Bond durability in erbium:yttrium-aluminum-garnet laser-irradiated enamel

This study sought to evaluate the influence of thermocycling and water storage on the microtensile bond strength of composite resin bonded to erbium:yttrium-aluminum-garnet (Er:YAG)-irradiated and bur-prepared enamel. Eighty bovine incisors were selected and sectioned. Specimens were ground to produce a flat enamel surface. Samples were randomly assigned according to cavity preparation device: (I) Er:YAG laser and (II) high-speed turbine, and were subsequently restored with composite resin. They were subdivided according to the duration of water storage (WS)/number of thermocycles (TCs): 24 h WS/no TCs; 7 days WS/500 TCs; 1 month WS/2,000 TCs; 6 months WS/12,000 TCs. The teeth were sectioned into 1.0 mm(2)-thick slabs and subjected to tensile stress in a universal testing machine. Data were submitted to two-way analysis of variance (ANOVA) and Tukey`s test at a 0.05 significance level. The different periods of water storage and thermocycling did not influence the microtensile bond strength (A mu TBS) values in the Er:YAG laser-prepared groups. In bur-prepared enamel, the group submitted to 12,000 TCs/6 months` WS (IID) showed a significant decrease in bond strength values when compared to the group stored in water for 24 h and not submitted to thermocycling (IIA), but values were statistically similar to those obtained in all Er:YAG laser groups and in the bur- prepared groups degraded with 500 TCs/1 week WS (IIB) or 2,000 TCs/1 month WS (IIC). It may be concluded that adhesion of an etch-and-rinse adhesive to Er:YAG laser-irradiated enamel was not affected by the methods used to simulate degradation of the adhesive interface and was similar to adhesion in the bur-prepared groups in all periods of water storage and thermocycling.

Electronic and optical properties of grossular garnet (Ca(3)Al(2)Si(3)O(12)): An ab initio study

The electronic and optical properties of grossular garnet are investigated using density functional theory (DFT) within generalized gradient approximation (GGA). The calculated lattice parameters are in good agreement with the experiment data. The electronic structure shows that grossular has a direct band gap of 5.22 eV. The dielectric functions, reflective index, extinction coefficient, reflectivity and energy-loss spectrum are calculated. The optical properties of grossular are discussed based on the band structure calculations. The O 2p states and Si 3s play a major role in these optical transitions as initial and final states, respectively. The absorption spectrum is localized in the ultraviolet range between 30 and 250 nm. Finally, we concluded that pure grossular crystal does not absorb radiation in the visible range. (c) 2009 Elsevier B.V. All rights reserved.

Infrared emissions, visible up-conversion, thermoluminescence and defect centres in Er(3)Al(5)O(12) phosphor obtained by solution combustion reaction

The Er(3)Al(5)O(12) phosphor powders were prepared using the solution combustion method. Formation and homogeneity of the Er(3)Al(5)O(12) phosphor powders have been verified by X-ray diffraction and energy-dispersive X-ray analysis respectively. The frequency up-conversion from Er(3)Al(5)O(12) phosphor powder corresponding to the (2)H(9/2) -> (4)I(15/2), (2)H(11/2) -> (4)I(15/2), (4)S(3/2) -> (4)I(15/2), (4)F(9/2) -> (4)I(15/2) and the infrared emission (IR) due to the (4)I(13/2) -> (4)I(15/2) transitions lying at similar to 410, similar to 524, similar to 556, 645-680 nm and at similar to 1.53 mu m respectively upon excitation with a Ti-Sapphire pulsed/CW laser have been reported. The mechanism responsible for the frequency up-conversion and IR emission is discussed in detail. Defect centres induced by radiation were studied using the techniques of thermoluminescence and electron spin resonance. A single glow peak at 430A degrees C is observed and the thermoluminescence results show the presence of a defect center which decays at high temperature. Electron spin resonance studies indicate a center characterized by a g-factor equal to 2.0056 and it is observed that this center is not related to the thermoluminescence peak. A negligibly small concentration of cation and anion vacancies appears to be present in the phosphor in accordance with the earlier theoretical predictions.

