Effect of boron on the water speciation in (alumino)silicate melts and glasses     

Burkhard C. Schmidt 《Geochimica et cosmochimica acta》2004,68(24):5013-5025

The investigation of hydrous boro(alumino)silicate melts and glasses with near infrared (NIR) spectroscopy revealed an important effect of boron on the water speciation. In the NIR spectra of B-bearing glasses new hydroxyl-related bands develop at the high frequency side of the 4500 cm⁻¹ peak. In NaAlSi₃O₈ + B₂O₃ glasses this new peak is present as a shoulder at 4650 cm⁻¹, and in NaAlSi₃O₈-NaBSi₃O₈ (Ab-Rd) glasses it appears as a resolved peak at 4710 cm⁻¹. These bands increase with increasing boron concentration, suggesting that they are due to B-OH complexes. Furthermore, the variations in the NIR spectra indicate that with increasing B-content, but constant total water concentration, the amount of structurally bonded hydroxyl groups increases at the expense of molecular H₂O. For example, at a total water concentration of 4 wt.%, pure Rd-glass contains ∼50% more water as hydroxyl groups than pure Ab-glass.In-situ NIR spectroscopy at high P and T using a hydrothermal diamond-anvil cell was used to gain information about the temperature dependence of the water speciation in NaBSi₃O₈ melts. The data demonstrate the conversion of molecular H₂O to hydroxyl groups with increasing temperature. However, a fully quantitative evaluation of the high T spectra was hampered by problems with defining the correct baseline in the spectra. As an alternative approach annealing experiments on a Rd-glass containing 2.8 wt.% water were performed. The results confirm the conversion of H₂O to OH groups with increasing T, but also suggest that the OH groups represented by the 4710 cm⁻¹ peak (B-OH) participate much less in the conversion reaction compared to X-OH, represented by the 4500 cm⁻¹ peak.  相似文献   

A note on the Raman spectra of water-bearing albite glasses     

Paul F. McMillan  Sigurdur Jakobsson  John R. Holloway  Lynn A. Silver 《Geochimica et cosmochimica acta》1983,47(11):1937-1943

The Raman spectra of albite glasses with 4.5 and 6.6 weight percent water have been obtained, and are compared with that of a dry sample. The hydrous glasses show bands near 3600 cm^?1 due to O-H stretching, and a previously unreported weak band near 1600 cm^?1 due to bending of molecular H₂O. Other weak spectral features are discussed, and the effect of dissolved water on the aluminosilicate framework vibrations is considered.  相似文献   

Temperature-induced changes in the NIR spectra of hydrous albitic and rhyolitic glasses between 300 and 100 K     

A. C. Withers  H. Behrens 《Physics and Chemistry of Minerals》1999,27(2):119-132

Near-infrared (NIR) absorption bands related to total water (4000 and 7050 cm⁻¹), OH groups (4500 cm⁻¹) and molecular H₂O (5200 cm⁻¹) were studied in two polymerised glasses, a synthetic albitic composition and a natural obsidian. The water contents of the glasses were determined using Karl Fischer titration. Molar absorption coefficients were calculated for each of the bands using albitic glasses containing between 0.54 and 9.16 wt.% H₂O and rhyolitic glasses containing between 0.97 and 9.20 wt.% H₂O. Different combinations of baseline type and intensity measure (peak height/area) for the combination bands at 4500 and 5200 cm⁻¹ were used to investigate the effect of evaluation procedure on calculated hydrous species concentrations. Total water contents calculated using each of the baseline/molar absorption coefficient combinations agree to within 5.8% relative for rhyolitic and 6.5% relative for albitic glasses (maximum absolute differences of 0.08 and 0.15 wt.% H₂O, respectively). In glasses with water contents >1 wt.%, calculated hydrous species concentrations vary by up to 17% relative for OH and 11% relative for H₂O (maximum absolute differences of 0.33 and 0.43 wt.% H₂O, respectively). This variation in calculated species concentrations is typically greater in rhyolitic glasses than albitic. In situ, micro-FTIR analysis at 300 and 100 K was used to investigate the effect of varying temperature on the NIR spectra of the glasses. The linear and integral molar absorption coefficients for each of the bands were recalculated from the 100 K spectra, and were found to vary systematically from the 300 K values. Linear molar absorption coefficients for the 4000 and 7050 cm⁻¹ bands decrease by 16–20% and integral molar absorption coefficients by up to 30%. Depending on glass composition and baseline type, the integral molar absorption coefficients for the absorption bands related to OH groups and molecular H₂O change by up to −5.8 and +7.4%, respectively, while linear molar absorption coefficients show less variation, with a maximum change of ∼4%. Using the new molar absorption coefficients for the combination bands to calculate species concentrations at 100 K, the maximum change in species concentration is 0.08 wt.% H₂O, compared with 0.39 wt.% which would be calculated if constant values were assumed for the combination band molar absorption coefficients. Almost all the changes in the spectra can therefore be interpreted in terms of changing molar absorption coefficient, rather than interconversion between hydrous species. Received: 17 December 1998 / Revised, accepted 8 July 1999  相似文献   

