Changes of physical properties of glass surfaces exposed to KNO3 vapors

Modifications of glass surfaces were studied after exposure of samples to an atmosphere resulting from the decomposition of molten KNO3. The diffusion coefficient of K+ ions migrating into the surfaces of float glass and synthesized glasses doped with up to 5 wt% SnO2 was calculated by the Boltzmann-Matano technique. The Vickers hardness and the refractive index increase with exposure time. Infrared spectra show that the migration of K+ is responsible for an increase in the number of non-bridging oxygens in the exposed samples. The spectra of the synthesized glasses present evidences that their surfaces undergo crystallization during the exposure. All results lead to the conclusion that the presence of tin in the glasses hinders the diffusion of K+ ions, thus affecting the Vickers hardness, the refractive index and the infrared spectra. It is shown that the exposure method can be used as an alternative process to promote the K+ migration into glass surfaces. (c) 2006 Elsevier B.V. All rights reserved.

Metamorphism and PGE-Au content of chromitite from the Ipanema mafic/ultramafic Complex, Minas Gerais, Brazil

The Santa Cruz massif, which forms part of the Ipanema mafic/ultramafic Complex, Minas Gerais, Brazil, has an exposed upward sequence of metadunite, metaharzburgite (including three separate chromitite layers), metapyroxenite, metagabbro, and metaanorthosite. Primary igneous chromite grains in the main chromitite layer are poikiloblastic and tectonically fragmented, and have a narrow (10-20 mum) margin of chromian spinel. Cataclased chromite fragments are extensively replaced and mantled by chromian spinel; they have a composite margin comprised of an inner zone of more aluminous spinel and an euhedral outer zone of more Cr-rich spinel, representing granulite and amphibolite facies metamorphic events, respectively. The contents of platinum-group elements (PGE) and Au in chromite separates are relatively high (Os 45, Ir 23, Ru 136, Rh 19, Pt 98, Pd 63, and Au 83 ppb), and significantly enriched (similar to 4x) over whole rock values. Platinum-group minerals are not observed and micrometre-sized inclusions of sulfide minerals (chalcopyrite and pentlandite) in relict chromite are rare. However, comparison of mineral proportions in the separated chromite and whole rock shows that the precious metals are hosted predominantly in the relict igneous chromite grains, rather than the secondary chromian spinel and primary and secondary Mg-rich silicates. The major element composition and average chondrite-normalized PGE pattern of the separated chromite correspond to S-poor stratiform chromitite. We suggest that the precious metals accumulated with chromite during crystallization of a S-poor magma, and were not remobilized in the relict chromite during the subsequent high grade metamorphism.

Lead-cadmium oxyfluoride glasses and glass-ceramics

Glasses and glass-ceramics have been obtained in oxyfluoride systems involving lead and cadmium fluorides and one of the well-known glass former oxides SiO2, B2O3 and TeO2. Vitreous domains were established and a wide range of compositions including high heavy metal contents lead to stable glasses. Amorphous structures have been studied by short-range order spectroscopy techniques (Raman scattering and x-ray absorption) and molecular basic structures have been identified. Besides the usual oxides, the role of glass former could also be proposed for cadmium ions. Special attention has been paid for crystallization process. Cubic lead fluoride, cubic lead tellurite, tetragonal tellurium oxide and a solid solution of the type Pb1-xCdxF2 are obtained as crystallization products depending on the composition and temperature of heat treatments. Pb1-xCdxF2 solid solutions are well known superionic materials and obtaining this solid solution as a crystal phase could be very interesting for applications concerning ionic electrical conduction properties. The addition of rare earth ions led to the control of the crystallization process. In the presence of the nucleating ion only the cubic form beta-PbF2 was identified. Rare earth ions are present in the crystal phase and crystal-like spectroscopic properties were observed suggesting interesting applications for these perfectly transparent glass ceramics in photonics.

Grazing incidence X-ray diffraction and atomic force microscopy analysis of BaBi2Ta2O9 thin films

