Lattice dynamics of BaFBr

A normal coordinate and force constant calculation for BaFBr was carried out on the basis of the rigid ion model. There is a strong anisotropy of the effective dynamical charges of the barium, fluoride, and bromide ions, which are 1.57e, ?0.78e, and ?0.79e for the degenerate vibrations and 1.04e, ?0.71e, and ?0.33e for the vibrations in the z-direction. In accordance with the ionic nature of BaFBr the short range force constants have only small values.     

Lattice dynamics of corundum

The short-range force constants and the contribution of the potential energy to the elastic constants have been calculated from explicit expressions for the elastic constants and for the optical frequencies. The large elastic constants of corundum are attributable to the contribution of the large short-range stretching forces. The frequencies of the phonon spectrum and the contribution of the potential energy to the frequencies have also been calculated based on a rigid-ion and polarizable-ion model. The effective charge of an oxygen ion is found to be ?0.955e. The electronic polarizability of an aluminium and oxygen ion is found to be 0.05 and 1.36 ų, respectively.     

Lattice dynamics of pyrite FeS2 — polarizable-ion model

Lattice dynamical calculations of the pyrite FeS₂ were performed using the polarizable-ion model (PIM) with different sets of short-range force constants. Not until the mean deviations between the observed and the calculated phonon energies become smaller than 3 cm^-1, the true force field can be established. In the case of only slightly greater deviations, the force fields computed differ strongly being without any physical meaning. The results are discussed with respect to the force constants K _i , F _i , and H _i , the effective dynamic charges and polarizabilities of the atoms involved, and the eigenvectors and potential energy distributions of the phonon modes. The most important short-range force constants are K ₁ (Fe-S stretching): 0.5 N cm^-1, K ₂ (internal stretching of the S₂ units): 1.0 N cm^-1, F ₁ (Fe^....Fe stretching): 0.2 N cm^-1, which indicate repulsive interactions of Fe atoms due to the occupied t _2g orbitals despite the relatively large Fe?Fe distances of 383 pm, and F ₂ and F ₃ (both intermolecular S₂?S₂ interactions): 0.2 N cm^-1. The great TO/LO splittings of some of the IR allowed phonon modes (species F _u) are caused by the large polarizabilities (2.4^.10⁶ and 3.3^.10⁶ pm³) of the atoms involved rather than by their effective charges (Fe: 0.2 e).     

Deformation-induced polymorphic transformation: experimental deformation of kyanite, andalusite, and sillimanite

Torsion experiments were performed on the Al₂SiO₅ polymorphs in the sillimanite stability field to determine basic rheological characteristics and the effect of deformation on polymorphic transformation. The experiments resulted in extensive transformation of andalusite and kyanite to sillimanite. No transformation occurred during the hot-press (no deformation) stage of sample preparation, which was carried out at similar P–T conditions and duration as the torsion experiments. Experiments were conducted on fine-grained (< 15 µm) aggregates of natural andalusite, kyanite and sillimanite at 1250 °C, 300 MPa, and a constant shear strain rate of 2 × 10^− 4/s to a maximum shear strain of 400%. Electron back-scattered diffraction (EBSD) analysis of the experiments revealed development of lattice-preferred orientations, with alignment of sillimanite and andalusite [001] slightly oblique to the shear plane. The kyanite experiment could not be analyzed using EBSD because of near complete transformation to sillimanite. Very little strain ( 30%) is required to produce widespread transformation in kyanite and andalusite. Polymorphic transformation in andalusite and kyanite experiments occurred primarily along 500 µm wide shear bands oriented slightly oblique and antithetic to the shear plane and dominated by sub-µm (100–150 nm) fibrolitic sillimanite. Shear bands are observed across the entire strain field preserved in the torsion samples. Scanning transmission electron microscope imaging shows evidence for transformation away from shear bands; e.g. fibrolitic rims on relict andalusite or kyanite. Relict grains typically have an asymmetry that is consistent with shear direction. These experimental results show that sillimanite is by far the weakest of the polymorphs, but no distinction can yet be made on the relative strengths of kyanite and andalusite. These observations also suggest that attaining high bulk strain energy in strong materials such as the Al₂SiO₅ polymorphs is not necessary for triggering transformation. Strain energy is concentrated along grain boundaries, and transformation occurs by a dynamic recrystallization type process. These experiments also illustrate the importance of grain-size sensitive creep at high strains in a system with simultaneous reaction and deformation.     