Dehydration process and structural development of cordierite ceramic precursors derived from FTIR spectroscopic investigations     

D. Voll  A. Beran 《Physics and Chemistry of Minerals》2002,29(8):545-551

 Cordierite precursors were prepared by a sol-gel process using tetraethoxysilane, aluminum sec.-butoxide, and Mg metal flakes as starting materials. The precursors were treated by 15-h heating steps in intervals of 100 °C from 200 to 900 °C; they show a continuous decrease in the analytical water content with increasing preheating temperatures. The presence of H₂O and (Si,Al)–OH combination modes in the FTIR powder spectra prove the presence of both H₂O molecules and OH groups as structural components, with invariable OH concentrations up to preheating temperatures of 500 °C. The deconvolution of the absorptions in the (H₂O,OH)-stretching vibrational region into four bands centred at 3584, 3415, 3216 and 3047 cm⁻¹ reveals non-bridging and bridging H₂O molecules and OH groups. The precursor powders remain X-ray amorphous up to preheating temperatures of 800 °C. Above this temperature the precursors crystallize to μ-cordierite; at 1000 °C the structure transforms to α-cordierite. Close similarities exist in the pattern of the 1400–400 cm⁻¹ lattice vibrational region for precursors preheated up to 600 °C. Striking differences are evident at preheating temperatures of 800 °C, where the spectrum of the precursor powder corresponds to that of conventional cordierite glass. Bands centred in the “as-prepared” precursor at 1137 and 1020 cm⁻¹ are assigned to Si–O-stretching vibrations. A weak absorption at 872 cm⁻¹ is assigned to stretching modes of AlO₄ tetrahedral units and the same assignment holds for a band at 783 cm⁻¹ which appears in precursors preheated at 600 °C. With increasing temperatures, these bands show a significant shift to higher wavenumbers and the Al–O stretching modes display a strong increase in their intensities. (Si,Al)–O–(Si,Al)-bending modes occur at 710 cm⁻¹ and the band at 572 cm⁻¹ is assigned to stretching vibrations of AlO₆ octahedral units. A strong band around 440 cm⁻¹ is essentially attributed to Mg–O-stretching vibrations. The strongly increasing intensity of the 872 and 783 cm⁻¹ bands demonstrates a clear preference of Al for a fourfold-coordinated structural position in the precursors preheated at high temperatures. The observed band shift is a strong indication for increasing tetrahedral network condensation along with changes in the Si–O and Al–O distances to tetrahedra dimensions similar to those occurring in crystalline cordierite. These structural changes are correlated to the dehydration process starting essentially above 500 °C, clearly demonstrating the inhibiting role of H₂O molecules and especially of OH groups. Received: 1 March 2002 / Accepted: 26 June 2002  相似文献   

Water speciation and diffusion in haploandesitic melts at 743-873 K and 100 MPa     

Huaiwei Ni  Yang Liu  Lijin Wang  Youxue Zhang 《Geochimica et cosmochimica acta》2009,73(12):3630-124

Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H₂O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H₂O (H₂O_m) and hydroxyl group (OH)] and total H₂O (H₂O_t) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H₂O speciation reaction H₂O_m+O?2OH, K = (X_OH)²/(X_H2OmX_O) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H₂O concentration, contrary to previous H₂O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H₂O is the diffusion species. Based on the above speciation model, H₂O_m and H₂O_t diffusivity (in m²/s) in haploandesite at 743-873 K, 100 MPa, and H₂O_t ? 2.5 wt.% can be formulated as