22 resultados para Zr
em Biblioteca Digital da Produção Intelectual da Universidade de São Paulo
Resumo:
Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.
Resumo:
High-grade metasedimentary rocks can preserve geochemical signatures of their sedimentary protolith if significant melt extraction did not occur. Retrograde reaction textures provide the main evidence for trapped melt in the rock fabrics. Carvalhos Klippe rocks in Southern Brasilia Orogen, Brazil, present a typical high-pressure granulite assemblage with evidence of mica breakdown partial melting (Ky + Grt + Kfs +/- Bt +/- Rt). The metamorphic peak temperatures obtained by Zr-in-Rt and ternary feldspar geothermometers are between 850 degrees C and 900 degrees C. The GASP bane peak pressure obtained using grossular rich garnet core is 16 kbar. Retrograde reaction textures in which the garnet crystals are partially to totally replaced by Bt + Qtz +/- Fsp intergrowths are very common in the Carvalhos Klippe rocks. These reactions are interpreted as a result of interactions between residual phases and trapped melt during the retrograde path. In the present study the geochemical signatures of three groups of Carvalhos Klippe metasedimentary rocks are analysed. Despite the high metamorphic grade these three groups show well-defined geochemical features and their REE patterns are similar to average compositions of post-Archean sedimentary rocks (PAAS, NASC). The high-pressure granulite facies Grt-Bt-Pl gneisses with immature arenite (wacke, arkose or lithic-arenite) geochemical signatures present in the Carvalhos Klippe are compared to similar rocks in amphibolite facies from the same tectonic framework (Andrelandia Nappe System). The similar geochemical signatures between Grt-Bt-Pl gneisses metamorphosed in high-pressure granulite facies and Grt-Bt-Pl-Qtz schists from the Andrelandia and Liberdade Nappes, with minimal to absent melting conditions, are suggestive of low rates of melt extraction in these high-grade rocks. The rocks with pelitic compositions most likely had higher melt extraction and even under such circumstances nevertheless tend to show REE patterns similar to average compositions of post-Archean sedimentary rocks (PAAS, NASC). (C) 2012 Elsevier Ltd. All rights reserved.
Resumo:
The north-western sector of the Gharyan volcanic field (northern Libya) consists of trachytic-phonolitic domes emplaced between similar to 41 and 38 Ma, and small-volume mafic alkaline volcanic centres (basanites, tephrites. alkali basalts. hawaiites and rare benmoreites) of Middle Miocene-Pliocene age (similar to 12-2 Ma). Two types of trachytes and phonolites have been recognized on the basis of petrography, mineralogy and geochemistry. Type-1 trachytes and phonolites display a smooth spoon-shaped REE pattern without negative Europium anomalies. Type-2 trachytes and phonolites show a remarkable Eu negative anomaly, higher concentration in HFSE (Nb-Ta-Zr-Hf), REE and Ti than Type-1 rocks. The origin of Type-1 trachytes and phonolites is compatible with removal of clinopyroxene, plagioclase, alkali feldspar, amphibole. magnetite and titanite starting from benmoreitic magmas. found in the same outcrops. Type-2 trachytes and phonolites could be the result of extensive fractional crystallization starting from mafic alkaline magma, without removal of titanite. In primitive mantle-normalized diagrams, the mafic rocks (Mg#= 62-68, Cr up to 514 ppm, Ni up to 425 ppm) show peaks at Nb and Ta and troughs at K. These characteristics, coupled with low Sr-87/Sr-86(i) (0.7033-0.7038) and positive epsilon(Nd) (from +4.2 to + 5.3) features typical of the mafic anorogenic magmas of the northern African plate and of HIMU-OIB-like magma in general. The origin of the mafic rocks is compatible from a derivation from low degree partial melting (3-9%) shallow mantle sources in the spinel/gamet facies. placed just below the rigid plate in the uppermost low-velocity zone. The origin of the igneous activity is considered linked to passive lithospheric thinning related to the development of continental rifts like those of Sicily Channel (e.g.. Pantelleria and Linosa) and Sardinia (e.g., Campidano Graben) in the Central-Western Mediterranean Sea. (C) 2012 Elsevier B.V. All rights reserved.
