An official website of the United States government
The varied atomic arrangements in face-centered cubic (FCC) solid solutions introduce atomic-scale fluctuations to their energy landscapes that influence the operation of dislocation-mediated deformation mechanisms. These effects are particularly pronounced in concentrated systems, which are of considerable interest to the community. Here, we examine the effect of local fluctuations in planar fault energies on the evolution of deformation twinning microstructures in randomly arranged FCC solid solutions. Our approach leverages the kinetic Monte Carlo (kMC) method to provide kinetically weighted predictions for competition between two processes: deformation twin nucleation and deformation twin thickening. The kinetic barriers underpinning each process are drawn from the statistics of planar fault energies, which are locally sampled using molecular statics methods. kMC results show an increase in the fault number densities of solid solutions relative to a homogenized reference, which is found to be driven by the fluctuations in planar fault energies. Based on kMC relations, an effective barrier model is derived to predict the competition between deformation twinning nucleation and thickening processes under a fluctuating planar fault energy landscape. A key result from this model is a measurement of the length-scale over which the influence of local fluctuations in planar fault energies diminish and nucleation/thickening-dominated behaviors converge to bulk predictions. More broadly, the tools developed in this study enable examination of the influence of chemistry and length-scale on the evolution of deformation twinning mechanisms in FCC solid solutions.
more »
« less
A kinetic Monte Carlo study of the C3S dissolution mechanism
Understanding the mechanism that controls cement hydration and its stages is a long-standing challenge. Over a decade ago, the mineral dissolution theory was adopted from geochemistry to explain the hydration rate evolution of alite. The theory is not fully accepted by the community and deserves further investigation. In this work, we apply Kinetic Monte Carlo (KMC) simulations with the mineral dissolution theory as a conceptual framework to investigate and discuss alite dissolution. We build a Kossel crystal model system and parameterize the dissolution activation energies and frequencies based on experimental data. The resulting KMC model is capable of reproducing the dissolution rate and activation energies as a function of the dissolution free energy. The simulations indicate that mineral dissolution theory easily explains the induction and acceleration stages due to a continuous increase of the reactive area as the etch pits open. However, the deceleration stage is hardly reconcilable with the mechanism suggested in the literature, i.e. dislocation coalescence. Still, within the mineral dissolution theory umbrella, we propose and discuss an alternative mechanism based on dislocation exhaustion.
more »
« less
- PAR ID:
- 10514419
- Editor(s):
- Flat, Robert
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Cement and Concrete Research
- Volume:
- 180
- Issue:
- C
- ISSN:
- 0008-8846
- Page Range / eLocation ID:
- 107502
- Subject(s) / Keyword(s):
- Kinetic Monte Carlo Dissolution mechanism C3S Alite Dislocations Dissolution rate Activation energy
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Cold sintering densification and coarsening mechanisms are considered from the perspective of the nonequilibrium chemo-mechanical process known in Earth Sciences as pressure solution creep (or dissolutionprecipitation creep). This is an important mechanism of densification and deformation in many geological rock formations in the Earth’s upper crust, and although very slow in nature, it is of direct relevance to the cold sintering process. In cold sintering, we select particulate materials and identify experimental processing parameters to significantly accelerate the kinetics of dissolution-precipitation phenomena, with appropriate consideration of chemistry, applied stress, particle size and temperatures. In the theory of pressure solution, pressure-driven densification is considered to involve the consecutive stages of dissolution at grain contact points, then diffusive transport along the grain boundaries towards open pore surfaces, and then precipitation, all driven by chemical potential gradients. In this study, it is shown that cold sintering of BaTiO3, ZnO and KH2PO4 (KDP) ceramic materials proceeds by the same type of serial process, with the pressure solution creep rate being controlled by the slowest kinetic step. This is demonstrated by the values of activation energy (Ea) for densification, which are in good agreement with the existing literature on dissolution, precipitation, or coarsening. The influence of pressure on the morphology of ZnO grains also supports the pressure solution mechanism. Other characteristics that can be understood qualitatively in terms of pressure solution are observed in the in systems such as BaTiO3 and KDP. We further consider activation energies for grain growth with respect to the precipitation process, as well as evidence for coalescence and Ostwald ripening during cold sintering. For completeness we also consider materials that show significant plastic deformation under compression. Our findings point the way for new advances in densification, microstructural control, and reductions in cold sintering pressure, via the use of appropriate transient solvents in metals and hybrid organic-inorganic systems, such as the Methylammonium lead bromide (MAPBr) perovskite.more » « less
