Ab initio study of high tridymite by the formalism generator coordinate Hartree-Fock

The Generator Coordinate Hartree-Fock (GCHF) Method is applied to generate extended 14s 8p and 17s 11p Gaussian basis sets for the atoms O and Si, respectively. The role of the weight functions in the assessment of the numerical integration range of the GCHF is shown. The Gaussian basis sets are contracted to [6s4p] O atom and [8s5p] Si atom by the Dunning's segmented contraction scheme. To evaluate the quality of our contracted [6s4p] and [8s5p] bases in molecular calculations we accomplish calculations of total and orbital energies in the Hartree-Fock-Roothaan method for O-2 and SiO molecules. We compare the results obtained with the our (14s 8p) and (17s 11p) bases sets with the of 6-311G basis and with values from the literature. The addition of one d polarization function in the silicon basis and its utilization with the basis for oxygen leads to the calculation of electronic properties and IR Spectrum of high tridymite in space group D-3d. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Effect of Al2O3 and Cr2O3 on loquidus temperatures in the cristobalite and tridymite primary phase fields of the MgO-"FeO"-SiO2 ststem in equilibrium with metallic iron

The effects of alumina and chromite impurities on the liquidus temperatures in the cristobalite/tridymite (SiO2) primary phase fields in the MgO-FeO-SiO, system in equilibrium with metallic iron have been investigated experimentally. Using high temperature equilibration and quenching followed by electron probe X-ray microanalysis (EPMA), liquiclus isotherms have been determined in the temperatures range 1 673 to 1 898 K. The results are presented in the form of pseudo-ternary sections of the MgO-FeO-SiO, system at 2, 3 and 5 wt% Al2O3, 2 wt% Cr2O3, and 2 wt% Cr2O3+2 wt% Al2O3. The study enables the liquidus to be described for a range of SiO2/MgO and MgO/FeO ratios. It was found that liquiclus temperatures in the cristobalite and tridymite primary phase fields, decrease significantly with the addition of Al2O3 and Cr2O3.

Analytical electron microscopy of Mg-SiO smokes; a comparison with infrared and XRD studies

Experimentally obtained Mg.SiO smokes were studied by analytical electron microscopy using the same samples that had been previously characterized by repeated infrared spectroscopy. Analytical electron microscopy shows that unannealed smokes contain some degree of microcrystallinity which increases with increased annealing for up to 30 hr. An SiO2 polymorph (tridymite) and MgO may form contemporaneously as a result of growth of forsterite (Mg2SiO4) microcrystallites in the initially nonstoichiometric smokes. After 4 hr annealing, forsterite and tridymite react to enstatite (MgSiO3). We suggest that infrared spectroscopy and X-ray diffraction analysis should be complemented by detailed analytical electron microscopy to detect budding crystallinity in vapor phase condensates.

Wet chemical syntheses of ultrafine multicomponent ceramic powders through gel to crystallite conversion

Coarse (BOn/2)-O-n+/xH(2)O (10tridymite structure and chromates. The nanosized crystallites are often in metastable phases, such as cubic BaTiO3 at room temperature or superparamagnetic hexaferrites. Through the same route, luminescent phosphors of aluminates doped with rare-earth metals could be prepared. The present results indicate the general features of the gel-crystallite (G-C) conversion involving the instability of the metal hydroxide gel brought about by the disruption of the ionic pressure in the gel as a result of the faster diffusion of A(2+) ions through the solvent cavities within the gel frame work. This is accompanied by the splitting of the bridging groups like B-(OH)-B or B-O-B, leading to the breakdown of the gel into crystallites. G-C conversion has advantages as a method of synthesis of ceramics in terms of operational cost and procedural simplicity.