Resumo:
The early phase of post-collisional granitic magmatism in the Camboriu region, south Brazil, is represented by the porphyritic biotite +/- hornblende Rio Pequeno Granite (RPG; 630-620 Ma) and the younger (similar to 610 Ma), equigranular, biotite +/- muscovite Serra dos Macacos Granite (SMG). The two granite types share some geochemical characteristics, but the more felsic SMG constitutes a distinctive group not related to RPG by simple fractionation processes, as indicated by its lower FeOt, TiO2, K2O/Na2O and higher Zr Al2O3, Na2O, Ba and Sr when compared to RPG of similar SiO2 range. Sr-Nd-Pb isotopes require different sources. The SMG derives from old crustal sources, possibly related to the Paleoproterozoic protoliths of the Camboriu Complex, as indicated by strongly negative epsilon Nd-t (-23 to -24) and unradiogenic Pb (e.g., Pb-206/Pb-204 = 16.0-16.3; Pb-207/Pb-204 = 15.3-15.4) and confirmed by previous LA-MC-ICPMS data showing dominant zircon inheritance of Archean to Paleoproterozoic age. In contrast, the RPG shows less negative epsilon Nd-t (-12 to -15) and a distinctive zircon inheritance pattern with no traces of post-1.6 Ga sources. This is indicative of younger sources whose significance in the regional context is still unclear; some contribution of mantle-derived magmas is indicated by coeval mafic dykes and may account for some of the geochemical and isotopic characteristics of the least differentiated varieties of the RPG. The transcurrent tectonics seems to have played an essential role in the generation of mantle-derived magmas despite their emplacement within a low-strain zone. It may have facilitated their interaction with crustal melts which seem to be to a large extent the products of reworking of Paleoproterozoic orthogneisses from the Camboriu Complex. (C) 2012 Elsevier Ltd. All rights reserved.
Resumo:
A new and simple criterion with which to quantitatively predict the glass forming ability (GFA) of metallic alloys is proposed. It was found that the critical cooling rate for glass formation (R-C) correlates well with a proper combination of two factors, the minimum topological instability (lambda(min)) and the Delta h parameter, which depends on the average work function difference (Delta phi) and the average electron density difference (Delta n(ws)(1/3)) among the constituent elements of the alloy. A correlation coefficient (R-2) of 0.76 was found between R-c and the new criterion for 68 alloys in 30 different metallic systems. The new criterion and the Uhlmann's approach were used to estimate the critical amorphous thickness (Z(C)) of alloys in the Cu-Zr system. The new criterion underestimated R-C in the Cu-Zr system, producing predicted Z(C) values larger than those observed experimentally. However, when considering a scale factor, a remarkable similarity was observed between the predicted and the experimental behavior of the GFA in the binary Cu-Zr. When using the same scale factor and performing the calculation for the ternary Zr-Cu-Al, good agreement was found between the predicted and the actual best GFA region, as well as between the expected and the observed critical amorphous thickness. (C) 2012 American Institute of Physics. [doi:10.1063/1.3676196]
Resumo:
The objective of this study was to determine the size and composition of atmospheric aerosols in the downtown area of the city of So Paulo, Brazil, for a polluted and an unpolluted period. Aerosols were sampled with a portable air sampler (PAS), Micro-Orifice Uniform Deposit Impactor (MOUDI), and Scanning Mobility Particle Sizer. At the study site, air quality is poor, especially during the winter, high concentrations of pollutants being emitted primarily by the light- and heavy-duty vehicle fleet. We analyzed mass, black carbon (BC), Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sn, Zr, and Pb. During the polluted period, diurnal PM(10) was higher than nocturnal PM(10), whereas the inverse was true during the unpolluted period. The FPM was rich in BC, S, and Pb, whereas CPM was rich in Al, Si, Ca, Ti, and Fe. Mass balance was performed by category: ammonium sulfate, sodium chloride, crustal material, BC, and other. The PAS-determined FPM was mainly BC. The MOUDI-determined FPM crustal material explained more mass than did ammonium sulfate and BC during the polluted period, whereas ammonium sulfate had the largest mass during the unpolluted period. Crustal material was the major CPM component, followed by ammonium sulfate and BC. During the unpolluted period, FPM concentrations were lower, whereas those of ammonium sulfate were relatively higher, especially at night, and particle number was inversely proportional to particle size. Aerosol growth was more intense during the polluted period.