-
null (Ed.)The dissolution of CaCO 3 minerals in the ocean is a fundamental part of the marine alkalinity and carbon cycles. While there have been decades of work aimed at deriving the relationship between dissolution rate and mineral saturation state (a so-called rate law), no real consensus has been reached. There are disagreements between laboratory- and field-based studies and differences in rates for inorganic and biogenic materials. Rates based on measurements on suspended particles do not always agree with rates inferred from measurements made near the sediment–water interface of the actual ocean. By contrast, the freshwater dissolution rate of calcite has been well described by bulk rate measurements from a number of different laboratories, fit by basic kinetic theory, and well studied by atomic force microscopy and vertical scanning interferometry to document the processes at the atomic scale. In this review, we try to better unify our understanding of carbonate dissolution in the ocean via a relatively new, highly sensitive method we have developed combined with a theoretical framework guided by the success of the freshwater studies. We show that empirical curve fits of seawater data as a function of saturation state do not agree, largely because the curvature is itself a function of the thermodynamics. Instead, we show that models that consider both surface energetic theory and the complicated speciation of seawater and calcite surfaces in seawater are able to explain most of the most recent data.This new framework can also explain features of the historical data that have not been previously explained. The existence of a kink in the relationship between rate and saturation state, reflecting a change in dissolution mechanism, may be playing an important role in accelerating CaCO 3 dissolution in key sedimentary environments.more » « less
-
Abstract High-entropy and medium-entropy alloys are presumed to have a configurational entropy as high as that of an ideally mixed solid solution (SS) of multiple elements in near-equal proportions. However, enthalpic interactions inevitably render such chemically disordered SSs rare and metastable, except at very high temperatures. Here we highlight the wide variety of local chemical ordering (LCO) that sets these concentrated SSs apart from traditional solvent-solute ones. Using atomistic simulations, we reveal that the LCO of the multi-principal-element NiCoCr SS changes with alloy processing conditions, producing a wide range of generalized planar fault energies. We show that the LCO heightens the ruggedness of the energy landscape and raises activation barriers governing dislocation activities. This influences the selection of dislocation pathways in slip, faulting, and twinning, and increases the lattice friction to dislocation motion via a nanoscale segment detrapping mechanism. In contrast, severe plastic deformation reduces the LCO towards random SS.more » « less
-
Oxide dissolution is important for metal extraction from ores and has become an attractive route for the preparation of inks for thin film solution deposition; however, oxide dissolution is often kinetically challenging. While binary “alkahest” systems comprised of thiols and N -donor species, such as amines, are known to dissolve a wide range of oxides, the mechanism of dissolution and identity of the resulting solute(s) remain unstudied. Here, we demonstrate facile dissolution of both bulk synthetic and natural mineral ZnO samples using an “alkahest” that operates via reaction with thiophenol and 1-methylimidazole (MeIm) to give a single, pseudotetrahedral Zn(SPh) 2 (MeIm) 2 molecular solute identified by X-ray crystallography. The kinetics of ZnO dissolution were measured using solution 1 H NMR, and the reaction was found to be zero-order in the presence of excess ligands, with more electron withdrawing para -substituted thiophenols resulting in faster dissolution. A negative entropy of activation was measured by Eyring analysis, indicating associative ligand binding in, or prior to, the rate determining step. Combined experimental and computational surface binding studies on ZnO reveal stronger, irreversible thiophenol binding compared to MeIm, leading to a proposed dissolution mechanism initiated by thiol binding to the ZnO surface with the liberation of water, followed by alternating MeIm and thiolate ligand additions, and ultimately cleavage of the ligated zinc complex from the ZnO surface. Design rules garnered from the mechanistic insight provided by this study should inform the dissolution of other bulk oxides into inks for solution processed thin films.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.cemconres.2024.107502