Infrared emission and defect centres in Er and Yb codoped Y(3)Al(5)O(12) phosphors

YAG phosphor powders doped/codoped with Er(3+)/(Er(3+) + Yb(3+)) have been synthesised by using the solution combustion method. The effect of direct pumping into the (4)I(11/2) level under 980 nm excitation of doped/codoped Er(3+)/Yb(3+)-Er(3+) in Y(3)Al(5)O(12) (YAG) phosphor responsible for an infrared (IR) emission peaking at similar to 1.53 mu m corresponding to the (4)I(13/2)->(4)I(15/2) transition has been studied. YAG exhibits three thermally-stimulated luminescence (TSL) peaks at around 140A degrees C, 210A degrees C and 445A degrees C. Electron spin resonance (ESR) studies were carried out to identify the centres responsible for the TSL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0176 is identified as O(-) ion, while centre II with an isotropic g-factor 2.0020 is assigned to an F(+) centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal-annealing experiments and this centre (assigned to F(+) centre) seems to originate from an F-centre (oxygen vacancy with two electrons) and these two centres appear to correlate with the observed high-temperature TSL peak in YAG phosphor.

TL, EPR and optical absorption in natural grossular crystal

Grossular is one of six members of silicate Garnet group. Two samples GI and GII have been investigated concerning their luminescence thermally stimulated (TL). EPR and optical absorption and the measurements were carried out to find out whether or not same point defects are responsible for all three properties. Although X-rays diffraction analysis has shown that both GI and GII have practically the same crystal structure of a standard grossular crystal, they presented different behavior in many aspects. The TL glow curve shape, TL response to radiation dose, the effect of annealing at high temperatures before irradiation, the dependence of UV bleaching parameters on peak temperature, all of them differ going from GI to GII. The EPR signals around g = 2.0 as well as at g = 4.3 and 6.0 have much larger intensity in GI than in GII. Very high temperature (> 800 degrees C annealing causes large increase in the bulk background absorption in GI, however, only very little in GII. In the cases of EPR and optical absorption, the difference in their behavior can be attributed to Fe3+ ions; however, in the TL case one cannot and the cause was not found as yet. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis of YAP nanopowder by a soft chemistry route

Polycrystalline fine powder of YAlO(3) (YAP) was synthesized by the modified polymeric precursor method. A preliminary gradual pyrolytic decomposition under nitrogen flux was crucial in the removal process of organic residues to avoid the formation of molecular level inhomogeneities. YAP single phase was crystallized at temperatures between 950 degrees C and 1000 degrees C using chemically homogeneous ball-milled amorphous particles and very fast heating rates, corresponding to the lowest synthesis temperature of pure YAP nanopowder by soft chemistry routes. (C) 2009 Elsevier Ltd. All rights reserved.

Synthesis of YAP phase by a polymeric method and phase progression mechanisms

The phase formation kinetics of YAP (YAlO(3)) synthesized through the polymeric precursor method was investigated by thermal analysis, X-ray diffraction and FT-IR spectroscopy. We demonstrated that the YAP synthesis is highly dependent on the heat and mass transport during all stages of the synthesis route. In the first stages, during the preparation of amorphous precursor, ""hot spots"" need to be suppressed to avoid the occurrence of chemical inhomogeneities. Very high heating rates combined with small amorphous particles are advantageous in the last stage during the formation of crystalline phase. We were able to synthesize nanosized particles of YAP single phase at temperatures around 1100 A degrees C for future preparation of phosphors or ceramics for optics.