Resumo:
This study aimed to test different protocols for the extraction of microbial DNA from the coral Mussismilia harttii. Four different commercial kits were tested, three of them based on methods for DNA extraction from soil (FastDNA SPIN Kit for soil, MP Bio, PowerSoil DNA Isolation Kit, MoBio, and ZR Soil Microbe DNA Kit, Zymo Research) and one kit for DNA extraction from plants (UltraClean Plant DNA Isolation Kit, MoBio). Five polyps of the same colony of M. harttii were macerated and aliquots were submitted to DNA extraction by the different kits. After extraction, the DNA was quantified and PCR-DGGE was used to study the molecular fingerprint of Bacteria and Eukarya. Among the four kits tested, the ZR Soil Microbe DNA Kit was the most efficient with respect to the amount of DNA extracted, yielding about three times more DNA than the other kits. Also, we observed a higher number and intensities of DGGE bands for both Bacteria and Eukarya with the same kit. Considering these results, we suggested that the ZR Soil Microbe DNA Kit is the best adapted for the study of the microbial communities of corals.
Resumo:
Two Zircaloy 4-Ta alloys (14 and 55 wt.% Ta) were produced by arc-melting. The alloys were hot-rolled at 900 degrees C and heat-treated under argon atmosphere for 100 h at 700 degrees C. The alloys were analyzed by scanning electron microscopy and X-ray diffractometry. The microstructure of both rolled and heat-treated alloys is constituted of (beta Zr,Ta)-II Ta-rich precipitates dispersed in a (alpha Zr) matrix. Corrosion tests performed in boiling concentrated H2SO4 solutions showed that the Zircaloy 4-Ta alloys are more corrosion resistant than Zircaloy 4 and that the corrosion resistance increases with increasing Ta content. (c) 2012 Elsevier Ltd. All rights reserved.
Resumo:
In this work, a Monte Carlo code was used to investigate the performance of different x-ray spectra in digital mammography, through a figure of merit (FOM), defined as FOM = CNR2/(D) over bar (g), with CNR being the contrast-to-noise ratio in image and (D) over bar (g) being the average glandular dose. The FOM was studied for breasts with different thicknesses t (2 cm <= t <= 8 cm) and glandular contents (25%, 50% and 75% glandularity). The anode/filter combinations evaluated were those traditionally employed in mammography (Mo/Mo, Mo/Rh, Rh/Rh), and a W anode combined with Al or K-edge filters (Zr, Mo, Rh, Pd, Ag, Cd, Sn), for tube potentials between 22 and 34 kVp. Results show that the W anode combined with K-edge filters provides higher values of FOM for all breast thicknesses investigated. Nevertheless, the most suitable filter and tube potential depend on the breast thickness, and for t >= 6 cm, they also depend on breast glandularity. Particularly for thick and dense breasts, a W anode combined with K-edge filters can greatly improve the digital technique, with the values of FOM up to 200% greater than that obtained with the anode/filter combinations and tube potentials traditionally employed in mammography. For breasts with t < 4 cm, a general good performance was obtained with the W anode combined with 60 mu m of the Mo filter at 24-25 kVp, while 60 mu m of the Pd filter provided a general good performance at 24-26 kVp for t = 4 cm, and at 28-30 and 29-31 kVp for t = 6 and 8 cm, respectively.
Resumo:
The Neoproterozoic post-collisional period in southern Brazil (650-580 Ma) is characterized by substantial volumes of magma emplaced along the active shear zones that compose the Southern Brazilian Shear Belt. The early-phase syntectonic magmatism (630-610 Ma) is represented by the porphyritic, high-K, metaluminous to peraluminous Quatro Ilhas Granitoids and the younger heterogranular, slightly peraluminous Mariscal Granite. Quatro II has Granitoids include three main petrographic varieties (muscovite-biotite granodiorite mbg; biotite monzogranite - bmz: and leucogranite - lcg) that, although sharing some significant geochemical characteristics, are not strictly comagmatic, as shown by chemical and Sr-Nd-Pb isotope data. The most primitive muscovite-biotite granodiorite was produced by contamination of more mafic melts (possibly with some mantle component) with peraluminous crustal melts; the biotite monzogranite, although more felsic, has higher Ca, MgO,TiO2 and Ba, and lower K2O, FeOt, Sr and Rb contents, possibly reflecting some mixing with coeval mafic magmas of tholeiitic affinity; the leucogranite may be derived from pure crustal melts. The Mariscal Granite is formed by two main granite types which occur intimately associated in the same pluton, one with higher K (5-6.5 wt.% K2O) high Rb and lower CaO, Na2O, Ba and Zr as compared to the other (3-5 wt.% of K2O). The two Mariscal Granite varieties have compositional correspondence with fine-grained granites (fgg) that occur as tabular bodies which intruded the Quatro Ilhas Granoitoids before they were fully crystallized, and are inferred to correspond to the Mariscal Granite feeders, an interpretation that is reinforced by similar U-Pb zircon crystallization ages. The initial evolution of the post-collisional magmatism, marked by the emplacement of the Quatro Ilhas Granitoids varieties, activated sources that produced mantle and crustal magmas whose emplacement was controlled both by flat-lying and transcurrent structures. The transition from thrust to transcurrent-related tectonics coincides with the increase in the proportion of crustal-derived melts. The transcurrent tectonics seems to have played an essential role in the generation of mantle-derived magmas and may have facilitated their interaction with crustal melts which seem to be to a large extent the products of reworking of orthogneiss protoliths. (C) 2012 Elsevier B.V. All rights reserved.
