Phonon spectra of 2∶1 mullite in infrared and Raman experiments

Single crystal Raman and infrared phonon spectra of mullite were measured. The number of modes, their frequencies and line profiles are analysed. The local structural changes associated with the formation of oxygen vacancies contribute to the appearence of modes in both the Raman and infrared spectra of mullite. The number of modes is increased compared with the degrees of freedom predicted by group theory for the mullite structure without oxygen vacancies.     

Quantum mechanical calculations of the vibrational spectra of quartz- and rutile-type GeO2

Heat-treatment and stepwise cooling of as-delivered, water-containing quartz-type GeO₂ powder resulted in transformation into a water-free form. A rutile-type modification could be prepared by impregnation of the quartz-type phase with RbOH solutions, drying and annealing. Raman- and FTIR-absorption spectra of quartz- and rutile-type GeO₂ were measured and compared to quantum-mechanical ab initio calculations based on a hybrid functional using the Perdew–Burke–Ernzerhof correlation functional with 16.7% Hartree–Fock exchange density functional. Maximum and mean deviations between measured spectral bands and assigned vibrational modes are 14 and ±8 cm⁻¹ for the quartz-type and 30 and ±13 cm⁻¹ for the rutile-type polymorphic form. Water is incorporated into GeO₄ entities of quartz-type GeO₂; a water-free and structurally stable form can be prepared by a heating up to 1,425 K, tempering at 1,323 K and stepwise cooling. Spectral bands not explained by the calculations suggest defects and distortions in both quartz- and rutile-type structures, in case of the quartz-type one by incomplete transformation into an ideal structure after removing the water, whereas the rutile-type modification most probably incorporates Rb during its synthesis.     

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…     

Structure of densified vitreous silica: Silicon and oxygen XANES spectra and multiple scattering calculations

The decrease of the mean Si-O-Si angle in vitreous silica upon densification from 2.20 to 2.36 gcm^-3 has been followed by oxygen and silicon K-edge XANES spectroscopy. Multiple scattering calculations using clusters of two shells around the oxygen and silicon atoms, respectively, are in good agreement with experimental absorption spectra and confirm mean Si-O-Si angles between 130 and 144° for these samples, and a decrease of the mean angle with densification. The experimental spectra also exhibit features due to scattering at outer (>2) shells around the photoabsorbers.     

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.     

Thorite versus huttonite: stability, electronic properties and X-ray emission spectra from first-principle calculations

The structural, electronic properties and stability of thorium orthosilicate ThSiO₄ polymorphs: thorite and huttonite are investigated by means of the full-potential linearized augmented-plane-wave method with the generalized gradient approximation for the exchange-correlation potential (FLAPW-GGA). The forbidden gaps of thorite and huttonite are estimated at about 7.8 and 7.6 eV, respectively. It is found that Th5f states in ThSiO₄ partially overlap with occupied O2p bands. The data obtained showed that thorite is more stable than huttonite; in turn both ThSiO₄ polymorphs are unstable with respect to their constituent binary oxides (thorianite ThO₂ and α-quartz SiO₂) in agreement with the experiments. The theoretical shapes of X-ray emission (XES) (Si,O)Kα,β spectra for thorite, huttonite as well as for SiO₂ and ThO₂ are calculated and discussed. We show that the XES spectroscopy near the (Si,O)K edge may be very useful technique not only for detailed investigation of the bulk-electronic structure of Th silicates but also for the phase analysis of complex mineral samples containing these species.     

Relationship between mössbauer spectra and defect structure in biotites from electric field gradient calculations

The electric field gradient at the octahedral sites in biotite is calculated by use of the point charge model for the ideal crystal structure. The contribution from the overlap distortions of cation orbitals by the surrounding ligands is included. The calculated values of the ferric quadrupole splittings are in good agreement with those obtained from Mössbauer spectra of micas. The effect of the neighbouring point defects and of real structure features of biotite on the electric field gradient are computed. It has been found that various point defects in adjacent sites produce varying values of ferric quadrupole splittings, which exceed the difference between the ideal parameters at the two distinct octahedral sites. A new interpretation of the biotite Mössbauer spectra is suggested.     

Raman spectroscopy of ferritungstite: Experimental and model spectra

Raman spectra of ferritungstite are interpreted on the basis of model calculations. The presence of two broad vibrational bands in the spectral range 600–1000 cm^?1 is explained through the combination of two factors. Mainly, two principle bands in the spectral ranges 600–750 and 850–1000 cm^?1 are characteristic of the pyrochlore-type structure attained by ferritungstite and correspond to symmetric and asymmetric stretching of the W-O bonds, respectively. Also, broadening of the Raman lines results from structural disorder caused by the presence of iron atoms.     

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.     

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.     

