Browsing by Author "Angel, Ross J."

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    Comparison between beryllium and diamond-backing plates in diamond-anvil cells: Application to single-crystal x-ray diffraction high-pressure data
    Periotto, Benedetta; Nestola, Fabrizio; Balic-Zunic, Tonci; Angel, Ross J.; Miletich, Ronald; Olsen, Lars A. (AIP Publishing, 2011-05)
    A direct comparison between two complete intensity datasets, collected on the same sample loaded in two identical diamond-anvil pressure cells equipped, respectively, with beryllium and diamond-backing plates was performed. The results clearly demonstrate that the use of diamond-backing plates significantly improves the quality of crystal structure data. There is a decrease in the internal R factor for averaging, structure refinement agreement factors, and in the errors and uncertainties of the atomic coordinates, atomic displacement parameters, and individual bond lengths. (C) 2011 American Institute of Physics. [doi:10.1063/1.3590776]
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    Compressible Convection and Subduction: Kinematic and Dynamic Modeling
    Lee, Changyeol (Virginia Tech, 2010-10-05)
    Subduction is a dynamic and time-dependent process which requires time-dependent models for its study. In addition, due to the very high pressures within the Earth's interior, an evaluation of the role of compressibility in subduction studies should be undertaken. However, most subduction studies have been conducted by using kinematic, steady-state, and/or incompressible mantle convection models; these simplifications may miss important elements of the subduction process. In this dissertation, I evaluate the effects of time-dependence and compressibility on the evolution of subduction by using 2-D Cartesian numerical models. The effect of compressibility on the thermal and flow structures of subduction zones is evaluated by using kinematically prescribed slab and steady-state models. The effect of compressibility is primarily expressed as an additional heat source created by viscous dissipation. The heat results in thinner thermal boundary layer on the subducting slab and increases slab temperatures. With that exception, the effect of compressibility is relatively small compared with, for example, the effect of the mantle rheology on the thermal and flow structures of the mantle wedge. Plate reconstruction models show that the convergence rate and age of the incoming plate to trench vary with time, which poses a problem for steady-state subduction models. Thus, I consider the time-dependent convergence rate and age of the incoming plate in the kinematic-dynamic subduction models in order to understand the localization of high-Mg# andesites in the western Aleutians. The results show that the localization of high-Mg# andesites is a consequence of the time-dependent convergence rate and slab age along the Aleutian arc. The influence of mantle and slab parameters as well as compressibility on the slab dynamics is evaluated by using 2-D dynamic subduction models. The results demonstrate that periodic slab buckling in the mantle results in periodic convergence rate and dip of the subducting slab; time-dependence is a natural expression of subduction. The effect of compressibility on the slab dynamics is not significant. The periodic convergence rate and dip of the subducting slab explain time-dependent seafloor spreading at the mid-ocean ridge, convergence rate of the oceanic plate at trench and arc-normal migration of arc volcanoes.
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    The Elastic Behavior of Plagioclase Feldspar at High Pressure
    Johnson, Eleda (Virginia Tech, 2007-12-07)
    Feldspars are one of the archetypical families of framework silicates. They not only comprise around 60% volumetrically of the Earth's crust, but are among some of the most structurally complicated minerals. Investigation into the structural behavior of various intermediate plagioclases at pressure has been undertaken with the intent of categorizing the elastic behavior with pressure across the solid solution series and establishing a conceptual model to characterize feldspar compression. Complex behavior has been observed in the Equation of State for plagioclase feldspars in excess of 3 GPa, including an anomalous softening of ordered albite in excess of 8.4 GPa (Benusa et al 2005: Am Min 90:1115-1120). This softening was not observed in the EoS for the more intermediate plagioclase compositions containing between 20 and 40 mol% of end-member anorthite. The calculated elastic compliance tensor sums at room pressure show a general stiffening with increasing anorthite component, small elastic changes at the C-1 to I-1 transition, and a dominantly first-order response at the P-1 to I-1 transition near end-member anorthite. The crystal structure of An37 plagioclase was determined by single-crystal X-ray diffraction. The compression mechanisms in An37 are similar to those in albite at lower pressures. The softening in albite at higher pressures is therefore attributed to the structural shearing in albite that is absent in An37 plagioclase up to 9.5 GPa.
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    General rules for predicting phase transitions in perovskites due to octahedral tilting
    Angel, Ross J.; Zhao, J.; Ross, Nancy L. (American Physical Society, 2005-07-08)
    Recent experiments on several oxide perovskites reveal that they undergo tilt phase transitions to higher-symmetry phases on increasing pressure and that dT(c)/dP < 0, contrary to a general rule previously proposed for such zone-boundary transitions. We show that the negative slope of the phase boundary is a consequence of the octahedra in these perovskites being more compressible than the extra-framework cation sites. Conversely, when the octahedra are stiffer than the extra-framework cation sites, the phase transition temperatures increase with increasing pressure, dT(c)/dP > 0.