Resumo:
The effects of substituting Si by M4+ cations in soda-lime silica glasses were analyzed by impedance spectroscopy in the frequency range of 1 Hz-1 MHz. The glass composition was (mol%) 22Na(2)O center dot 8CaO center dot 65SiO(2)center dot 5MO(2), M = Si, Ti, Ge, Zr, Sn, and Ce. Although the Na+ concentration in the glasses is constant, the Zr-containing glass exhibits the highest dc conductivity and the lowest activation energy, while the Ce-containing glass exhibits the lowest conductivity. The activation energies obtained experimentally agree with those obtained by a theoretical equation proposed by Anderson and Stuart. The differences in electrical conductivity presented by the several M-containing glasses are attributed to the effect that the M4+ ion has on the mobility of the diffusing Na+ ion. (C) 2012 Elsevier B.V. All rights reserved.
Resumo:
Major and trace-element microanalyses of the main minerals from the 610 Ma Pedra Branca Syenite, southeast Brazil, allow inferences on intensive parameters of magmatic crystallization and on the partition of trace-elements among these minerals, with important implications for the petrogenetic evolution of the pluton. Two main syenite types make up the pluton, a quartz-free syenite with tabular alkali feldspar (laminated silica-saturated syenite, LSS, with Na-rich augite + phlogopite + hematite + magnetite + titanite + apatite) and a quartz-bearing syenite (laminated silica-oversaturated syenite, LSO, with scarce corroded plagioclase plus diopside + biotite +/- hornblende + ilmenite magnetite +/- titanite + apatite). Both types share a remarkable enrichment in incompatible elements as K, Ba, Sr, P and LREE. Apatite saturation temperatures of similar to 1060-1090 degrees C are the best estimates of liquidus, whereas the pressure of emplacement, based on Al-in-hornblende barometry, is estimated as 3.3 to 4.8 khan Although both units crystallized under oxidizing conditions, oxygen fugacity was probably higher in LSS, as shown by higher mg# of the mafic minerals and higher hematite contents in Hem-Ilm(ss). In contrast with the Ca-bearing alkali-feldspar from LSO, which hosts most of the whole-rock Sr and Pb, virtually Ca-free alkali-feldspar from LSS hosts similar to 50% of whole-rock Sr and similar to 80% of Pb, the remainder of these elements being shared by apatite, pyroxene and titanite. This contrast reflects a strong crystal-chemical control, whereby a higher proportion of an element with similar ratio and charge (Ca2+) enhances the residence of Sr and Pb in the M-site of alkali feldspar. The more alkaline character of the LSS magma is inferred to have inhibited zircon saturation; Zr + Hf remained in solution until late in the crystallization, and were mostly accommodated in the structure of Ca-Na pyroxene and titanite, which are one order of magnitude richer in these elements compared to the same minerals in LSO, where most of Zr and Hf are inferred to reside in zircon. The REE, Th and U reside mostly in titanite and apatite; D(REE)Tit/Ap raises steadily from 1 to 6 from La to Tb then remains constant up to Lu in the LSO sample; these values are about half as much in the LSS sample, where lower contents of incompatible elements in titanite are attributed to its greater modal abundance and earlier crystallization. (C) 2012 Elsevier B.V. All rights reserved.