新疆芒拉克艾肯红柱石矿床地质特征及成因

芒拉克艾肯红柱石矿床位于南天山博洛霍坦北坡,南天山古生代裂陷槽之石炭纪野云沟拗拉槽东部,北与霍拉山地块相邻,二者之间为霍拉沟大断裂.区域出露地层为下元古界和下石炭统野云沟组以及中上石炭统塔拉克组.以霍拉沟大断裂为界,北部为角闪岩相,由下元古界中深变质岩系组成,岩性有黑云母角闪石英片岩、云母石英片岩、角闪斜长片麻岩等;南部为低绿片岩相,由石炭系组成,岩性有变砂岩、千枚岩、粉砂岩、含红柱石板岩等.本区岩浆活动比较强烈,岩浆岩分布严格受区域大断裂的控制.其构造线呈NWW向展布(图1). 图1 区域地质矿产…     

Phonon spectra and rigid-ion model calculations on andalusite

Polarised Raman and infrared spectra of (ir) andalusite (Al₂SiO₅) single crystals have been measured and interpreted on the basis of a rigid-ion model calculation. The Al-O bond strength is found to be about 70% ionic in character whereas the mainly covalently bound SiO₄ tetrahedra show ca. 40% ionicity. The interatomic short range forces are strongest between silicon and oxygen and rather weak around the fivefold coordinated aluminium. Thermal soft modes appear above 200°C and are correlated with a weakening of the Al-O bonds.     

Lattice dynamics and Raman spectroscopy of protoenstatite Mg2Si2O6

Enstatites (Mg₂Si₂O₆) are important rock forming silicates of the pyroxene group whose structures are characterised by double MgO₆ octahedral bands and single silicate chains. Orthoenstatite transforms to protoenstatite above 1273 K with a doubling of the a axis and a rearrangement of the silicate chains with respect to the Mg₂₊ ions. Lattice dynamical calculations based on a rigid-ion model in the quasi-harmonic approximation provide theoretical estimates of elastic constants, long wavelength phonon modes, phonon dispersion relations, total and partial density of states and inelastic neutron scattering cross-sections of protoenstatite. The computed elastic constants are in good agreement with experimental data. The computed density of states of a chain silicate such as protoenstatite is distinct from that of olivines (forsterite, Mg₂SiO₄ and fayalite, Fe₂-SiO₄) with isolated silicate tetrahedra. The band gaps in the density of states in forsterite are largely due to the separation in the frequency ranges of the external and internal vibrations of the isolated silicate group, whereas in protoenstatite these gaps are filled by the vibrations of the bridging oxygens of the silicate chain. The computed density of states is used to calculate the specific heat, the mean square atomic displacements and temperature factors. Validity of these calculations are supported by Raman scattering measurements. Polarised and unpolarised Raman spectra are obtained from small single crystals of protoenstatite (Li,Sc)_0.6Mg_1.4Si₂O₆ stable at room temperature using the 488 nm or 514.5 nm lines of an Ar⁺ ion laser and a micro-Raman spectrometer with backscattering geometry. The Raman spectra were analysed and interpreted based on the lattice dynamical model. The experimental Raman frequencies and mode assignments (based on polarised single crystal spectra) are in good agreement with those obtained from lattice dynamical calculations.     

