A Phase-field Model for Computer Simulation of Lamellar Structure Formation in y-TiAI

In the present paper, a phase-field model is developed to simulate the formation and evolution of lamellar microstructure in γ-TiAl alloys. The mechanism of formation of TiAl lamellae proposed by Denquin and Naka is incorporated into the model. The model describes the formation and evolution of the face-centered cubic (fcc) stacking lamellar zone followed by the subsequent appearance and growth of the γ-phase, involving both the chemical composition change by atom transfer and the ordering of the fcc lattice. The thermodynamics of the model system and the interaction between the displacive and diffusional transformations are described by a non-equilibrium free energy formulated as a function of concentration and structural order parameter fields. The long-range elastic interactions, arising from the lattice misfit between the α, fcc (A1) and the various orientation variants of the γ-phase are taken into account by incorporating of the elastic strain energy into the total free energy. Simulation studies based on the model successfully predicted some essential features of the lamellar structure. It is found that the formation and evolution of the lamellar structure are predominantly controlled by the minimization of the elastic energy of the interfaces between the different fcc stacking groups, low-symmetry product phase γ and the high-symmetry α-phase, as well as between the various orientation variants of the product phase.

Interplay between proton ordering and ferroelectric polarization in H-bonded KDP-type crystals

The origin of ferroelectricity in KH2PO4 (KDP) is studied by first-principles electronic structure calculations. In the low-temperature phase, the collective off-centre ordering of the protons is accompanied by an electronic charge delocalization from the near and localization at the far oxygen within the O-H...O bonds. Electrostatic forces. then, push the K+ ions towards off-centre positions, and induce a macroscopic polarization. The analysis of the correlation between different geometrical and electronic quantities, in connection with experimental data. supports the idea that the role of tunnelling in isotopic effects is irrelevant. Instead, geometrical quantum effects appear to play a central role. (C) 2001 Elsevier Science B.V. All rights reserved.

On the structure and dynamics of ionic liquids

The structure and dynamics of the ionic liquid 1-ethyl-3-methylimidazolium nitrate is studied by molecular dynamics simulations. We find long-range spatial correlations between the ions and a three-dimensional local structure that reflects the asymmetry of the cations. The main contribution to the configurational energy comes from the electrostatic interactions which leads to charge-ordering effects. Radial screening and threedimensional distribution of charge are also analyzed. The motion of a single ion is studied via velocity and reorientational correlation functions. It is found that ions "rattle" in a long-lived cage, while the orientational structure relaxes on a time scale longer than 200 ps. As in a supercooled liquid, the mean square displacements reveal a subdiffusive dynamics. In addition, the presence of dynamic heterogeneities can be detected by analyzing the non-Gaussian behavior of the van Hove correlation function and the spatial arrangement of the most mobile ions. The short-time collective dynamics is also studied through the electric current time correlation function.

Liquid structure of the ionic liquid, 1-methyl-4-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide determined from neutron scattering and molecular dynamics simulations

The liquid structure of 1-methyl-4-cyanopyridinium bis {(trifluoromethyl)sulfonyl}imide, a prototypical ionic liquid containing an electron-withdrawing group on the cation, has been investigated at 368 K. Experimental neutron scattering combined with empirical potential structure refinement analysis of the data and classical molecular dynamics simulations have been used to probe the liquid structure in detail. Both techniques generated highly consistent results that provide valuable validation of the force fields and refinement approaches. A significant degree of apparent charge ordering is found in the liquid structure, although the nonspherical shape of the ions results in interpenetration of cations into the first shell of adjacent cations, with much shorter closest contact distances than the averaged center-of-mass cation-cation and cation-anion separations.

Structure and solvation in ionic liquids

This Account describes experimental data used to understand the structure of ionic liquids and solute-solvent interactions of both molecular solutes and dissolved metal complexes. In general, the structures of the ionic liquids determined from experimental data show good agreement with both simulated structures and solid-state structures. For all ionic liquids studied, strong charge ordering is found leading to long-range order even in the presence of a solute. For dissolved metal complexes, the ionic liquid is not innocent and a clear dependence on the speciation is observed with variations in both the cation and anion.