Resumo:
We present a detailed study of carbon-enhanced metal-poor (CEMP) stars, based on high-resolution spectroscopic observations of a sample of 18 stars. The stellar spectra for this sample were obtained at the 4.2 m William Herschel Telescope in 2001 and 2002, using the Utrecht Echelle Spectrograph, at a resolving power R similar to 52 000 and S/N similar to 40, covering the wavelength range lambda lambda 3700-5700 angstrom. The atmospheric parameters determined for this sample indicate temperatures ranging from 4750 K to 7100 K, log g from 1.5 to 4.3, and metallicities -3.0 <= [Fe/H]<=-1.7. Elemental abundances for C, Na, Mg, Sc, Ti, Cr, Cu, Zn, Sr, Y, Zr, Ba, La, Ce, Nd, Sm, Eu, Gd, Dy are determined. Abundances for an additional 109 stars were taken from the literature and combined with the data of our sample. The literature sample reveals a lack of reliable abundance estimates for species that might be associated with the r-process elements for about 67% of CEMP stars, preventing a complete understanding of this class of stars, since [Ba/Eu] ratios are used to classify them. Although eight stars in our observed sample are also found in the literature sample, Eu abundances or limits are determined for four of these stars for the first time. From the observed correlations between C, Ba, and Eu, we argue that the CEMP-r/s class has the same astronomical origin as CEMP-s stars, highlighting the need for a more complete understanding of Eu production.
Resumo:
In this study, catalysts containing 5 wt.% Ni deposited on a support composed of a CeO2-ZrO2 solid solution deposited on alumina were tested in the steam reforming of methane. The supports, with various ratios of Ce to Zr, were prepared by co-precipitation of the oxide precursors, followed by calcination in synthetic air. The catalysts were then prepared by Ni impregnation of the supports. The prepared solids were characterized by temperature-programmed reduction with H-2 (TPR-H-2), in situ X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES) spectroscopy. The XRD analysis confirmed the formation of a solid solution between ZrO2 and CeO2. In the catalytic tests, it was found that catalysts with higher Ce content did not exhibit deactivation during 6 h of reaction. The catalyst with highest Ce content, Ni(0.8Ce0.2Zr)AI, provided the best result, with the highest rate of conversion of methane and the lowest carbon deposition, which may be partly due to the smaller Ni-0 crystallites in this sample and also the segregated CeO2 particles may have favored H2O adsorption which could lead to higher C gasification. (C) 2012 Elsevier B.V. All rights reserved.
Resumo:
Background: Metastasis is the main factor responsible for death in breast cancer patients. Matrix metalloproteinases (MMPs) and their inhibitors, known as tissue inhibitors of MMPs (TIMPs), and the membrane-associated MMP inhibitor (RECK), are essential for the metastatic process. We have previously shown a positive correlation between MMPs and their inhibitors expression during breast cancer progression; however, the molecular mechanisms underlying this coordinate regulation remain unknown. In this report, we investigated whether TGF-beta 1 could be a common regulator for MMPs, TIMPs and RECK in human breast cancer cell models. Methods: The mRNA expression levels of TGF-beta isoforms and their receptors were analyzed by qRT-PCR in a panel of five human breast cancer cell lines displaying different degrees of invasiveness and metastatic potential. The highly invasive MDA-MB-231 cell line was treated with different concentrations of recombinant TGF-beta 1 and also with pharmacological inhibitors of p38 MAPK and ERK1/2. The migratory and invasive potential of these treated cells were examined in vitro by transwell assays. Results: In general, TGF-beta 2, T beta RI and T beta RII are over-expressed in more aggressive cells, except for T beta RI, which was also highly expressed in ZR-75-1 cells. In addition, TGF-beta 1-treated MDA-MB-231 cells presented significantly increased mRNA expression of MMP-2, MMP-9, MMP-14, TIMP-2 and RECK. TGF-beta 1 also increased TIMP-2, MMP-2 and MMP-9 protein levels but downregulated RECK expression. Furthermore, we analyzed the involvement of p38 MAPK and ERK1/2, representing two well established Smad-independent pathways, in the proposed mechanism. Inhibition of p38MAPK blocked TGF-beta 1-increased mRNA expression of all MMPs and MMP inhibitors analyzed, and prevented TGF-beta 1 upregulation of TIMP-2 and MMP-2 proteins. Moreover, ERK1/2 inhibition increased RECK and prevented the TGF-beta 1 induction of pro-MMP-9 and TIMP-2 proteins. TGF-beta 1-enhanced migration and invasion capacities were blocked by p38MAPK, ERK1/2 and MMP inhibitors. Conclusion: Altogether, our results support that TGF-beta 1 modulates the mRNA and protein levels of MMPs (MMP-2 and MMP-9) as much as their inhibitors (TIMP-2 and RECK). Therefore, this cytokine plays a crucial role in breast cancer progression by modulating key elements of ECM homeostasis control. Thus, although the complexity of this signaling network, TGF-beta 1 still remains a promising target for breast cancer treatment.