Thin films of BaBi2Ta2O9 (BBT) composition were prepared through the metal organic decomposition method. The crystallinity, phase formation, crystallite size and morphology of the thin films were measured as a function of the type of substrate, stoichiometry of solution and process variables such as thickness and temperature. The thin films were investigated by grazing incidence X-ray diffractometry and atomic force microscopy (AFM) techniques. For the sample without excess of bismuth, diffraction peaks other than that of the BBT phase were observed. A well crystallized BBT single phase was observed for films prepared from a solution with 10% excess of bismuth, deposited on Si/Pt substrate, with a thickness up to 150 nm and sintered at temperatures of 700 degreesC. The thin BBT phase films heat-treated at 600 degreesC presented a diffraction pattern characteristic of samples with lower degree of crystallinity whereas for the thin films heat-treated at 800 degreesC, we observed the presence of other phases than the BBT. For the thin film deposited on the Sin+ substrate, we observe that the peaks corresponding to the BBT phase are broader than that observed on the samples deposited on the Pt and Si/Pt substrates. No variation of average crystallite size was observed as the excess of Bi increased from 10 to 20%. AFM images for the samples showed that the increasing the amount of bismuth promotes grain growth. The average surface roughness measured was in the range of 16-22 nm showing that the bismuth amount had no or little effect on the roughness of films. (C) 2002 Elsevier B.V. B.V. All rights reserved.

SrBi2Nb2O9 thin films deposited by dip coating using aqueous solution

A new approach for SrBi2Nb2O9 (SBN) thin films synthesis using aqueous solution was successfully experienced. The deposition solution was prepared from Sr-Bi-Nb mixed-citrate solution, requiring no special atmosphere and using common reagents. Films were deposited by dip coating onto Pt/Ti/SiO2/Si(100) substrates and hear treated at temperatures ranging from 300 to 700 degrees C. The process of formation and crystallization of SrBi2Nb2O9 thin films, prepared by the aqueous solution method have been studied with particular emphasis on the microstructure of crystallized films. Crystalline phases formation were followed by grazing incident X-ray diffraction (GIXRD), microstructure characterization was evaluated by scanning electron microscopy (SEM) and surface roughness were observed using atomic for ce microscopy (AFM). To reach the desired thickness, substrates were dipped in the deposition solution twice, forming double-layered films. The thickness of each layer ranged from 80 to 100 nm. (C) 1999 Elsevier B.V. Limited. All rights reserved.

Thermal behavior of the maleic anhydride modified poly(3-hydroxybutyrate)

Poly(3-hydroxybutyrate), PHB has been structurally modified through reaction with maleic anhydride, MA. Transesterification reaction was carried out fixing the PHB and MA and besides time and temperature the concentration of the triethylamine (used as catalyst) was changed. Glass transition, melting and crystallization temperature obtained from DSC curves and thermal degradation temperatures obtained from TG traces were used to evaluate the influence of the reaction conditions on the modification of PHB according to factorial design. on the base of the results the optimum conditions are to perform the PHB modification reaction with MA reaction at 110 degrees C for 1 h with 5% v/v triethylamine.

Synthesis and luminescence properties of water dispersible Eu3+-doped boehmite nanoparticles

Nanocrystallized boehmite gamma-AlOOH center dot nH(2)O had been synthesized by spray-drying (SD) of a solution of aluminium tri-sec-butoxide peptized by nitric acid. The sub-micronic spherical particles obtained had an average diameter of 500 nm and were built of 100 nm or less platelet-like sub-particles. The average crystallite size calculated from XRD was 1.6 nm following the b axis (i.e. one unit cell) and 3-4 nm perpendicular to b. As a result of the nanometric sizes of crystallites, there was a large surface free for water adsorption and it was found to be n = 1.18 +/- 0.24H(2)O per AlOOH. The SD spheres spontaneously dispersed in water at room temperature and formed stable-over months-suspensions with nanometre-size particles (25-85 nm). Luminescent europium-doped nanocrystallized boehmites AlOOH: Eu (Al0.98Eu0.02OOH center dot nH(2)O) were synthesized the same way by SD and demonstrated the same crystallization properties and morphologies as the undoped powders. It is inferred from the Eu3+ luminescence spectroscopy that partly hydrated europium species are immobilized on the boehmite nanocrystals where they are directly bonded to alpha(OH) groups of the AlOOH surface. The europium coordination is schematically written [Eu3+(OH)(alpha)(H2O)(7-alpha/2)]. The europium-doped boehmite from SD spontaneously dispersed in water: the luminescence spectroscopy proves that most of the Eu3+ ions were detached from the NPs during water dispersion. The AlOOH: Eu nanoparticles were modified by the amine acid asparagine (ASN). The modification aimed to render the NPs compatible for further bio-functionalization. After surface modification, the NPs easily dispersed in water; the luminescence spectra after dispersion prove that the Eu3+ ions were held at the boehmite surface.