Liquid structure of the ionic liquid 1,3-dimethylimidazolium bis{(trifluoromethyl)sulfonyl}amide

Neutron diffraction has been used to determine the liquid structure of 1,3-dimethylimidazolium bis{( trifluoromethyl) sulfonyl} amide ([dmim][NTf2]). Significantly smaller charge ordering is found in this liquid compared with analogous chloride and hexafluorophosphate salts due to the diffuse charge density and size of the [NTf2](-) anion. This is manifested in a much larger cation-cation and cation-anion separation and an overlap of the cation-cation and cation-anion shells. Comparison of the liquid structure with the crystal structure reported by Holbrey et al. ( Dalton Trans. 2004, 2267) indicates little correlation, for example, the [NTf2](-) anion adopts a trans orientation predominantly in the liquid whereas a cis orientation is found in the solid phase.

Influence of ionic liquids on the crystalline structure of nanocolloids

This communication demonstrates that ionic liquids can alter the crystallinity and chemical ordering of nanocolloids synthesized in solution.

Magnetic and electronic structure of TICo2S2

An extensive investigation of the ferromagnetic compound TlCo2S2 has resulted in new information on the electronic and magnetic structure. Electronic structure calculations showed that magnetic ordering is energetically favorable with a clear driving force for ferromagnetic coupling within the cobalt layers. TlCo2S2 is metallic and the conductivity is due to holes in the valence band. XPS single crystal measurements did not show evidence of mixed oxidation states of cobalt. Neutron powder diffraction resulted in a ferromagnetic structure with the magnetic moment in the ab-plane. The derived magnetic moment of the cobalt atom is 0.65(2) mu(B) at 10 K and is in very good agreement with the value, mu(sat) = 0.65(1) mu(B) at 10 K, inferred from the magnetic hysteresis curve. (C) 2004 Elsevier Inc. All rights reserved.

Proton ordering energetics in ice phases

Results from first-principles calculations on the subtle energetics of proton ordering in ice phases are shown only to depend on the electrostatic components of the total energy. Proton ordered ice phases can therefore be predicted using electronic structure methods or a tailored potential model. However, analysis of the electron density reveals that high order multipole components, up to hexadecapole, are needed to adequately capture total energy differences between proton ordered and disordered phases. This suggests that current potential models may be unable to reproduce the position of proton ordered ice phases in the phase diagram without extensions to describe high order electrostatics. (c) 2006 Elsevier B.V. All rights reserved.

Structure of molten 1,3-dimethylimidazolium chloride using neutron diffraction

The model room temperature ionic liquid, 1,3-dimethylimidazolium chloride, has been studied by neutron diffraction for the first time. The diffraction data are used to derive a structural model of this liquid using Empirical Potential Structure Refinement. The model obtained indicates that significant charge ordering is present in the liquid salt and that the local order in this liquid closely resembles that found in the solid state. As in the crystal structure, hydrogen-bonding interactions between the ring hydrogens and the chloride dominate the structure. The model is compared with the data reported previously for both simple alkyl substituted imidazolium halides and binary mixtures with AlCl3. (C) 2003 American Institute of Physics.

Influence of strain and polycrystalline ordering on magnetic properties of high moment rare earth metals and alloys

Despite being the most suitable candidates for solenoid pole pieces in state-of-the-art superconductor- based electromagnets, the intrinsic magnetic properties of heavy rare earth metals and their alloys have gained comparatively little attention. With the potential of integration in micro- and nanoscale devices, thin films of Gd, Dy, Tb, DyGd and DyTb were plasma-sputtered and investigated for their in-plane magnetic properties, with an emphasis on magnetisation vs. temperature profiles. Based on crystal structure analysis of the polycrystalline rare earth films, which consist of a low magnetic moment FCC layer at the seed interface topped with a higher moment HCP layer, an experimental protocol is introduced which allows the direct magnetic analysis of the individual layers. In line with the general trend of heavy lanthanides, the saturation magnetisation was found to drop with increasing unit cell size. In-situ annealed rare earth films exceeded the saturation magnetisation of a high-moment Fe65Co35 reference film in the cryogenic temperature regime, proving their potential for pole piece applications; however as-deposited rare earth films were found completely unsuitable. In agreement with theoretical predictions, sufficiently strained crystal phases of Tb and Dy did not exhibit an incommensurate magnetic order, unlike their single-crystal counterparts which have a helical phase. DyGd and DyTb alloys followed the trends of the elemental rare earth metals in terms of crystal structure and magnetic properties. Inter-rare-earth alloys hence present a desirable blend of saturation magnetisation and operating temperature.