Modelling the effects of salt solutions on the hydration of calcium ions

Classical molecular dynamics simulations of several aqueous alkali halide salt solutions have been used to determine the effect of electrolytes on the structure of water and the hydration properties of calcium ions. Compared with the simulations of Ca2+ ions in pure liquid water, the frequency of water exchange in the first hydration shell of calcium, which is a fundamental process in controlling the reactivity of calcium(II) aqua-ions, is drastically reduced in the presence of other electrolytes in solution. The strong stabilization of the hydration shell of Ca2+ occurs not only when the halide anions are directly coordinated to calcium, but also when the alkali and halide ions are placed at or outside the second coordination shell of Ca2+, suggesting that the reactivity of the first solvation shell of the calcium ion can be influenced by the specific affinity of other ions in solution for the water molecules coordinated to Ca2+. Analysis of the hydrogen-bonded structure of water in the vicinity of the calcium ion shows that the average number of hydrogen bonds per water molecules, which is 1.8 in pure liquid water, decreases as the concentration of alkali–halide salts in solution increases, and that the temporal fluctuations of hydrogen bonds are significantly larger than those obtained for Ca2+ in pure liquid water. This effect has been explained in terms of the dynamics of reorganization of the O–H X (X = F, Cl and Br) hydrogen bond. This work shows the importance of solution composition in determining the hydrogen-bonding network and ligand-exchange dynamics around metal ions, both in solution and at the mineral–water interfaces, which in turn has implications for interactions occurring at the mineral–water interface, ultimately controlling the mobilization of ions in the environment as well as in industrial processes

Formation and kinetics of transient metastable states in mixtures under coupled phase ordering and chemical demixing

We present theory and simulation of simultaneous chemical demixing and phase ordering in a polymer-liquid crystal mixture in conditions where isotropic- isotropic phase separation is metastable with respect to isotropic-nematic phase transition. It is found that mesophase formation proceeds by a transient metastable phase that surround the ordered phase, and whose lifetime is a function of the ratio of diffusional to orientational mobilities. It is shown that kinetic phase ordering in polymer-mesogen mixtures is analogous to kinetic crystallization in polymer solutions.Comment: 17 pages, 5 figures accepted for publication in EP

Determination of the Nature of the Tetragonal to Orthorhombic Phase Transition in SrFe_2As_2 by Measurement of the Local Order Parameter

SrFe2As2 is the end-member for a series of iron-pnictide superconductors and has a tetragonal-to-orthorhombic phase transition near 200 K. Previous macroscopic measurements to determine the nature of the transition gave seemingly inconsistent results so we use electron microscopy to monitor the local order parameter showing that the transformation is first order and that the orthorhombic phase grows as needle domains. This suggests the transition occurs via the passage of transformation dislocations, explaining the apparent inconsistencies. This mechanism may be common to similar transitions.Comment: 4 pages, 4 figures submitted to Physical Review Letters. Supplementary information can be found at http://cook.msm.cam.ac.uk/~supp_info/ An extra sentence in the second last paragraph and reference 16 has been adde

Reaction mechanism for the replacement of calcite by dolomite and siderite: Implications for geochemistry, microstructure and porosity evolution during hydrothermal mineralisation

Carbonate reactions are common in mineral deposits due to CO2-rich mineralising fluids. This study presents the first in-depth, integrated analysis of microstructure and microchemistry of fluid-mediated carbonate reaction textures at hydrothermal conditions. In doing so, we describe the mechanisms by which carbonate phases replace one another, and the implications for the evolution of geochemistry, rock microstructures and porosity. The sample from the 1.95 Moz Junction gold deposit, Western Australia, contains calcite derived from carbonation of a metamorphic amphibole—plagioclase assemblage that has further altered to siderite and dolomite. The calcite is porous and contains iron-rich calcite blebs interpreted to have resulted from fluid-mediated replacement of compositionally heterogeneous amphiboles. The siderite is polycrystalline but nucleates topotactically on the calcite. As a result, the boundaries between adjacent grains are low-angle boundaries (<10°), which are geometrically similar to those formed by crystal–plastic deformation and recovery. Growth zoning within individual siderite grains shows that the low-angle boundaries are growth features and not due to deformation. Low-angle boundaries develop due to the propagation of defects at grain faces and zone boundaries and by impingement of grains that nucleated with small misorientations relative to each other during grain growth.The cores of siderite grains are aligned with the twin planes in the parent calcite crystal showing that the reactant Fe entered the crystal along the twin boundaries. Dolomite grains, many of which appear to in-fill space generated by the siderite replacement, also show alignment of cores along the calcite twin planes, suggesting that they did not grow into space but replaced the calcite. Where dolomite is seen directly replacing calcite, it nucleates on the Fe-rich calcite due to the increased compatibility of the Fe-bearing calcite lattice relative to the pure calcite. Both reactions are interpreted as fluid-mediated replacement reactions which use the crystallography and elemental chemistry of the calcite. Experiments of fluid-mediated replacement reactions show that they proceed much faster than diffusion-based reactions. This is important when considering the rates of reactions relative to fluid flow in mineralising systems

AFM study on the influence of Mn over calcite growing

Depto. de Mineralogía y PetrologíaFac. de Ciencias GeológicasFALSEpu

Statics and dynamics of domain patterns in hexagonal-orthorhombic ferroelastics

We study the statics and the dynamics of domain patterns in proper hexagonal-orthorhombic ferroelastics; these patterns are of particular interest because they provide a rare physical realization of disclinations in crystals. Both our static and dynamical theories are based entirely on classical, nonlinear elasticity theory; we use the minimal theory consistent with stability, symmetry and ability to explain qualitatively the observed patterns. After scaling, the only parameters of the static theory are a temperature variable and a stiffness variable. For moderate to large stiffness, our static results show nested stars, unnested stars, fans and other nodes, triangular and trapezoidal regions of trapped hexagonal phase, etc observed in electron microscopy of Ta4N and Mg-Cd alloys, and also in lead orthovanadate (which is trigonal-monoclinic); we even find imperfections in some nodes, like those observed. For small stiffness, we find patterns like those observed in the mineral Mg-cordierite. Our dynamical studies of growth and relaxation show the formation of these static patterns, and also transitory structures such as 12-armed bursts, streamers and striations which are also seen experimentally. The major aspects of the growth-relaxation process are quite unlike those in systems with conventional order parameters, for it is inherently nonlocal; for example, the changes from one snapshot to the next are not predictable by inspection.Comment: 9 pages, 3 figures (1 b&w, 2 colour); animations may be viewed at http://huron.physics.utoronto.ca/~curnoe/sim.htm

Crystallization of (Ca,Sr)CO3 over the {1014} surface of calcite

Depto. de Mineralogía y PetrologíaFac. de Ciencias GeológicasFALSEpu