High T/P evolution and metamorphic ages of the migmatitic basement of northern Sierras Pampeanas, Argentina: Characterization of a mid-crustal segment of the Famatinian belt

New petrologic, thermobarometric and U-Pb monazite geochronologic information allowed to resolve the metamorphic evolution of a high temperature mid-crustal segment of an ancient subduction-related orogen. The EI Portezuelo Metamorphic-Igneous Complex, in the northern Sierras Pampeanas, is mainly composed of migmatites that evolved from amphibolite to granulite metamorphic facies, reaching thermal peak conditions of 670-820 degrees C and 4.5-5.3 kbar. The petrographic study combined with conventional and pseudosection thermobarometry led to deducing a short prograde metamorphic evolution within migmatite blocks. The garnet-absent migmatites represent amphibolite-facies rocks, whereas the cordierite-garnet-K-feldspar-sillimanite migmatites represent higher metamorphic grade rocks. U-Pb geochronology on monazite grains within leucosome record the time of migmatization between approximate to 477 and 470 Ma. Thus, the El Portezuelo Metamorphic-Igneous Complex is an example of exhumed Early Ordovician anatectic middle crust of the Famatinian mobile belt. Homogeneous exposure of similar paleo-depths throughout the Famatinian back-arc and isobaric cooling paths suggest slow exhumation and consequent longstanding crustal residence at high temperatures. High thermal gradients uniformly distributed in the Famatinian back-arc can be explained by shallow convection of a low-viscosity asthenosphere promoted by subducting-slab dehydration. (C) 2011 Elsevier Ltd. All rights reserved.

Quartz recrystallization regimes, c-axis texture transitions and fluid inclusion reequilibration in a prograde greenschist to amphibolite facies mylonite zone (Ribeira Shear Zone, SE Brazil)

The crystal-plastic behavior of quartz mylonites from the Ribeira Shear Zone (SE Brazil), a major strike-slip structure that was active during a prograde metamorphic phase related to the Neoproterozoic Brasiliano-Pan African Orogeny, was investigated using a multi-method approach. Geothermobarometry results indicate deformational conditions ranging from similar to 300 to similar to 630 degrees C and 500-700 MPa. A strong correlation between mapped metamorphic zones and a dominance of different dynamic recrystallization mechanisms of quartz occurs within the mylonite zone. Bulging recrystallization (BLG) dominates within the chlorite zone between 300 and 410 degrees C, subgrain rotation recrystallization (SGR) operates within the biotite zone from 410 to 520 degrees C, and grain boundary migration recrystallization (GBM) dominates in the garnet zone above 520 degrees C. The development of quartz c-axis textures is mainly governed by temperature and dynamic recrystallization mechanisms. Textures from BLG zone mylonites are characterized by maxima around Z; SGR zone mylonites display single girdles or asymmetric type I crossed girdles; and GBM zone mylonites comprise maxima around Y and intermediate between X and Z. The scarcity or absence of water-bearing fluid inclusions in quartz mylonites from the SGR and GBM zones, which are dominated by carbonic inclusions, suggests water-deficient conditions, whereas BLG zone mylonites are dominated by water-bearing inclusions. This evidence indicates that water was available in the protoliths but has been eliminated with increasing deformation and deformation temperature. No effect of the water content variation on the quartz microstructural and recrystallized grain size evolution was detected, and little influence on c-axis texture development was observed. Most of the fluid inclusion densities were reequilibrated during the shear zone exhumation history, recording a decompression in the range of 300-500 MPa, while microstructural reequilibration effects related to the prograde metamorphism are largely preserved. Fluid inclusion microstructures and densities from two SGR zone samples preserved evidence for a near isothermal compression within the interior of the Ribeira Shear Zone during the prograde metamorphism. (C) 2009 Elsevier B.V. All rights reserved.

