Titanato de Bário e cálcio: influência da substituição parcial d modificador de rede nas propriedades fotoluminescentes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

In silico infrared and Raman spectroscopy under pressure: The case of CaSnO3 perovskite

The CaSnO3 perovskite is investigated under geochemical pressure, up to 25 GPa, by means of periodic ab initio calculations performed at B3LYP level with local Gaussian-type orbital basis sets. Structural, elastic, and spectroscopic (phonon wave-numbers, infrared and Raman intensities) properties are fully characterized and discussed. The evolution of the Raman spectrum of CaSnO3 under pressure is reported to remarkably agree with a recent experimental determination [J. Kung, Y. J. Lin, and C. M. Lin, J. Chem. Phys. 135, 224507 (2011)] as regards both wave-number shifts and intensity changes. All phonon modes are symmetry-labeled and bands assigned. The single-crystal total spectrum is symmetry-decomposed into the six directional spectra related to the components of the polarizability tensor. The infrared spectrum at increasing pressure is reported for the first time and its main features discussed. All calculations are performed using the CRYSTAL14 program, taking advantage of the new implementation of analytical infrared and Raman intensities for crystalline materials. (C) 2015 AIP Publishing LLC.

Copper ore type definition from Sossego Mine using X-ray diffraction and cluster analysis technique

This paper presents the classification of 110 copper ore samples from Sossego Mine, based on X-ray diffraction and cluster analysis. The comparison based on the position and the intensity of the diffracted peaks allowed the distinction of seven ore types, whose differences refer to the proportion of major minerals: quartz, feldspar, actinolite, iron oxides, mica and chlorite. There was a strong correlation between the grouping and the location of the samples in Sequeirinho and Sossego orebodies. This relationship is due to different types and intensities of hydrothermal alteration prevailing in each body, which reflect the mineralogical composition and thus the X-ray diffractograms of samples.

Spin-strain coupling in a 3-D transition metal oxides

ab-initio Hartree Fock (HF), density functional theory (DFT) and hybrid potentials were employed to compute the optimized lattice parameters and elastic properties of perovskite 3-d transition metal oxides. The optimized lattice parameters and elastic properties are interdependent in these materials. An interaction is observed between the electronic charge, spin and lattice degrees of freedom in 3-d transition metal oxides. The coupling between the electronic charge, spin and lattice structures originates due to localization of d-atomic orbitals. The coupling between the electronic charge, spin and crystalline lattice also contributes in the ferroelectric and ferromagnetic properties in perovskites. The cubic and tetragonal crystalline structures of perovskite transition metal oxides of ABO3 are studied. The electronic structure and the physics of 3-d perovskite materials is complex and less well considered. Moreover, the novelty of the electronic structure and properties of these perovskites transition metal oxides exceeds the challenge offered by their complex crystalline structures. To achieve the objective of understanding the structure and property relationship of these materials the first-principle computational method is employed. CRYSTAL09 code is employed for computing crystalline structure, elastic, ferromagnetic and other electronic properties. Second-order elastic constants (SOEC) and bulk moduli (B) are computed in an automated process by employing ELASTCON (elastic constants) and EOS (equation of state) programs in CRYSTAL09 code. ELASTCON, EOS and other computational algorithms are utilized to determine the elastic properties of tetragonal BaTiO3, rutile TiO2, cubic and tetragonal BaFeO3 and the ferromagentic properties of 3-d transition metal oxides. Multiple methods are employed to crosscheck the consistency of our computational results. Computational results have motivated us to explore the ferromagnetic properties of 3-d transition metal oxides. Billyscript and CRYSTAL09 code are employed to compute the optimized geometry of the cubic and tetragonal crystalline structure of transition metal oxides of Sc to Cu. Cubic crystalline structure is initially chosen to determine the effect of lattice strains on ferromagnetism due to the spin angular momentum of an electron. The 3-d transition metals and their oxides are challenging as the basis functions and potentials are not fully developed to address the complex physics of the transition metals. Moreover, perovskite crystalline structures are extremely challenging with respect to the quality of computations as the latter requires the well established methods. Ferroelectric and ferromagnetic properties of bulk, surfaces and interfaces are explored by employing CRYSTAL09 code. In our computations done on cubic TMOs of Sc-Fe it is observed that there is a coupling between the crystalline structure and FM/AFM spin polarization. Strained crystalline structures of 3-d transition metal oxides are subjected to changes in the electromagnetic and electronic properties. The electronic structure and properties of bulk, composites, surfaces of 3-d transition metal oxides are computed successfully.