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    Inorganic-Organic Hybrid Networks Constructed from Different Metal Ions and Ligands
    Hu, Liangming (Virginia Tech, 2009-04-15)
    Hybrid inorganic-organic networks have been studied in both chemistry and materials science due to properties, (e.g. porosity, magnetic and electronic behaviors) that may lead to applications in catalysis, gas absorption and storage. It is important to understand the different structural topologies shown by hybrid networks to help develop practical applications for these materials. The research is focused on the design and synthesis of well-defined hybrid network structures that have potential to contain molecular size cavities that can be used for catalysis and gas storage. In the field of organic-inorganic hybrid networks, the goals are to design and synthesize 1D, 2D and 3D networks with cavities, and to characterize them by X-ray, TGA and surface area measurements. Twenty-six networks have been successfully made with interesting structure topologies. These hybrid network structures are classified into three series based on their ligands. Series I contains ten hybrid networks constructed from the flexible ligand, 4, 4′-trimethylenedipyridine (TMDP), Zn2+ ions, and H3PO3, and with aromatic alcohols as templates to direct the formation of various hybrid network structures. Series II consists of five structures constructed from the relatively rigid ligand, 4, ′-bisimidazolelybipyridine (BIB) with metal ions (Cu2+, Ni2+) and the conjugated bases of H3PO3 and H3PO4. The BIB ligand is not commercially available so is produced and characterized by NMR, mass spectrometry and TGA. Rigid network structures were expected to construct with pores of molecular dimensions with the BIB ligand. To date, the BIB ligand has not yield the desired porous network, however, these 3D hybrid networks have interesting topologies, one of which is an interdigitated network that is the precursor for 3D interpenetrated networks. Series III contains five hybrid structures constructed from various organic ligands, such as tartaric acid, picolinic acid and 1, 2, 4-triazole. In addition to the hybrid networks, six hydrogen bonded networks were prepared. Graph-Analysis is applied to study these hydrogen bonded network structures. The Ï â ¦.Ï interaction is also discussed within the hydrogen bonded networks.
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    Prehnite at the Atomic Scale: Al/Si Ordering, Hydrogen Environment, and High-Pressure Behavior
    Detrie, Theresa A. (Virginia Tech, 2008-11-03)
    The mineral prehnite, Ca2(Al,Fe,Mn)(AlSi3O10)(OH)2, is a layered structure consisting of double-sheets of (Al,Si)O4 and SiO4 tetrahedra alternating with single sheets of AlO4(OH)2 octahedra. To understand the ordering in the structure and differences between various samples of prehnite, single-crystal X-ray diffraction data at ambient conditions were collected on four single crystals of prehnite from different localities. The positions of the H atoms have been determined for the first time, from a combination of X-ray and neutron diffraction data. The equation of state and high-pressure behavior of prehnite have been investigated using single-crystal X-ray diffraction up to 9.75(3) GPa. A second-order Birch–Murnaghan equation of state fit to the isothermal P-V data to 8.7 GPa yields a bulk modulus, K = 109.29(18) GPa. Structural data collected at high pressures indicate that the structure compresses uniformly. Above 8.7 GPa there is additional softening of the volume and the b-axis related to polyhedral tilting. However, the average structure is maintained across the transition. Ambient and high-pressure Raman and synchrotron infrared spectra were collected from 1 bar to 20 GPa. Raman spectra measured at ambient conditions of four prehnite crystals with different compositions confirmed that there are no structural changes with different compositions. High-pressure results showed the majority of modes shift to higher frequencies (in a smooth, linear fashion) with increasing pressure. The greatest change in the spectra is the softening of the modes in the OH-stretching region above 9 GPa, thought to be related to the polyhedral tilting around the H environment.
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    Pressure impact on the structure, elasticity, and electron density distribution of CaSi2O5
    Yu, Yonggang G.; Angel, Ross J.; Ross, Nancy L.; Gibbs, Gerald V. (American Physical Society, 2013-05)
    Ab initio molecular dynamics simulations were used to reveal the mechanism of the fivefold to sixfold transition in Si coordination numbers of CaSi2O5. The longest first-neighbor Si-O distance drops from 2.8 to 1.8 angstrom upon the triclinic to monoclinic transition. We find significant bulk modulus softening during the structure crossover, which is due to appearance of intermediate Si-O connections in the triclinic phase under slightly nonhydrostatic stress. Nonetheless, no soft phonon modes were found in either structure, indicating that both structures are dynamically stable. Across the transition, c(33) doubles and c(35) increases sixfold in magnitude due to the formation of new Si-O bonds. Chemical bonding analysis reveals distinctions in the electron localization function and bond ellipticity between the regular (1.8 angstrom) and the dangling Si-O bonds (2.8 angstrom), both of which suggest an impending disassociation of the dangling Si-O bond.
