM) and the tropical sea surface temperatures (SSTs) at the interannual to multi-decadal time scales. Such teleconnections are indeed responsible for the main modes of precipitation variability observed over West Africa and represent an interesting benchmark for the models that have contributed to the fourth Assessment Report of the Intergovernmental Panel on Climate Change (IPCC4). The evaluation is based on a maximum covariance analysis (MCA) applied on tropical SSTs and WAM rainfall. To distinguish between interannual and multi-decadal variability, all datasets are partitioned into low-frequency (LF) and high-frequency (HF) components prior to analysis. First applied to HF observations, the MCA reveals two major teleconnections. The first mode highlights the strong influence of the El Niño Southern Oscillation (ENSO). The second mode reveals a relationship between the SST in the Gulf of Guinea and the northward migration of the monsoon rainbelt over the West African continent. When applied to HF outputs of the twentieth century IPCC4 simulations, the MCA provides heterogeneous results. Most simulations show a single dominant Pacific teleconnection, which is, however, of the wrong sign for half of the models. Only one model shows a significant second mode, emphasizing the OAGCMs’ difficulty in simulating the response of the African rainbelt to Atlantic SST anomalies that are not synchronous with Pacific anomalies. The LF modulation of these HF teleconnections is then explored through running correlations between expansion coefficients (ECs) for SSTs and precipitation. The observed time series indicate that both Pacific and Atlantic teleconnections get stronger during the twentieth century. The IPCC4 simulations of the twentieth and twenty-first centuries do not show any significant change in the pattern of the teleconnections, but the dominant ENSO teleconnection also exhibits a significant strengthening, thereby suggesting that the observed trend could be partly a response to the anthropogenic forcing. Finally, the MCA is also applied to the LF data. The first observed mode reveals a well-known inter-hemispheric SST pattern that is strongly related to the multi-decadal variability of the WAM rainfall dominated by the severe drying trend from the 1950s to the 1980s. Whereas recent studies suggest that this drying could be partly caused by anthropogenic forcings, only 5 among the 12 IPCC4 models capture some features of this LF coupled mode. This result suggests the need for a more detailed validation of the WAM variability, including a dynamical interpretation of the SST–rainfall relationships

Diffusion of point defects in crystalline silicon using the kinetic activation-relaxation technique method

We study point-defect diffusion in crystalline silicon using the kinetic activation-relaxation technique (k-ART), an off-lattice kinetic Monte Carlo method with on-the-fly catalog building capabilities based on the activation-relaxation technique (ART nouveau), coupled to the standard Stillinger-Weber potential. We focus more particularly on the evolution of crystalline cells with one to four vacancies and one to four interstitials in order to provide a detailed picture of both the atomistic diffusion mechanisms and overall kinetics. We show formation energies, activation barriers for the ground state of all eight systems, and migration barriers for those systems that diffuse. Additionally, we characterize diffusion paths and special configurations such as dumbbell complex, di-interstitial (IV-pair+2I) superdiffuser, tetrahedral vacancy complex, and more. This study points to an unsuspected dynamical richness even for this apparently simple system that can only be uncovered by exhaustive and systematic approaches such as the kinetic activation-relaxation technique

The Activation-Relaxation Technique : ART nouveau and kinetic ART

The evolution of many systems is dominated by rare activated events that occur on timescale ranging from nanoseconds to the hour or more. For such systems, simulations must leave aside the full thermal description to focus specifically on mechanisms that generate a configurational change. We present here the activation relaxation technique (ART), an open-ended saddle point search algorithm, and a series of recent improvements to ART nouveau and kinetic ART, an ART-based on-the-fly off-lattice self-learning kinetic Monte Carlo method

Kinetic Activation Relaxation Technique

We present a detailed description of the kinetic Activation-Relaxation Technique (k-ART), an off-lattice, self-learning kinetic Monte Carlo algorithm with on-the-fly event search. Combining a topological classification for local environments and event generation with ART nouveau, an efficient unbiased sampling method for finding transition states, k-ART can be applied to complex materials with atoms in off-lattice positions or with elastic deformations that cannot be handled with standard KMC approaches. In addition to presenting the various elements of the algorithm, we demonstrate the general character of k-ART by applying the algorithm to three challenging systems: self-defect annihilation in c-Si (crystalline silicon), self-interstitial diffusion in Fe and structural relaxation in a-Si (amorphous silicon).Comment: 13 pages, 11 figures. Final version as published, Figs. 6 and 7 exchanged, minor typographical and stylistic correction