Flows with 'Cu-type' characteristics at ODP Hole 104-642E (Table 1)

Native Cu occurs in amygdules, fractures and groundmass of tholeiites from Ocean Drilling Program Site 642 on the Vøring Plateau. Similar occurrences have been reported in other tholeiites of the early Tertiary North Atlantic Volcanic Province drilled at Deep Sea Drilling Project Sites 342 on the Vøring Plateau and 553 on the Rockall Plateau. The flows containing the native Cu have distinctive alteration patterns characterized by the combination of reddened flow tops, distinctive pastel coloration of the upper parts of the flows, relative abundance of celadonite, and the presence of native Cu. These associations suggest that subaerial weathering and subsequent seawater-basalt interaction are related to the occurrence of native Cu. An additional factor may be the increase in compatibility of Cu in silicates and Fe- Ti oxides that may accompany sub-solidus oxidation of basaltic flows. Native Cu occurrences in Site 642 tholeiites have some striking similarities to the large native Cu deposits in the Precambrian basalts of the Keweenaw Peninsula, Michigan, that are suggestive of similar mineralization processes.

Major element oxides of minerals from a lava pond at ODP Site 206-1256

At Ocean Drilling Program Site 1256 (6°44.2'N, 91°56.1'W), during Leg 206, a thick massive unit was cored in two neighboring penetrations of the uppermost basement, Holes 1256C and 1256D. This thick massive lava flow, commonly referred to as the "Lava Pond," is identified as Unit 18 (>30 m thick) in Hole 1256C and Unit 1 (>74.2 m thick) in Hole 1256D (Wilson et al., 2003, doi:10.2973/odp.proc.ir.206.2003). In the coarse-grained basalt that comprises this lithological unit, low-temperature "background" alteration events are present. This report provides microprobe analyses of both primary and secondary minerals present in this massive lava pond. The analyses of typically magmatic minerals (titanomagnetite, plagioclase, and clinopyroxene) are given for comparison with secondary minerals.

Major-oxides and trace-elements at DSDP Hole 78-543A

Four chemically distinct basalts were cored in 44 m of basement penetration at Deep Sea Drilling Project Site 543, in Upper Cretaceous crust just seaward of the deformation front of the Barbados Ridge and north of the Tiburon Rise. All four types are moderately fractionated abyssal tholeiites. The four types have different magnetic inclinations, all of reversed polarity, suggesting eruption at different times which recorded secular variation of the earth's magnetic field. Extensive replacement of Plagioclase by K-feldspar has occurred at the top of the basalts, giving analyses with K2O contents up to 5 %. The earliest stages of alteration were dominantly oxidative, resulting in fractures lined with celadonite and dioctahedral smectite, and pervasive replacement of olivine and most intersertal glass with iron hydroxides and green clay minerals. Latef, non-oxidative alteration resulted in formation of olive-green clays and pyrite veins in a portion of the rocks. Basalts affected by this alteration actually lost K2O (to abundances lower than in adjacent fresh basalt glasses), and gained MgO (to abundances higher than in the glasses). Finally, fractures and interpillow voids were lined with calcite, sealing in much fresh glass. Oxygen-isotope measurements on the calcite indicate that this occurred at 12 to 25C. Either altering fluids were warm or the basalts had become buried with a considerable thickness of sediments, such that temperatures increased until a conductive thermal gradient was established, when the veining occurred.

Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).

Mineral composition and major element oxides of gabbros from ODP Hole 179-1105A, southwest Indian Ridge