The relationship of elasticity and crystal structure in andalusite and sillimanite

The nine elastic constants of andalusite and sillimanite have been determined, using the technique of Brillouin scattering. They are, in megabars, for andalusite: c ₁₁=2.334, c ₂₂=2.890, c ₃₃=3.801, c ₄₄=0.995, c ₅₅=0.878, c ₆₆=1.123, c ₂₃=0.977, c ₁₃=1.162, c ₁₂=0.814; for sillimanite: c ₁₁=2.873, c ₂₂=2.319, c ₃₃=3.884, c ₄₄=1.224, c ₅₅=0.807, c ₆₆=0.893, c ₂₃=1.586, c ₁₃=0.834, c ₁₂=0.947. Both structures are characterized by chains of edge-linked coordination octahedra extending parallel to the crystallographic c direction, cross-linked by polyhedra of lower coordination. In each structure the stiffness measured parallel to c is greater than that measured normal to c. The shear moduli can be directly correlated with the relative rigidity of the cross-linking structures.     

Deformation of shock-loaded andalusite studied with X-ray diffraction techniques

The structural deformation of an andalusite single crystal, shockloaded up to 400 kb with shock wave direction approximately parallel to c, was investigated by means of X-ray powder (Guinier) and single crystal techniques (Weissenberg, precession). Exposure to the dynamic pressure revealed a fracturing of the crystal into lattice blocks, with a mean size >1,000 Å. No change of the lattice constants could be observed after pressure release. From the streaks of X-ray reflection spots measured within the hk0, h0l, 0kl, and hhl planes the shock-induced lattice deformation is interpreted in terms of rotational gliding and/or microfracturing. The distortion mode is highly structure controlled. It follows preferrably two different structural motion systems: (1) Gliding parallel to (001) occurs, which produces lamellae parallel to (001), mainly arranged in two sublattices with common c-axis. The stacking sequence of lamellae along c is irregular. The lamellae-type structure may also result from an orientated transformation into a high pressure phase of lower symmetry and subsequent inversion into the original phase after pressure release. (2) Gliding parallel to (100) occurs. In this case the deformation mode is asymmetrical with respect to the undistorted crystal. The common direction b of the (001) and (100) deformation planes is probably the main direction of the shock-induced lattice deformation.     

Analysis of three-dimensional strain modified uniform distributions: andalusite fabrics from a granite aureole

A method of analysing finite strain from an initial random distribution of lines or planes is presented. The shape of the strain ellipsoid is mapped to the eigenvalue ratios of an orientation matrix. The method is used to interpret the andalusite fabrics from the aureole of the Ardara granite, County Donegal, Ireland. The high flattening strains determined in the aureole are accompanied by oblate strains in the granite margins and support the concept of deformation produced by expansion of the pluton.     

粉石英与红柱石的浮选分离机理研究

本文以油酸钠作为捕收剂,研究了磷酸氢二钠、柠檬酸和硅酸钠等抑制剂对粉石英与红柱石浮选分离效果的影响.结果表明,磷酸氢二钠是红柱石与粉石英浮选分离的一种优良的抑制剂;在其最佳浓度0.47×10-2 mol /L,浮选液pH值为8.5时,粉石英与红柱石浮选回收率差高达47.86％.红外光谱及Zeta电位分析结果表明,油酸钠对红柱石兼有物理和化学吸附作用,对粉石英仅有物理吸附作用,因而对红柱石有更强的捕收能力;磷酸氢二钠对粉石英表面起解吸作用,能有效抑制粉石英起浮,从而实现粉石英与红柱石的分离.     