Role of B2O3 on the phase stability and long phosphorescence of SrAl2O4 : Eu, Dy

The role of B2O3 addition on the long phosphorescence of SrAl2O4:Eu2+, Dy3+ has been investigated. B2O3 is just not an inert high temperature solvent (flux) to accelerate grain growth, according to SEM results. B2O3 has a substitutional effect, even at low concentrations. by way of incorporation of BO4 in the corner-shared AlO4 framework of the distorted 'stuffed' tridymite structure of SrAl2O4. which is discernible from the IR and solid-state MAS NMR spectral data. With increasing concentrations, B2O3 reacts with SrAl2O4 to form Sr4Al4O25 together with Sr-borate (SrB2O4) as the glassy phase, as evidenced by XRD and SEM studies. At high B2O3 contents, Sr4Al14O25 converts to SrAl2B2O7 (cubic and hexagonal), SrAl12O19 and Sr-borate (SrB4O7) glass. Sr4Al14O25:Eu2+, Dy3+ has also been independently synthesized to realize the blue emitting (lambda(em)approximate to490 nm) phosphor. The afterglow decay as well as thermoluminescence studies reveal that Sr4Al14O25:Eu, Dy exhibits equally long phosphorescence as that of SrAl2O4:Eu2+, Dy3+. In both cases, long phosphorescence is noticed only when BO4 is present along with Dy3+ and Eu2+. Here Dy3+ because of its higher charge density than Eu2+ prefers to occupy the Sr sites in the neighbourhood of BO4, as the effective charge on borate is more negative than that of AlO4. Thus. Dy3+ forms a substitutional defect complex with borate and acts as an acceptor-type defect center. These defects Eu2+ ions and the subsequent thermal release of hole at room temperature followed by the trap the hole generated by the excitation of recombination with electron resulting in the long persistent phosphorescence. (C) 2003 Elsevier Science B.V. All rights reserved.

The phase transitions of hetero atoms substituted molecular sieves Me-VPI-5(Me=Mg, Ti, Sn, Si) and their influence on spectra structures of Eu(III) ion

The hetero atom substituted aluminophosphate molecular sieves Me-VPI-5(Me = Mgt Ti, Sn, Si) were synthesized hydrothermally. Rare earth ions are originally doped into these microporous materials by aqueous solution ion exchange procedures. The phase transitions of the microporous materials are investigated by high-temperature and high-pressure experimental techniques. The influence of the phase transitions on the rare earth ions' spectral structures is discussed, With the increase of temperature, Eu(II)Mg-VPI-5 is converted into Eu(II)Mg-AIPO(4)-8, then into tridymite phase. The pressure has a notable influence on Eu(II) ion's spectral structures. The spectral structures have changed regularly with the increase of pressure.

Stoichiometric changes in lithium conducting materials based on Li1+xAlxTi2−x(PO4)3: impedance, X-ray and NMR studies

The lithium fast-ion conductor, Li_1+xAl_xTi_2−x(PO₄)₃ (LATP) has been modified via changes in stoichiometry during the processing steps. The resultant changes have been followed using ²⁷Al MAS NMR, X-ray powder diffraction and impedance spectroscopy. The most important changes were those of the form Li_1.3+4yAl_0.3Ti_1.7−y(PO₄)₃. It was possible to remove the AlPO₄ phase (both tridymite and berlinite polymorphs), as monitored by X-ray diffractograms and ²⁷Al NMR spectra. Consequently, these changes appear to result in increased grain boundary conductivity of the LATP material.

Obtenção de filtro cerâmico a partir da diatomita e casca de arroz carbonizada visando tratamento de efluente têxtil