The link between partial melting, granitization and granulite development in central Ribeira Fold Belt, SE Brazil: New evidence from elemental and Sr-Nd isotopic geochemistry

Elemental and Sr-Nd isotopic data on metatexites, diatexites, orthogneisses and charnockites from the central Ribeira Fold Belt indicate that they are LILE-enriched weakly peraluminous granodiorites. Harker and Th-Hf-La correlation trends suggest that these rocks represent a co-genetic sequence, whereas variations on CaO, MnO, Y and HREE for charnockites can be explained by garnet consumption during granulitic metamorphism. Similar REE patterns and isotopic results of epsilon(565)(Nd) = -5.4 to -7.3 and (87)Sr/(86)Sr(565) = 0.706-0.711 for metatexites, diatexites, orthogneisses and charnockites, as well as similar T(DM) ages between 2.0 and 1.5 Ga are consistent with evolution from a relatively homogeneous and enriched common crustal (metasedimentary) protolith. Results suggest a genetic link between metatexites, diatexites, orthogneisses and charnockites and a two-step process for charnockite development: (a) generation of the hydrated igneous protoliths by anatexis of metasedimentary rocks; (b) continuous high-grade metamorphism that transformed the ""S-type granitoids"" (leucosomes and diatexites) into orthogneisses and, as metamorphism and dehydration progressed, into charnockites. (C) 2011 Elsevier Ltd. All rights reserved.

Thermochronology of central Ribeira Fold Belt, SE Brazil: Petrological and geochronological evidence for long-term high temperature maintenance during Western Gondwana amalgamation

The studied sector of the central Ribeira Fold Belt (SE Brazil) comprises metatexites, diatexites, charnockites and blastomylonites. This study integrates petrological and thermochronological data in order to constrain the thermotectonic and geodynamic evolution of this Neoproterozoic-Ordovician mobile belt during Western Gondwana amalgamation. New data indicate that after an earlier collision stage at similar to 610 Ma (zircon, U-Pb age), peak metamorphism and lower crust partial melting, coeval with the main regional high grade D(1) thrust deformation, occurred at 572-562 Ma (zircon, U-Pb ages). The overall average cooling rate was low (<5 degrees C/Ma) from 750 to 250 degrees C (at similar to 455 Ma; biotite-WR Rb-Sr age), but disparate cooling paths indicate differential uplift between distinct lithotypes: (a) metatexites and blastomylonites show a overall stable 3-5 degrees C/Ma cooling rate; (b) charnockites and associated rocks remained at T>650 degrees C during sub-horizontal D(2) shearing until similar to 510-470 Ma (garnet-WR Sm-Nd ages) (1-2 degrees C/Ma), being then rapidly exhumed/cooled (8-30 degrees C/Ma) during post-orogenic D(3) deformation with late granite emplacement at similar to 490 Ma (zircon, U-Pb age). Cooling rates based on garnet-biotite Fe-Mg diffusion are broadly consistent with the geochronological cooling rates: (a) metatexites were cooled faster at high temperatures (6 degrees C/Ma) and slowly at low temperatures (0.1 degrees C/Ma), decreasing cooling rates with time; (b) charnockites show low cooling rates (2 degrees C/Ma) near metamorphic peak conditions and high cooling rates (120 degrees C/Ma) at lower temperatures, increasing cooling rates during retrogression. The charnockite thermal evolution and the extensive production of granitoid melts in the area imply that high geothermal gradients were sustained fora long period of time (50-90 Ma). This thermal anomaly most likely reflects upwelling of asthenospheric mantle and magma underplating coupled with long-term generation of high HPE (heat producing elements) granitoids. These factors must have sustained elevated crustal geotherms for similar to 100 Ma, promoting widespread charnockite generation at middle to lower crustal levels. (C) 2010 Elsevier B.V. All rights reserved.

Relics of eclogite facies assemblages in the Ceara Central Domain, NW Borborema Province, NE Brazil: Implications for the assembly of West Gondwana