Sillimanite and andalusite produced by base-cation leaching and contact metamorphism of felsic igneous rocks

Abstract Contact metamorphism adjacent to a porphyritic quartz-monzodiorite at Kentucky, New South Wales, Australia has produced hornfelses in porphyritic leucogranite at a peak temperature of about 650–700° C and a maximum confining pressure of about 2 kbar (200 MPa). A gradation appears to exist from normal slightly peraluminous to modified strongly peraluminous metagranite hornfelses, which have also been enriched in sulphur. The strongly peraluminous hornfelses, containing cordierite, andalusite, sillimanite, biotite, pyrite and pyrrhotite, retain residual porphyritic igneous microstructures. These rocks appear to have been formed by leaching of base cations, during and possibly just before the contact metamorphism. Folia of fibrous sillimanite anastomose between lenticular grains of quartz and feldspar and truncate igneous zoning in plagioclase grains, suggesting that cation leaching and solution transfer occurred during growth of the sillimanite. Fibrous sillimanite also grew in grain boundaries of polygonal aggregates formed by the contact metamorphism. Therefore, at least some of the cation leaching appears to have occurred at the highest metamorphic grade. Metasandstones that are locally strongly peraluminous adjacent to the monzodiorite stock also, have probably undergone similar leaching.     

The phase equilibrium between sillimanite and andalusite as determined from lattice vibrations

The thermodynamic equilibrium between sillimanite and andalusite has been determined from the measured phonon spectra. The corresponding aluminium silicate triple point is found to be in the range T=420° C-440° C and P=3.0–3.2 kbars. From the comparison of calorimetrically determined specific heat functions with those calculated from lattice vibrations additional effects of lattice faults of sillimanite are found to increase the temperature and pressure of the triple point considerably. The thermodynamic functions G(T), S(T) and H(T) are given for both structures.     

Pseudomorphous replacement of cordierite by symplectic intergrowths of andalusite, biotite and quartz

High-grade metapelitic gneisses rich in cordierite and K-feldspar at Cooma, N.S.W., Australia, show microstructural evidence of partial to complete replacement of cordierite grains with biotite inclusions by fine-grained, symplectic intergrowths of andalusite, biotite and quartz. The replacement occurred during the later stages of the history of the Cooma Complex, under retrograde conditions. An equation for the local reaction: cordierite+red-brown biotite+H₂O+K⁺ andalusite+green-brown biotite+quartz+H⁺ can be balanced approximately, using compositions obtained from microprobe analyses of the minerals involved. The volumes occupied by the solid reactants and solid products are nearly identical. The potassium and water were derived from an unknown external source, possibly connected with the replacement of K-feldspar by muscovite in nearby rocks.     

Lattice dynamics of α-quartz including the effect of the width of the atomic electron distribution

On the basis of the polarizable-ion model (PIM) the effect of the width of the atomic electron distribution on the lattice dynamics of α-quartz was taken into account using the Birman method. The frequencies of optical mode, elastic constants and piezoelectric constants were reproduced using the parameters of this model (an effective charge z, a width parameter w, an electronic polarizability α, and force constants). The width parameter of oxygen atom was found to be about 0.59 Å, and the effective charge of the silicon atom 1.42 electron charges.     

Sequential growth of cordierite and andalusite porphyroblasts, Cooma Complex, Australia: microstructural evidence of a prograde reaction

Abstract Low-pressure prograde metamorphism of pelitic rocks in the Cooma Complex, south-east Australia, has produced cordierite-andalusite schists at intermediate grades. The first foliation (S₁) is preserved largely as inclusion trails in cordierite porphyroblasts. Microstructural evidence indicates that the cordierite porphyroblasts grew during the early stages of development of a crenulation-foliation (S₂) and that andalusite porphyroblasts grew during the development of a later crenulation-foliation (S₃). Microstructural evidence also indicates that the andalusite was a product of the prograde reaction: cordierite + muscovite ± andalusite + biotite + quartz. The occurrence of the products of this reaction in 'beard'structures between cordierite microboudins formed by extension in S₃ confirms that the andalusite grew during the development of S₃. The investigation shows that porphyroblast-matrix relationships can preserve the orientation of an early S-surface that has been largely obliterated from the matrix, as well as providing relatively direct evidence of sequential mineral growth and metamorphic reactions.     