The effluents released by the textile industry have high concentrations of alkali, carbohydrates, proteins, in addition to colors containing heavy metals. Therefore, a filter was prepared aiming primarily to the removal of color. In order to prepare this filter, rice hulls and diatomite were used, which have in their structure, basically amorphous hydrated silica. The silica exists in three crystalline forms: quartz, tridymite and cristobalite. In accordance with the above considerations, this study was divided into two stages; the first corresponds to the preparation of the filter and the second to carry out the tests in the effluent/filter in order to verify the efficiency of the color removal. First, the raw material was subjected to a chemical analysis and XRD, and then the diatomite was mixed, via humid, with a planetarium windmill with 20 %, 40 %, 60 % and 80 % of rice husk ash. To the mixture, 5 % carboxymethylcellulose (CMC) was added as a binder at room temperature. The samples were uniaxially compacted into metallic matrix of 0.3 x 0.1 cm² of area at a pressure of 167 MPa by means of hydraulic press and then sintered at temperatures of 1,000 °C, 1,200 °C and 1,400 °C for 1 h and submitted to granulometry test using laser, linear retraction, water absorption, apparent porosity and resistance to bending, DTA, TMA and XRD. To examine the pore structure of the samples scanning electron microscope (SEM) was used. Also tests were carried out in a mercury porosimeter to verify the average size of the pores and real density of the samples. In the second stage, samples of the effluent were collected from a local industry, whose name will be preserved, located in Igapó, in the State of Rio Grande do Norte - RN. The effluent was first pretreated before filtration and then subjected to a treatment of flotation. The effluent was then characterized before and after filtration, with parameters of color, turbidity, suspended solids, pH, chemical and biochemical oxygen demand (COD and BOD). Thus, through the XRD analysis the formation of cristobalite α in all samples was observed. The best average size of pore was found to be 1.75 μm with 61.04 % apparent porosity, thus obtaining an average 97.9 % color removal and 99.8 % removal of suspended solid

Pirometamorfismo nos arenitos da Formação Açu, Bacia Potiguar, NE do Brasil

Pyrometamorphism results from conditions of high temperatures and very low pressures provoked by the intrusion of hypabyssal basic bodies into sedimentary or metassedimentary hosting rocks. The onshore portion of the Potiguar Basin in NE Brazil offers examples of this type of metamorphism nearby the contacts of Paleogene to Neogene plugs, sills and dikes of diabases and basalts crosscutting sandstones, siltstones and shales of the Açu Formation (Albian-Cenomanian). The thermal effects over these rocks are reflected on textures and minerals assemblages that characterize the sanidinite facies of metamorphism, often with partial melting of the feldspathic and mica-rich matrix. The liquid formed is potassic and peraluminous, with variably colored rhyolitic glass (colorless, yellow, brown) comprising microcrystals of tridymite, sanidine and clinoenstatite, besides residual detrital clasts of quartz and rarely zircon, staurolite and garnet. Lenses of shale intercalated within the sandstones display crystallites of Fe-cordierite (sekaninaite), mullite, sanidine, armalcolite (Fe-Ti oxide) and brown spinel. The rocks formed due to the thermal effect of the intrusions are called buchites for which two types are herein described: a light one derived from feldspathic sandstone and siltstone protoliths; and a dark one derived from black shale protoliths. Textures indicating partial melting and minerals such as sanidine, mullite, tridymite and armalcolite strongly demonstrate that during the intrusion of the basic bodies the temperature reached 1,000-1,150°C, and was followed by quenching. Cooling of the interstitial melts has as consequences the closure of pores and decrease of the permeability of the protolith, which varies from about 17-11% in the unaffected rocks to zero in the thermally modified types. Although observed only at contacts and over small distances, the number of basic intrusions hosted within the Potiguar Basin in both onshore and offshore portions leaves opened the possibility of important implications of the thermal effects over the hydrocarbon exploration in this area as well in other Cretaceous and Paleozoic basins in Brazil

Opalas gemológicas do Piauí: gênese revelada por microtermometria e minerais associados

