A kinetic model for the ultrasound catalyzed hydrolysis of solventless TEOS-water mixtures and the role of the initial additions of ethanol

The acid and ultrasound catalyzed hydrolysis of solventless TEOS-water mixtures are studied, as a function of the initial additions of ethanol to the mixtures, by means of flux calorimetry measurements. A device was specially designed for this purpose. Under acid conditions, our proposed method has been able to resolve hydrolysis from other condensation reactions, by detecting the exothermal hydrolysis reaction heat. The process has been explained by a dissolution and reaction mechanism. Ultrasound forces the dissolution process to start the reaction. The alcohol produced in the reaction helps the dissolution process to further enhance the hydrolysis. Initial amounts of pure ethanol added to the mixtures shorten the start time of the reaction, due to an additional effect of dissolution, and diminish the reaction rate, as a result of the solvent dilution effect. Our dissolution and reaction mechanism modeling describes the main points arising from the experimental data and yields k(H) = 0.24 M(-1) min(-1) for the second-order hydrolysis rate constant at 39 degrees C.

Study on the initial stages of water corrosion of fluorozirconate glasses

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, ZBLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)) was investigated using X-ray photoelectron spectroscopy (XPS), grazing-incidence small angle X-ray scattering (GISAXS), X-ray reflectivity (XRR) and scanning electron microscopy (SEM). After a short exposure period (25 min) of the glass surface to deionized water the XPS data indicate an increase of the oxygen content accompanied by a decrease of fluorine concentration. The analysis of the chemical bonding structure identified the predominant surface reaction products as zirconium hydroxyfluoride and oxyfluoride species. The second most abundant glass component, bariumfluoride, remains almost unaffected by oxygen, while sodium fluoride is completely removed from the attacked surface region. The detected structural and compositional changes are related to the selective dissolution of the glass components leading to the formation of a new surface phase. This process is accompanied by a visible surface roughening caused by reprecipitated species, observed by SEM. The modification of the glass surface is responsible for an increase of the GISAXS intensity. The scattering was attributed to nanovoids formed at the surface region of the glass with an average size of 2.4 +/- 0.05 nm. (C) 2004 Elsevier B.V. All rights reserved.

Mesoproterozoic rapakivi granites of the Rondonia Tin Province, southwestern border of the Amazonian craton, Brazil - I. Reconnaissance U-Pb geochronology and regional implications

Rapakivi granites and associated mafic and ultramafic rocks in the Rondonia Tin Province, southwestern Amazonian craton, Brazil were emplaced during six discrete episodes of magmatism between ca 1600 and 970 Ma. The seven rapakivi granite suites emplaced at this time were the Serra da Providencia Intrusive Suite (U-Pb ages between 1606 and 1532 Ma); Santo Antonio Intrusive Suite(U-Pb age 1406 Ma), Teotonio Intrusive Suite (U-Pb age 1387 Ma); Alto Candeias Intrusive Suite (U-Pb ages between 1346 and 1338 Ma); Sao Lourenco-Caripunas Intrusive Suite (U-Pb ages between 1314 and 1309 Ma); Santa Clara Intrusive Suite (U-Pb ages between 1082 and 1074 Ma); and Younger Granites of Rondonia (U-Pb ages between 998 and 974 Ma). The Serra da Providencia Intrusive Suite intruded the Paleoproterozoic (1.80 to 1.70 Ga) Rio Negro-Juruena crust whereas the other suites were emplaced into the 1.50 to 1.30 Ga Rondonia-San Ignacio crust. Their intrusion was contemporaneous with orogenic activity in other parts of the southwestern Amazonian craton, except for the oldest, Serra da Providencia Intrusive Suite. Orogenic events coeval with emplacement of the Serra da Providencia Intrusive Suite are not clearly recognized in the region. The Santo Antonio, Teotonio, Alto Candeias and Sao Lourenco-Caripunas Intrusive Suites are interpreted to represent extensional anorogenic magmatism associated with the terminal stages of the Rondonian-San Ignacio orogeny. At least the Sao Lourenco-Caripunas rapakivi granites and coeval intra-continental rift sedimentary rocks may, in contrast, represent the products of extensional tectonics and rifting preceding the Sunsas/Aguapei orogeny (1.25 to 1.0 Ga). The two youngest rapakivi suites, the Santa Clara Intrusive Suite and Younger Granites of Rondonia, seemingly represent inboard magmatism in the Rondonian-San Ignacio Province during a younger episode of reworking in the Rio Negro-Juruena Province during the waning stages of the collisional 1.1 to 1.0 Ga Sunsas/Aguapei orogeny. The six intra-plate rapakivi granite episodes in the southwestern part of the Amazonian craton form three broad periods of anorogenic magmatism that have age-correlative events composed of similar rocks and geologic environments in eastern Laurentia and Baltica, although the exact timing of magmatism appears slightly different. Recognition of lithologic and chronological correlations between various cratons provide important constraints to models explaining the interplay between rapakivi granite magmatism and deep crustal evolution of an early Mesoproterozoic supercontinent. They are, furthermore, important to plate tectonic models for the assembly, dispersal and reassembly of Amazonia, Laurentia and Baltica in the Mesoproterozoic and Neoproterozoic. (C) 1999 Elsevier B.V. B.V. All rights reserved.