滇西大石坡超大型红柱石矿床成因:岩浆岩侵位的约束

滇西大石坡矿床是近年来新发现的超大型红柱石矿床。红柱石属于蓝晶石族矿物,是制造高级耐火材料的原料,在新兴产业、高新技术产业中也具有重要经济价值。红柱石矿物原料地质工作程度在云南省比较低,趋于空白。本文通过岩石地球化学和主要矿物相关性分析,深化认识大石坡红柱石矿床成矿特征与成因。大石坡红柱石矿体赋存在高黎贡山群红柱石石英云母片岩、含红柱石云母石英片岩、红柱石长石云母石英片岩中,矿体厚度大、品位中等,矿床规模达超大型。红柱石是受古近纪花岗岩侵位发生低压高温接触变质作用而形成,分布杂乱,无定向性,与区域片理产状斜交。研究显示,红柱石与矽线石相关系数为-0.369,说明二者之间成因不相关,红柱石与矽线石不是同一变质时期形成的。该矿床的形成明显受高黎贡山群片岩和古近纪钙碱性过铝质S型花岗岩制约。     

Lattice dynamics and inelastic neutron scattering from forsterite,Mg2SiO4: Phonon dispersion relation,density of states and specific heat

Magnesium-rich olivine (Mg_0.9Fe_0.1)₂SiO₄ is considered to be a major constituent of the Earth's upper mantle. Because of its major geophysical importance, the temperature and pressure dependence of its crystal structure, elastic and dielectric constants, long-wavelength phonon modes and specific heat have been measured using a variety of experimental techniques. Theoretical study of lattice dynamics provides a means of analyzing and understanding a host of such experimental data in a unified manner. A detailed study of the lattice dynamics of forsterite, Mg₂SiO₄, has been made using a crystal potential function consisting of Coulombic and short-range terms. Quasiharmonic lattice dynamical calculations based on a rigid molecular-ion model have provided theoretical estimates of elastic constants, long-wavelength modes, phonon dispersion relation for external modes along the three high symmetry directions in the Brillouin zone, total and partial density of states and inelastic neutron scattering cross-sections. The neutron cross-sections were used as guides for the coherent inelastic neutron scattering experiment on a large single crystal using a triple axis spectrometer in the constant Q mode. The observed and predicted phonon dispersion relation show excellent agreement. The inelastically scattered neutron spectra from a powder sample have been analyzed on the basis of a phonon density of states calculated from a rigid-ion model, which includes both external and internal modes. The experimental data from a powder sample show good agreement with the calculated spectra, which include a multiphonon contribution in the incoherent approximation. The computed phonon densities of states are used to calculate the specific heat as a function of temperature using both the rigid molecular-ion and rigid ion models. These results are in very good agreement with the calorimetric measurement of the specific heat. The interatomic potential developed here can be used with some confidence to study physical properties of forsterite as a function of pressure and temperature.     

堆积层滑坡水动力位移耦合预测参数及其评价方法研究

在系统分析滑坡的物质组成和失稳动因的基础上,分析和研究了地下水在滑坡稳定性演化过程中的卸载与加载动力作用及其位移响应规律和特点。从非线性系统动力学角度,提出了运用地下水卸加载动力与位移响应耦合预测参数来评价边坡稳定性演化规律与失稳特征,即以地下水位变化量作为堆积层滑坡的卸加载动力参数,以相应的位移作为其卸加载响应参数,建立和确定了地下水卸加载动力与位移响应比预测参数与评价模型。同时,运用损伤力学基本原理,建立了其卸加载响应比与坡体损伤变量和稳定性系数的定量关系以及失稳判据。以三峡库区典型堆积层滑坡分析为例,运用地下水动力与位移耦合预测模型对其稳定性进行了分析与评价,发现地下水动力位移耦合预测参数变化与边坡稳定性实际动态演化规律基本吻合。研究成果表明,所确定的参数是水诱发型堆积层滑坡的一种有效位移动力评价参数,可运用该参数对该类滑坡的动态稳定性进行实时监测预警与评价。