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    Pressure-induced structural transformations in pure and Ru-doped 0.9PbZn(1/3)Nb(2/3)O(3)-0.1PbTiO(3) near the morphotropic phase boundary
    Waeselmann, N.; Maier, B. J.; Mihailova, B.; Angel, Ross J.; Zhao, J.; Gospodinov, M.; Paulmann, C.; Ross, Nancy L.; Bismayer, U. (American Physical Society, 2012-01-17)
    Pressure-induced structural transformations in relaxor-based perovskite-type (ABO(3)) 0.9PbZn(1/3)Nb(2/3)O(3)-0.1PbTiO(3) single crystals which have a very high piezoelectric response were studied by single-crystal x-ray diffraction and Raman spectroscopy at room temperature and pressures up to 18.1 GPa. Changes in the state of long-range order were observed near 1.0, 2.1, and 5.9 GPa. Initially, upon pressure increase, the ferroic deviation of the atomic positions from the cubic structure is reduced, but the ferroelectric twinning is enhanced, and near 1.0 GPa, the intrinsic ferroelectric multiphase domain pattern formed in the as-synthesized crystals is changed. At 2.1 GPa, the system undergoes a phase transition from a ferroelectric to a relaxor state, which exhibits an average cubic structure but still contains polar nanoregions. At 5.9 GPa, a reversible phase transition typical of Pb-based perovskite-type relaxors occurs, namely a cubic-to-antiferrodistortive phase transition resulting in a long-range order of antiphase octahedral tilts. On decompression, the ferroelectric state reappears below 2.1 GPa, and the local atomic structure is fully recovered at ambient pressure, but the final domain texture differs from the initial one. Ruthenium doping on the B site does not influence the pressure-induced structural transformations.
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    Some Aspects of the Crystal Chemistry of Perovskites under High Pressures
    Wang, Di (Virginia Tech, 2012-04-26)
    This thesis makes contributions to the methodology of quantitative description of the tilting systems of perovskite structures and theoretical analysis of high-pressure phase transitions of representative perovskites. Chapter 1 and 2 introduce the perovskite structures, tilting classification and descriptions. The structures in each of the 15 tilt systems have been decomposed in to the amplitudes of symmetry-adapted modes in order to provide a clear and unambiguous definition of the tilt angles. A general expression in terms of tilt angles for the ratio of the volumes of the two polyhedra within the perovskite structure is derived. Chapter 3 uses the first-principles plane-wave pseudopotential calculations to investigate the high-pressure to phase transition and elasticity of LaAlO3 perovskite. This second order transition is determined to occur at ~14 GPa by the pressure variation of the squared frequency of the soft R-point mode in the structure. Elastic moduli are inverted from the calculated stress-strain data by the singular value decomposition method. The Landau parameters for this phase transition are calibrated from the calculation results. Chapter 4 uses the same method to investigate the high-pressure phase transitions and elasticity of YAlO3 perovskite. The Pnma, Imma, I4/mcm, , perovskite structures and the NH4CdCl3-, Gd2S3-, U2S3-, CaIrO3-type structures are considered. A continuous Pnma to Imma transition occurs at ~89 GPa, determined from the soft Z-point mode of the Imma structure. Then, a discontinuous Imma to I4/mcm transition occurs at ~100 GPa, suggested by the relative enthalpies and phonon dispersions. The elasticities of the Pnma, Imma and I4/mcm structures show mechanical stabilities compatible with the phase transitions. The NH4CdCl3- and CaIrO3-type structures are dynamically stable although not energetically favorable. The relative A/B site polyhedral volume ratios are found to qualitatively reproduce the relative enthalpies of the perovskite structures.