As opalas de Pedro II e Buriti dos Montes, no estado do Piauí, constituem as mais importantes ocorrências brasileiras dessa gema, tanto em termos de volume quanto pela qualidade gemológica, que é comparável à das famosas opalas australianas. No entanto, a informalidade na extração e comercialização destas opalas, assim como a falta de informações quanto à gênese destes depósitos não permitem a prospecção por novas jazidas e o estabelecimento de um certificado de procedência para as opalas do Piauí que permitisse sua inserção formal no mercado gemológico internacional. Alguns autores têm se dedicado ao estudo dessas opalas, revelando fortes evidências de sua origem hidrotermal, mas até então, nenhum trabalho abordou as características físico-químicas dos fluidos que teriam originado esses depósitos de opalas. Diante disso, o principal objetivo deste trabalho foi entender o sistema hidrotermal responsável pela gênese das opalas do Piauí, ou seja, caracterizar os fluidos que originaram a mineralização e mostrar sua relação com o contexto geológico da região. Os municípios de Pedro II e Buriti dos Montes se localizam na porção nordeste do estado do Piauí, a aproximadamente 230 km a leste da capital Teresina, e as ocorrências de opala se encontram na porção basal da Bacia do Parnaíba, constituindo veios e vênulas nos arenitos dos grupos Serra Grande (Buriti dos Montes) e Canindé (Pedro II), os quais são seccionados por soleiras e diques de diabásio da Formação Sardinha. Elas também ocorrem cimentando brechas e como depósitos coluvionares e de paleocanal. Associados às opalas, localmente encontram-se veios de quartzo, calcedônia, barita e hematita (ou goethita). De maneira geral, as opalas de Pedro II apresentam jogo de cores, são predominantemente brancas ou azuladas com aspecto leitoso, semitranslúcidas a opacas e com inclusões sólidas pouco aparentes. Em contrapartida, as opalas de Buriti dos Montes não apresentam jogo de cores, a cor varia entre amarelo claro e vermelho amarronzado, são semitransparentes a translúcidas e contêm grande variedade de inclusões sólidas. Os dados obtidos revelam que as opalas de Pedro II são tipicamente do tipo amorfo (opala-A), enquanto as opalas de Buriti dos Montes variam entre amorfas e cristobalita-tridimita (opala-CT). Na opala preciosa, o típico jogo de cores é causado pelo arranjo regular das esferas de sílica que as constituem. A ausência de cimento opalino entre as esferas reforça a beleza desse efeito. Em contrapartida, as opalas laranja não apresentam jogo de cores, mas têm maior transparência devido ao diminuto tamanho das esferas. As inclusões sólidas também produzem belos efeitos nas opalas estudadas, principalmente na variedade laranja, que é mais transparente. Além disso, o conjunto de inclusões sólidas revela características intrínsecas aos processos hidrotermais que originaram as opalas estudadas. Agregados botrioidais, dendríticos e nodulares são exemplos de inclusões formadas por fragmentos dos arenitos hospedeiros carreados pelos fluidos hidrotermais que geraram as opalas. As inclusões sólidas também têm relação direta com a cor das opalas. Nas opalas de Buriti dos Montes, os tons de vermelho, laranja e amarelo são produzidos pela dissolução parcial das inclusões constituídas por oxihidróxidos de Fe. De maneira semelhante, a cor verde nas opalas preciosas está relacionada aos microcristais de Co-pentlandita inclusos nas mesmas. O conjunto de minerais associados às opalas conduz a uma assinatura mineralógicogeoquímica marcada pelos elevados teores de Fe e Al nas opalas com inclusões de hematita/goethita e caulinita, e assim também com aumento considerável dos teores de elementos terras raras nas opalas em que se concentram as inclusões de caulinita e apatita. Entre os elementos-traço, Ba é o mais abundante, e provavelmente foi incorporado pelo fluido hidrotermal, tendo em vista que veios de barita são encontrados com frequência nessa região da Bacia do Parnaíba. Várias feições como estruturas de fluxo nas opalas, corrosão e dissolução parcial dos cristais de quartzo hialino e de inclusões mineralógicas, vênulas de quartzo hidrotermal sobrecrescidas aos grãos detríticos, e zoneamento dos cristais de quartzo confirmam que essas opalas têm origem hidrotermal. A ruptura do Gondwana teria provocado um vasto magmatismo básico fissural, que por sua vez foi responsável pelo aporte de calor que gerou as primeiras células convectivas de fluidos quentes. A água contida nos arenitos certamente alimentou o sistema e se enriqueceu em sílica através da dissolução parcial ou total dos próprios grãos de quartzo dos arenitos. Este fluido hidrotermal foi posteriormente aprisionado em sistemas de fraturas e nelas se resfriou, precipitando a opala e minerais associados.