Montmorillonite (MMT) effect on the structure of poly(oxyethylene) (PEO)-MMT nanocomposites and silica-PEO-MMT hybrid materials

In this work we report the effects of incorporation of variable amounts (0.5-25%w/w) of montmorillonite in poly(oxyethylene) based materials in order to decrease the polymer crystallinity. Two different classes of materials were studied: silica-poly(oxyethylene)-montmorillonite hybrids prepared by the sol-gel route and poly(oxyethylene)-montmorillonite nanocomposites prepared by mixing the dry clay or the clay aqueous suspension into the melt poly(oxyethylene). The effects of monternorillonite loading on the poly(oxyethylene) crystallization control and on the nanostructural features were investigated by X-ray powder diffraction, small-angle X-ray scattering and differential scanning calorimetry. Experimental results show that free montmorillonite layers coexist with open aggregates and tactoids in the poly(oxyethylene)-montmorillonite nanocomposites, with different features depending on the filler proportion and preparation route. The intercalation of polymer chains in montmorillonite galleries markedly hinders the crystallization of the poly(oxyethylene) matrix. For hybrids materials the silica phase favors the exfoliation of montmorillonite tactoids, so that samples are predominantly constituted by dispersed platelets. (c) 2006 Elsevier B.V. All rights reserved.

Effect of the heat flux direction on electrical properties of SrBi2Nb2O9 thin films crystallized using a microwave oven

Ferroelectric SrBi2Nb2O9 (SBN) thin films were prepared by the polymeric precursors method and deposited by spin coating onto Pt/Ti/SiO2/Si substrate and crystallized using a domestic microwave oven. It was studied the influence of the heat flux direction and the duration of the thermal treatment on the films crystallization. An element with high dielectric loss, a SiC susceptor, was used to absorb the microwave energy and transfers the heat to the film. Influence of the susceptor position to the sample crystallization was verified, the susceptor was, placed or below the substrate or above the film. The SBN perovskite phase was observed after a thermal treatment at 700 degreesC for 10 min when the susceptor was placed below the substrate and for 30 min when the susceptor was placed above the film. Electrical measurements revealed that the film crystallized at 700 degreesC for 10 min, with the susceptor placed below the film, presented dielectric constant, dielectric loss, remanent polarization and coercive field of, 67, 0.011, 4.2 muC/cm(2) and 27.5 kV/cm, respectively. When the films were crystallized at 700 degreesC for 30 min, with the susceptor placed above the film, the dielectric constant was 115 and the dissipation factor was around of 0.033, remanent polarization and coercive field were 10.8 muC/cm(2) and 170 kV/cm, respectively. (C) 2003 Elsevier B.V. All rights reserved.

Zirconia needles synthesized inside hexagonal swollen liquid crystals

We report the synthesis of zirconia microneedles by the direct nucleation of particles inside a hexagonal swollen liquid crystal (SLC) (cell parameter a = 27 nm) prepared by mixing with the proper ratio, an aqueous solution of sulfated zirconium colloids, a cationic surfactant (cetylpyridinium chloride), cychlohexane as swelling agent with an oil over water ratio of 2.5 (vol.), and 1-pentanol as cosurfactant. After a slow crystallogenesis that can be enhanced by an initial induction step under moderate temperature, particles in the centimeter range can be obtained, with a very high shape ratio (over 100). These particles are made of crystalline octahydrate zirconium oxychloride containing pores of 20 nm diameter, aligned along the main axis of the liquid crystal, as the fingerprint of the oil cylinders present in the hexagonal phase. The morphology of these particles confirms that the shaping mechanism is based on true liquid crystal templating (TLCT). Further thermal treatment of these particles, after extraction from the SLC, leads to the crystallization of zirconia with the same needlelike morphology as the zirconium oxychloride.

The effect of isostructural seeding on the microstructure and piezoelectric properties of PZT ceramics

Pechini's method was used to prepare lead titanate zirconate with Zr/Ti ratio equal to 53/47. X-ray diffraction data revealed the presence of a rhombohedral phase, rich in zirconium, due to difference in carbonate stabilities, in PZT ceramics calcined at 600 degrees C. Infrared spectroscopy presented COO- bonds in the 1400 cm(-1) region, which disappeared after calcining at 700 degrees C. Seeds with rhombohedral (PZT 57/43) or tetragonal structure (PZT 45/55) were added to the precursor. The microstructure was differentially influenced by the nature of seed particles. Rhombohedral nuclei promoted preferential crystallization of lead zirconate. This heterogeneity directly reflected on values of k(p) and d(33). (C) 1999 Elsevier B.V. Limited and Techna S.r.l. All rights reserved.