Hole 1105A penetrated 158 m of gabbros at a site offset 1.3 km east-northeast from Hole 735B on the Atlantis Bank near the Atlantis II Fracture Zone. A total of 118 m of dominantly medium- to coarse-grained intercalated Fe-Ti oxide gabbro and olivine gabbro was recovered from Hole 1105A that shows many petrographic features similar to those recovered from the upper part of Hole 735B. The main rock types are distinguished based on the constituent cumulus phases, with the most primitive gabbros consisting of olivine, plagioclase, and clinopyroxene. The inferred crystallization order is subsequently Fe-Ti oxides (ilmenite and titanomagnetite), followed by orthopyroxene, then apatite, and finally biotite. Orthopyroxene appears to replace olivine in a narrow middle interval. The magmatic evolution is likewise reflected in the mineral compositions. Plagioclase varies from An66 to An28. Olivine varies from Fo78 to Fo35. The gap in olivine crystallization occurs between Fo46 and Fo40 and coincides approximately with the appearance of orthopyroxene (~En50). The clinopyroxenes show large compositional variation in Mg/(Mg + Fe total) from 0.84 to 0.51. The nonquadrilateral cations of clinopyroxene similarly show large variations with Ti increasing for the olivine gabbros and decreasing for the Fe-Ti oxide gabbros with the decrease in Mg/(Mg + Fe total). The apatites are mainly flourapatites. The compositional variation in the gabbros is interpreted as a comagmatic suite resulting from fractional crystallization. Pyroxene geothermometry suggests equilibration temperatures from 1100°C and below. The coexisting Fe-Ti oxide minerals indicate subsolidus equilibration temperatures from 900°C for olivine gabbros to 700°C for the most evolved apatite-bearing gabbros. The cryptic variation in the olivine gabbros defines two or three lenses, 40 to 60 m thick, each characterized by a distinct convex zoning with a lower segment indicating upward reverse fractionation, a central maximum, and an upper segment showing normal fractionation. The Fe-Ti oxide gabbros show cryptic variations independent of the host olivine gabbros and reveal a systematic upward normal fractionation trend transgressing host olivine gabbro boundaries. Forward fractional crystallization modeling, using a likely parental magma composition from the Atlantis II Fracture Zone (MgO = 7.2 wt%; Mg/[Mg + Fe2+] = 0.62), closely matches the compositions of coexisting olivine, plagioclase, and clinopyroxene. This modeling suggests cosaturation of olivine, plagioclase, and clinopyroxene from 1155°C and the addition of Fe-Ti oxides from 1100°C. The liquid line of descent initially shows increasing FeO with moderately increasing SiO2. After saturation of Fe-Ti oxides, the liquid strongly decreases in FeO and TiO2 and increases in SiO2, reaching dacitic compositions at ~10% liquid remaining. The calculations indicate that formation of olivine gabbros can be accounted for by <65% fractionation and that only the residual 35% liquid was saturated in Fe-Ti oxides. The modeling of the solid fractionation products shows that both the olivine gabbro and the Fe-Ti oxide gabbros contain very small amounts of trapped liquid (<5%). The implications are that the gabbros represent crystal mush that originated in a recharging and tapping subaxial chamber. Compaction and upward melt migration in the crystal mush appear to have been terminated with relatively large amounts of interstitial liquid remaining in the upper parts of the cumulate mush. This termination may have been caused by tectonic disturbances, uplift, and associated withdrawal of magma into the subaxial dike and sill system. Prolonged compaction and cooling of the trapped melt in the mush formed small differentiated bodies and lenses by pressure release migration and crystallization along syntectonic channels. This resulted in differentiation products along lateral and vertical channelways in the host gabbro that vary from olivine gabbro, to Fe-Ti oxide gabbro, gabbronorite, and apatite gabbros and show large compositional variations independent of the host olivine gabbros.

Major element oxides and 40Ar/39Ar plateau and isochron ages of ODP Hole 165-1001A

40Ar-39Ar incremental heating experiments and electron microprobe analyses were performed on basaltic rocks recovered from Site 1001 during Ocean Drilling Program Leg 165. The lower Nicaraguan Rise, on which Site 1001 lies, appears to be part of a larger Caribbean oceanic plateau that makes up the core of the Caribbean plate. Our results indicate an eruption age of 81 ± 1 Ma. A single flow-rim glass is tholeiitic and almost identical to the shipboard X-ray fluorescence analyses of the whole rock. The slightly porphyritic basalts have at least two populations of plagioclase, groundmass, and glomerocrystic plagioclase laths that appear to be in equilibrium with the surrounding melt and corroded tabular phenocrysts that have a higher An content (An84-86).

Mineral content, major oxides and trace elements concentrations in clay from different IODP Holes of 331-C0013, 331-C0017, East China sea shelf and different Taiwan rivers

The Okinawa Trough (OT) in the East Asian continental margin is characterized by thick terrigenous sediment and ubiquitous volcanic-hydrothermal activities. In this study, the clays collected during IODP Expedition 331 to the middle OT (Iheya North Knoll) were analyzed for mineralogical and geochemical compositions. By comparing with the clays from the East China Sea shelf and surrounding rivers, we examine different clay origins. The hydrothermal field in the mid-OT is dominated by Mg-rich chlorite, while the recharge zone has clay mineral assemblages similar to the shelf and rivers, showing high content of illite, subordinate chlorite and kaolinite and scarce smectite. Compared to the terrigenous clays, the hydrothermal clays in the OT have high concentrations of Mg, Mn and Zr but low Fe, Na, K, Ca, Ba, Sr, P, Sc and Ti, while the hydrothermal clays in the mid-ocean ridge are relatively enriched in Fe and V and depleted in Al, Mg, Zr, Sc and Ti. Different fractionation patterns of rare earth elements also register in the terrigenous and hydrothermal clays, diagnostic of variable clay origins. We infer that the OT hydrothermal clay was primarily formed by the chemical alteration of detrital sediments subject to the hydrothermal fluids. The remarkably different compositions of hydrothermal clays between the sediment-rich back arc basin like OT and the sediment-starved ocean ridge suggest different physical and chemical processes of hydrothermal fluids and fluid-rock/sediment reactions under various geologic settings.