Interpretation of cosmogenic nuclides in meteorites on the basis of accelerator experiments and physical model calculations

Cosmogenic nuclides in extraterrestrial matter provide a wealth of information on the exposure and collision histories of small objects in space and on the history of the solar and galactic cosmic radiation. The interpretation of the observed abundances of cosmogenic nuclides requires detailed and accurate knowledge of their production rates. Accelerator experiments provide a quantitative basis and the ground truth for modeling cosmogenic nuclide production by measurements of the relevant cross sections and by realistic simulations of the interaction of galactic protons with meteoroids under completely controlled conditions, respectively. We review the establishment of physical model calculations of cosmogenic nuclide production in extraterrestrial matter on the basis of such accelerator experiments and exemplify this approach by presenting new experimental and theoretical results for the cosmogenic nuclide⁴⁴Ti. The model calculations describe all aspects of cosmogenic nuclide production and allow the determination of long-term solar and galactic cosmic ray spectra and a consistent interpretation of cosmogenic nuclides in extraterrestrial matter.     

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.     

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.     

The electronic structure and absorption spectrum of MnO 6 9− octahedra in manganian andalusite

The energy levels of MnO ₆ ^9? clusters, with D _4h approximated and C _2v actual symmetry of the M ₁ site of Mn³⁺-bearing andalusite, are calculated using the multiple scattering method. The energies of the electronic d-d transition of Mn³⁺ in the clusters with D _4h symmetry are calculated to be 6,000–7,000 cm^?1 (⁵ B _1g → ⁵ A _1g ), ～18,000 cm^?1 (⁵ B _1g → ⁵ B _2g ) and ～19,000 cm^?1 (⁵ B _1g → ⁵ E _g ). Apart from a splitting of the ⁵ E _g -level into two levels separated by 300–350 cm^?1, no significant changes of these transition energies are noted for the corresponding cluster with C _2v symmetry. The calculated transition energies give a good fit to the structure of the optical absorption spectra of Mn³⁺-bearing andalusites and support recent assignments of the major absorption bands observed in these spectra.     

X-ray K-edge absorption spectra of Fe minerals and model compounds: Near-edge structure

Synchrotron radiation has been used to collect high-resolution Fe K absorption near-edge spectra of a suite of Fe minerals and compounds having a range of Fe environments. These spectra, along with those of previous workers, indicate that the number, position, and intensity of near-edge features are characteristic of Fe valence and general site geometry. For example, the crest of the K-edge for Fe²⁺ in a six-coordinated site in the oxides studied is about 3 eV lower in energy than that for Fe³⁺ in a similar site. The K-edge crest for Fe³⁺ in a four-coordinated site is 1 to 2 eV lower than for Fe³⁺ in a regular site. The shape of the edge crest is sensitive to the details of first-neighbor bonding distances, tending to be broader in species with irregular Fe sites and varying in energy according to the average bond length. Comparison with Ca²⁺ and Zn²⁺ spectra from the literature is made and the applicability and utility of edge measurements discussed.     

X-ray K-edge absorption spectra of Fe minerals and model compounds: II. EXAFS

K-edge extended X-ray absorption fine structure (EXAFS) spectra of Fe in varying environments in a suite of well-characterized silicate and oxide minerals were collected using synchrotron radiation and analyzed using single scattering approximation theory to yield nearest neighbor Fe-O distances and coordination numbers. The partial inverse character of synthetic hercynite spinal was verified in this way. Comparison of the results from all samples with structural data from X-ray diffraction crystal structure refinements indicates that EXAFS-derived first neighbor distances are generally accurate to ±0.02 Å using only theoretically generated phase information, and may be improved over this if similar model compounds are used to determine EXAFS phase functions. Coordination numbers are accurate to ±20 percent and can be similarly improved using model compound EXAFS amplitude information. However, in particular cases the EXAFS-derived distances may be shortened, and the coordination number reduced, by the effects of static and thermal disorder or by partial overlap of the longer Fe-O first neighbor distances with second neighbor distances in the EXAFS structure function. In the former case the total information available in the EXAFS is limited by the disorder, while in the latter case more accurate results can in principle be obtained by multiple neighbor EXAFS analysis. The EXAFS and XANES spectra of Fe in Nain, Labrador osumulite and Lakeview, Oregon plagioclase are also analyzed as an example of the application of X-ray absorption spectroscopy to metal ion site occupation determination in minerals.     

固溶体矿物的性质对计算河南西峡红柱石矿形成条件的影响

自然界的大多数造岩矿的是由两种或多种组分混合而成的固溶体。因此，在矿物，岩石和矿床等地质体的平衡热力学研究中不可避免地要涉及固溶体矿物热力学地为的问题。河南省西峡县杨乃沟红柱石矿泥质片岩中仅出现红柱石而没有蓝晶石和夕线石，红柱石矿物包裹体测温结果为420－600℃。通过矿物共生平衡p-t曲线所计算出的片岩形成温度和压力条件也应位于上述岩石学和岩相学等特征所限定的范围内。以此为基础，通过构筑矿物共生p-t平衡曲线的方法，对片岩中若干固溶体矿物理想性／非理想性问题进行了研究。其中斜长石必须以非理想固溶体处理，而石榴子石，黑云母和白云母视作理想固溶体的计算结果同片岩的岩石学和岩相学等特征相一致。