The Borborema Province, in the NE of Brazil, is a rather complex piece in the Brazil-Africa puzzle as it represents the junction of the Dahomeyide/Pharusian, Central African, Aracuai and Brasilia fold belts located between the West-African/Sao Luis, Congo/Sao Francisco and Amazonas craton. The correlation between the Dahomeyides from W-Africa (Ghana, Benin, Togo, and Mali) and the Borborema Province involves the Medio Coreau and Central Ceara domains. The inferred continuation of the main oceanic suture zone exposed in the Dahomeyides of W Africa is buried beneath the Phanerozoic Parnaiba Basin in Brazil (northwest of the Medio Coreau domain) where some high density gravity anomalies may represent hidden remnants of an oceanic suture. In addition to this major suture a narrow, nearly continuous strip composed of mainly mafic pods containing relics of eclogite-facies assemblages associated with partially migmatized granulite-facies metapelitic gneisses has been found further east in the NW Borborema Province. These high pressure mafic rocks, interpreted as retrograded eclogites, are located between the Transbrasiliano Lineament and the Santa Quiteria continental arc and comprise primitive to evolved arc-related rocks with either arc- or MORB-type imprints that can indicate either deep subduction of oceanic lithosphere or roots of continental and oceanic magmatic arcs. Average peak P-T conditions under eclogite-facies metamorphism (T=770 degrees C and P = 17.3 kbar) were estimated using garnet-clinopyroxene thermometry and Jd content in clinopyroxene. Transition to granulite-facies conditions, as well as later widespread re-equilibration under amphibolite facies, were registered both in the basic and the metapelitic rocks and suggest a clockwise P-T path characterized by an increase in temperature followed by strong decompression. A phenomenon possibly related to the exhumation of a highly thickened crust associated with the suturing of the Medio Coreau and Central Ceara domains, two distinct crustal blocks separated by the Transbrasiliano Lineament. (C) 2009 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Reaction microtextures of monazite: Correlation between chemical and age domains in the Nazare Paulista migmatite, SE Brazil

Back-scattered imaging, X-ray element mapping and electron microprobe analyzer (EMPA) chemical dating reveal complex compositional and age zoning in monazite crystals from different layers and textural positions in a garnet-bearing migmatite in SE Brazil. Y-rich (variable Y(2)O(3), averaging 2.5 wt.%) relict cores are preserved in mesosome and melanosome monazite, and correspond to 793 +/- 6 Ma inherited crystals possibly generated in a previous metamorphic event. These cores are overgrown and widely replaced by two generations of monazite, which are present in all migmatite layers. The first, also Y-rich (average 2.5 wt.% Y(2)O(3)), was produced at similar to 635 Ma during prograde metamorphism under subsolidus conditions, while the second has an Y-poor (<1.5 wt.% Y(2)O(3)), low Th/U signature, and precipitated from low Y and HREE anatectic melts produced by reactions in which garnet was inert. Quartz-rich trondhjemitic leucosome represents lower temperature melt (bearing some subsolidus quartz and garnet with included monazite) formed at temperatures below muscovite breakdown; its Y-poor monazite indicates an age of 617 +/- 6 Ma. Granitic leucosomes formed close to peak metamorphic conditions (T>750 degrees C) above muscovite breakdown have their slightly younger character confirmed by a 609 +/- 7 Ma low-Y monazite age. A similar 606 +/- 5 Ma age was obtained for low-Y monazite rims and domains in mesosome and melanosome, and reflects the time of monazite saturation in interstitial granitic melt that was trapped in these layers. Our results confirm that inherited monazite crystals can be preserved during partial melting at temperatures above muscovite breakdown. Moreover, careful textural control aided by X-ray chemical mapping may allow monazite generated at different stages in a similar to 25 Myr prograde metamorphic path to be identified and dated using an electron microprobe. (C) 2008 Elsevier B.V. All rights reserved.