Structural features of phosphate and sulfate modified zirconia prepared by sol-gel route

This paper describes the effect of sulfate, phosphate and nitrate complexing ligands on the structural features of amorphous xerogels and on the crystallization of metastable zirconia phases during the xerogel-ceramic conversion. Powdered samples were prepared by a sol-gel route using zirconyl chloride precursors chemically modified by complexing ligands. The structural evolution of ZrO2 phases as function of firing temperature was analyzed by XRPD, EXAFS and P-13 NMR/MAS. The experimental results show the formation of metastable t-ZrO2 during the low firing temperature of xerogels modified by sulfate or phosphate groups. The martensitic tetragonal-monoclinic transformation occurs during desorption of sulfate groups. The largest temperature interval of stability of metastable tetragonal zirconia was observed for phosphate-modified xerogels.

Plutonism in three orogenic pulses, Eastern Blue Ridge Province, southern Appalachians

The Eastern Blue Ridge Province of the southern Appalachians contains, in part, remnants of an Ordovician accretionary wedge complex formed during subduction of an oceanic tract before mid-Ordovician accretion with Laurentia. The Eastern Blue Ridge Province consists of metapelite and amphibolite intruded by low-K plutons, high-temperature (T > 750 degrees C) Ordovician eclogite, and other high-pressure metamafic and meta-ultramatic rocks. Felsic plutons in the Eastern Blue Ridge Province are important time markers for regional-scale tectonics, deformation, and metamorphism. Plutons were thought to be related to either Taconian (Ordovician) or Acadian (Devonian-Silurian) tectonothermal events.We dated five plutonic or metaplutonic rocks to constrain pluton crystallization ages better and thus the timing of tectonism. The Persimmon Creek gneiss yielded a protolith crystallization age of 455.7 +/- 2.1 Ma, Chalk Mountain 377.7 +/- 2.5 Ma, Mt. Airy 334 +/- 3 Ma, Stone Mountain 335.6 +/- 1.0 Ma, and Rabun 335.1 +/- 2.8 Ma. The latter four plutons were thought to be part of the Acadian Spruce Pine Suite, but instead our new ages indicate that Alleghanian (Carboniferous-Permian) plutonism is widespread and voluminous in the Eastern Blue Ridge Province. The Chattahoochee fault, which was considered an Acadian structure, cuts the Rabun pluton and thus must have been active during the Alleghanian orogeny. The new ages indicate that Persimmon Creek crystallized less than 3 m.y. after zircon crystallization in Eastern Blue Ridge eclogite and is nearly synchronous with nearby high-grade metamorphism and migmatization. The three phases of plutonism in the Eastern Blue Ridge Province correspond with established metamorphic ages for each of the three major orogenic pulses along the western flank of the southern Appalachians.

Wet-chemical synthesis of magnesium niobate nanoparticles powders

Nanosized and highly reactive magnesium mobate (MgNb2O6) powders were successfully synthesized by a new wet-chemical method by means of the dissolution of Nb2O5 center dot 5H(2)O and in a solution of oxalic acid followed by the addition of stoichiometric amounts of magnesium carbonate. The Nb-Mg-oxalic acid solution was evaporated resulting in a dry and amorphous powder that was calcined in the temperature range from 200 to 900 degrees C for 2 h. The crystallization process from the amorphous state to the crystalline MgNb2O6 was followed by thermal analysis. The calcined powders characterized by FT-Raman spectroscopy, X-ray diffraction (XRD) and their morphology examined by high resolution scanning electron microscopy (HR-SEM). Pure MgNb2O6, free from the second phases and obtained at 800 degrees C was confirmed by a combined analysis using XRD and FT-Raman. The average diameter of the particles was calculated from the HR-SEM image as 70 urn approximately. This technique allows a better mixing of the constituent elements and thus a better reactivity of the mixture to obtain pre-reaction products with high purity at lower temperatures and reducing cost. It can offer a great advantage in the PMN-PT formation with respect to the solid-state synthesis. (c) 2006 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Synthesis by the polymeric precursor method and characterization of undoped and Sn, Cr and V-doped ZrTiO4

In this work, zirconium titanate doped with 0. 1, 0.2, and 0.4 mole% of tin, chromium and vanadium was synthesized by the polymeric precursors method and characterized by thermal analysis (TG/DTA), X-ray diffraction (XRD), nitrogen adsorption and scanning electronic microscopy (SEM). The powder presented two mass losses attributed to the exit of water and to the pyrolysis of the organic material. The surface area reduction observed from 500 degrees C indicates the beginning of the sintering process. All the dopants led to changes in the lattice parameters and to the decrease of both crystallite size and particle size. (c) 2005 Elsevier B.V. All rights reserved.