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    Structural variations of feldspars at high pressure and high temperature
    Kolbus, Lindsay Marie (Virginia Tech, 2012-04-24)
    Feldspar minerals are framework aluminosilicates that comprise approximately 60 percent of the Earth's crust. The elastic and thermodynamic properties of this important mineral group are needed for the interpretation of seismic wave velocities, for understanding cation partioning patterns and for the determination of phase boundaries and reactions involving feldspars in the Earth's crust. Until recently, no systematic approach has been applied to describe the structural behavior of feldspars as a function of pressure, temperature and composition. In this thesis, high-pressure and high-temperature X-ray diffraction data were collected for feldspars over a range of compositions which has led to the development a structural model that allows one to predict the structural evolution of feldspars at depth in the Earth's crust. Specifically, the equations of state have been determined for two plagioclase feldspars (An20 and An78) with different states of Al/Si ordering using single-crystal X-ray diffraction. This study has shown that the introduction of Al,Si disorder into plagioclase structures at constant composition softens the structure by 4(1)% for An0, 2.5(9)% for An20 and is essentially zero for An78 compositions. The effect of pressure on the structure of an ordered An20 was also determined up to 9.15 GPa using single-crystal X-ray diffraction and it was found that the dominant compression mechanism involves tilting of the AlO4 and SiO4 tetrahedra. Similarly, high-temperature single-crystal X-ray diffraction data collected from an ordered An26 plagioclase and powder X-ray diffraction collected on a suite of Na-rich plagioclases that were refined using the Rietveld method indicate that the major structural response to increased temperature involves tilting of the tetrahedra. Building on ideas originally proposed by Dr. Helen Megaw, the changes in the conformation of the tetrahedral framework of feldspars can be described in terms of four distinct tilt systems of rigid tetrahedra. This model demonstrates that the fundamental reason for the observed anisotropy and volume change of feldspars lies in the topology of the tetrahedral framework with the greatest contribution attributed to tilt systems 2 and 3.
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    Thermoreversible Gelation, Crystallization and Phase Separation Kinetics in Polymer Solutions under High Pressure
    Fang, Jian (Virginia Tech, 2008-09-10)
    This thesis is an experimental investigation of phase behavior, crystallization, gelation and phase separation kinetics of polymer solutions in dense fluids at high pressures. The miscibility and dynamics of phase separation were investigated in solutions of atactic polystyrene with low polydispersity (Mw = 129,200; PDI = 1.02) in acetone. Controlled pressure quench experiments were conducted at different polymer concentrations to determine both the binodal and the spinodal envelops using time- and angle resolved light scattering techniques. At each concentration, a series of rapid pressure quenches with different penetration depths in a range from 0.1 MPa to 3 MPa were imposed and the time evolution of the angular distribution of the scattered light intensities was monitored. The solution with 11.4 wt % polymer concentration underwent phase separation by spinodal decomposition mechanism for both shallow and deep quenches. Below this critical polymer concentration, phase separation was found to proceed by nucleation and growth mechanism for shallow quenches, but by spinodal decomposition for deeper quenches. Gelation and crystallization processes and the influence of pressure and the fluid [Cho et al. 1993]composition were investigated in solutions of poly(4-methyl-1-pentene) [P4MP1] in n-pentane + CO₂ and in solutions of syndiotactic polystyrene [sPS] in toluene + CO₂, and also in acetophenone + CO₂ fluid mixtures over a pressure range up to 55 MPa and carbon dioxide levels up to 50 wt %. In pure pentane, P4MP1 undergoes crystallization and leads to Form III polymorph at low pressures, but to Form II at high pressures. In n-pentane + CO₂ mixture fluids, the polymorphic state changes from a mixture of Forms III and II to Form II and eventually to Form I with increasing CO₂ content. High level of carbon dioxide (≥40 wt %) in the solution was found to lead to gelation instead of crystallization. No liquid-liquid phase boundaries could be observed in any of the P4MP1 solutions. In contrast to P4MP1 in n-pentane, syndiotactic polystyrene was found to undergo gelation in toluene or acetophenone forming a polymer-solvent compound with the δ crystal form. Also in contrast to P4MP1 systems, addition of carbon dioxide to sPS solutions alters the process from that of gelation to crystallization leading to the β crystal form. In solutions with high CO₂ level, in addition to the gelation or crystallization boundaries, a liquid-liquid phase separation boundary was also observed. The phase separation path followed was found to influence the eventual morphology and the crystal state of the polymer. In sPS solutions in toluene + CO₂, if the sol-gel boundary were crossed first by cooling the solution at a fixed pressure, the resulting morphology was found to be fibrillar and the polymer displayed the δ crystal form. If instead, the liquid—liquid phase boundary were crossed first by reducing pressure at a fixed temperature, the polymer-rich phase leads to a stacked-lamellar morphology with the β crystal form while the polymer-lean phase leads to a mixed morphology with lamellar layers connected by fibrils with the polymer displaying δ + β crystal forms. In solutions in acetophenone + carbon dioxide, when the gelation boundary is crossed first, the resulting structure is the δ form as in the toluene + CO₂ case. At comparable CO₂ levels, when the L-L phase boundary is crossed first, in the acetophenone system, polymer-rich phase was found to generate a mixture of δ + β forms while only the δ form was found in the polymer-lean phase, in contrast to the observations in the toluene + CO₂ systems. Based on crystallographic, spectral and microscopic data, a thermodynamic framework was developed which provides a mechanistic account for the formation of the different polymorphs.