Metamorphic P-T evolution of granulites in the central Ribeira Fold Belt, SE Brazil

Pseudosections, geothermobarometric estimates and careful petrographic observations of gneissic migmatites and granulites from Neoproterozoic central Ribeira Fold Belt (SE Brazil) were performed in order to quantify the metamorphic P-T conditions during prograde and retrograde evolution of the Brasiliano Orogeny. Results establish a prograde metamorphic trajectory from amphibolite facies conditions to metamorphic peak (T = 850 +/- 50 A degrees C; P = 8 +/- 1 kbar) that promoted widespread dehydrationmelting of 30 to 40% of the gneisses and high-grade granitization. After the metamorphic peak, migmatites evolved with cooling and decompression to T a parts per thousand 500 A degrees C and P a parts per thousand 5 kbar coupled with aH2O increase, replacing the high-grade paragenesis plagioclase-quartz-K-feldspar-garnet by quartz-biotite-sillimanite-(muscovite). Cordierite absence, microtextural observations and P-T results constrain the migmatite metamorphic evolution in the pseudosections as a clockwise P-T path with retrograde cooling and decompression. High-temperature conditions further dehydrated the lower crust with biotite and amphibole-dehydration melting and granulite formation coupled with 10% melt generation. Granulites can thus be envisaged as middle to lower crust dehydrated restites. Granulites were slowly (nearly isobarically) cooled, followed by late exhumation/retrograde rapid decompression and cooling, reflecting a two step P-T path. This retrograde evolution, coupled with water influx, chemically reequilibrated the rocks from granulite to amphibolite/greenschist facies, promoting the replacement of the plagioclase-quartz-garnet-hypersthene peak assemblage by quartz-biotite- K-feldspar symplectites.

Age and geochemistry of mantle peridotites and diorite dykes from the Baldissero body: Insights into the Paleozoic-Mesozoic evolution of the Southern Alps

Trace element and isotopic data obtained for mantle spinel Iherzolites and diorite dykes from the Baldissero massif (Ivrea-Verbano Zone, Western Italy) provide new, valuable constraints on the petrologic and geodynamic evolution of the Southern Alps in Paleozoic to Mesozoic times. Whole rock and mineral chemistry indicates that Baldissero Iherzolites can be regarded as refractory mantle residues following limited melt extraction. In particular, the Light Rare Earth Elements (LREE)-depleted and fractionated compositions of whole rock and clinopyroxene closely match modelling results for refractory residues after low degrees (similar to 4-5%) of near-fractional melting of depleted mantle, possibly under garnet-facies conditions. Following this, the peridotite sequence experienced subsolidus re-equilibration at lithospheric spinel-facies conditions and intrusion of several generations of dykes. However, Iherzolites far from dykes show very modest metasomatic changes, as evidenced by the crystallisation of accessory titanian pargasite and the occurrence of very slight enrichments in highly incompatible trace elements (e.g. Nb). The Re-Os data for Iherzolites far from the dykes yield a 376 Ma (Upper Devonian) model age that is considered to record a partial melting event related to the Variscan orogenic cycle s.l. Dioritic dykes cutting the mantle sequence have whole rock, clinopyroxene and plagioclase characterised by high radiogenic Nd and low radiogenic Sr, which point to a depleted to slightly enriched mantle source. Whole rock and mafic phases of diorites have high Mg# values that positively correlate with the incompatible trace element concentrations. The peridotite at the dyke contact is enriched in orthopyroxene, iron and incompatible trace elements with respect to the Iherzolites far from dykes. Numerical simulations indicate that the geochemical characteristics of the diorites can be explained by flow of a hydrous, silica-saturated melt accompanied by reaction with the ambient peridotite and fractional crystallisation. The composition of the more primitive melts calculated in equilibrium with the diorite minerals show tholeiitic to transitional affinity. Internal Sm-Nd, three-point isochrons obtained for two dykes suggest an Upper Triassic-Lower Jurassic emplacement age (from 204 31 to 198 29 Ma). Mesozoic igneous events are unknown in the southern Ivrea-Verbano Zone (IVZ), but the intrusion of hydrous melts, mostly silica-saturated, have been well documented in the Finero region, i.e. the northernmost part of IVZ and Triassic magmatism with calc-alkaline to shoshonitic affinity is abundant throughout the Central-Eastern Alps. The geochemical and chronological features of the Baldissero diorites shed new light on the geodynamic evolution of the Southern Alps before the opening of the Jurassic Tethys. (C) 2010 Elsevier B.V. All rights reserved.