Comparison of model potentials for molecular dynamics simulation of crystalline silica

Simulationen von SiO2 mit dem von van Beest, Kramer und vanSanten (BKS) entwickelten Paarpotenzial erzeugen vielezufriedenstellende Ergebnisse, aber auch charakteristischeSchwachstellen. In dieser Arbeit wird das BKS-Potenzial mitzwei kürzlich vorgeschlagenen Potenzialen verglichen, dieeffektiv Mehrteilchen-Wechselwirkungen beinhalten. Der ersteAnsatz erlaubt dazu fluktuierende Ladungen, der zweiteinduzierbare Polarisierungen auf den Sauerstoffatomen. Die untersuchten Schwachstellen des BKS Potenzialsbeinhalten das Verhältnis der zwei Gitterkonstanten a und cim Quarzübergang, das von BKS falsch beschrieben wird.Cristobalit und Tridymit erscheinen instabil mit BKS.Weiterhin zeigt die BKS-Zustandsdichte charakteristischeAbweichungen von der wahren Zustandsdichte. DerÜbergangsdruck für den Stishovit I-II Übergang wird deutlichüberschätzt. Das Fluktuierende-Ladungs-Modell verbesserteinige der genannten Punkte, reproduziert aber viele andereEigenschaften schlechter als BKS. DasFluktierende-Dipol-Modell dagegen behebt alle genanntenArtefakte. Zusätzlich wird der druckinduzierte Phasenübergang imalpha-Quarz untersucht. Alle Potentiale finden die selbeStruktur für Quarz II. Bei anschliessender Dekompressionerzeugt BKS eine weitere Phase, während die beiden anderenPotentiale wieder zum alpha-Quarz zurückkehren. Weiterhinwerden zwei Methoden entwickelt, um die piezoelektrischenKonstanten bei konstantem Druck zu bestimmen. Die Ergebnissegeben Hinweise auf eine möglicherweisenicht-elektrostatische Natur der Polarisierungen imFluktuierende-Dipole-Modell. Mit dieser Interpretation scheint das Fluktuierende-DipolPotential alle verfügbaren experimentellen Daten am bestenvon allen drei untersuchten Ansätzen zu reproduzieren.

Geochemistry and mineralogy of Eocene-Oligocene sediments of IODP Hole 302-M0002A

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.

Biogenic silica in ODP Hole 105-647A

Eocene to Holocene sediments from Ocean Drilling Program (ODP) Site 647 (Leg 105) in the southern Labrador Sea, approximately 200 km south of the Gloria Drift deposits, were investigated for their biogenic silica composition. Three sections of different diagenetic alteration products of primary siliceous components could be distinguished: (1) opal-A was recorded in the Miocene and the early Oligocene time intervals with strongly corroded siliceous skeletons in the Miocene and mostly well preserved biogenic opal in the early Oligocene; (2) opal-CT precipitation occurs between 250-440 meters below seafloor (mbsf) (earliest Oligocene to late Eocene); (3) between 620-650 mbsf (early/middle Eocene), biogenic opal was transformed to clay minerals by authigenesis of smectites. Using accumulation rates of biogenic opal, paleoproductivity was estimated for the early Oligocene to late Eocene interval. A maximum productivity of biogenic silica probably occurred between 35.5 and 34.5 Ma (early Oligocene). No evidence for opal sedimentation during most of middle Eocene was found. However, at the early/middle Eocene boundary (around 52 Ma), increased opal fluxes were documented by diagenetic alteration products of siliceous skeletons.

Geochemistry and mineralogy of variably altered dacite volcanic rocks from ODP Leg 193 sites, PACMANUS field

A geochemical, mineralogical, and isotopic database comprising 75 analyses of Ocean Drilling Program (ODP) Leg 193 samples has been prepared, representing the variable dacitic volcanic facies and alteration types observed in drill core from the subsurface of the PACMANUS hydrothermal system (Table T1. The data set comprises major elements, trace and rare earth elements (REE), various volatiles (S, F, Cl, S, SO4, CO2, and H2O), and analyses of 18O and 86Sr/87Sr for bulk rock and mineral separates (anhydrite). Furthermore, normative mineral proportions have been calculated based on the results of X-ray diffraction (XRD) analysis (Table T2) using the SOLVER function of the Microsoft Excel program. Several of the samples analyzed consist of mesoscopically distinctive domains, and separate powders were generated to investigate these hand specimen-scale heterogeneities. Images of all the samples are collated in Figure F1, illustrating the location of each powder analyzed and documenting which measurements were performed.