Wim J. Malfait

Amorphous materials: Properties, structure, and durability: Quantitative Raman spectroscopy: Speciation of Na-silicate glasses and melts

Abstract In situ, high-temperature Raman spectroscopy was used to study the Qn speciation in binary Nasilicate glasses and melts. Over 300 Raman spectra in the compositional range from 25 to 40 mol% Na2O were collected at room and high temperatures between 800 and 1200 K. Quantitative information on the relative abundances of species in melts was obtained from the Raman spectra through a quantification procedure that does not require any a priori assumptions about the line shapes or external calibration of the Raman scattering efficiencies for the various Qn species. The ΔH° associated with the speciation reaction 2Q3 = Q4 + Q2 was found to be 20.3 ± 7.9 kJ/mol. For a given temperature, the speciation is more disordered in sodium than in potassium silicate melts. Because of the smaller temperature dependence of the speciation in the sodium silicate system, the difference in the speciation for the sodium and potassium silicate system decreases with increasing temperature. In addition to the speciation data, the partial Raman spectra for the different species were obtained. The experimentally observed variation of the partial Raman spectra with temperature, and, to a minor extent, with composition, should stimulate future theoretical studies on the vibrational properties of silicate glasses and melts.

Amorphous mAteriAls: properties, structure, And durAbility† Compositional dependent compressibility of dissolved water in silicate glasses

Abstract The sound velocities and elastic properties of a series of hydrous rhyolite, andesite, and basalt glasses have been determined by Brillouin scattering spectroscopy at ambient conditions to elucidate the effect of glass composition on the compressibility of dissolved water. Both the adiabatic bulk (KS) and shear modulus (μ) of the dry glasses decrease with increasing silica content (KS,basalt > KS,andesite > KS,rhyolite and μbasalt > μandesite > μrhyolite). For each composition, the shear modulus systematically decreases with increasing water content. Although the addition of up to 14 mol% water decreases the KS of andesite and basalt glasses by up to 6%, there is no discernable effect of water on the KS of the rhyolite glasses. The partial molar KS of dissolved water (KS) in rhyolite, andesite, and basalt glasses are 37 ± 5, 19 ± 7, and 40 ± 3 GPa, corresponding to partial molar isothermal compressibilities (β̅T) of 0.029 ± 0.005, 0.042 ± 0.004, and 0.026 ± 0.002 GPa−1, respectively. These results indicate that the compressibility of dissolved water strongly depends on the bulk composition of the glass; hence, the partial molar volume of water cannot be independent of the bulk composition at elevated pressure. If the compressibility of dissolved water also depends on composition in the analog melts at high temperature and pressure, these observations will have important consequences for magmatic processes such as magma mixing/unmixing and fractional crystallization.

The 4500 cm―1 infrared absorption band in hydrous aluminosilicate glasses is a combination band of the fundamental (Si,Al)-OH and O-H vibrations

Abstract The position of the infrared absorption band near 4500 cm-1 shifts from 4520 to 4440 cm-1 as the Al content increases along the SiO2-NaAlSiO2 join and closely follows the sum of the positions of the Raman bands near 900 and 3600 cm-1. This confirms the idea that the 4500 cm-1 band is a combination band of the fundamental (Si,Al)-OH vibration near 900 cm-1 and the fundamental O-H stretching vibration near 3600 cm-1. As a consequence, the 4500 cm-1 band should not be used to quantify the water speciation for glass compositions for which significant amounts of free hydroxyls are expected as these do not contribute to the band’s intensity.

Fate of MgSiO3 melts at core–mantle boundary conditions

Significance A new technique has been developed to measure in situ the density of amorphous material composed of light elements under extreme conditions of pressure using the X-ray absorption method. At core–mantle boundary (CMB) pressure, the densities of MgSiO3 glass and melts are similar to the one of the crystalline bridgmanite, within uncertainty. Due to the affinity of iron oxide for silicate liquids, melting in the MgSiO3–FeSiO3 system will produce dense melts that could accumulate above the CMB, leading to the formation of a dense basal magma ocean in the early Earths mantle. One key for understanding the stratification in the deep mantle lies in the determination of the density and structure of matter at high pressures, as well as the density contrast between solid and liquid silicate phases. Indeed, the density contrast is the main control on the entrainment or settlement of matter and is of fundamental importance for understanding the past and present dynamic behavior of the deepest part of the Earth’s mantle. Here, we adapted the X-ray absorption method to the small dimensions of the diamond anvil cell, enabling density measurements of amorphous materials to unprecedented conditions of pressure. Our density data for MgSiO3 glass up to 127 GPa are considerably higher than those previously derived from Brillouin spectroscopy but validate recent ab initio molecular dynamics simulations. A fourth-order Birch–Murnaghan equation of state reproduces our experimental data over the entire pressure regime of the mantle. At the core–mantle boundary (CMB) pressure, the density of MgSiO3 glass is 5.48 ± 0.18 g/cm3, which is only 1.6% lower than that of MgSiO3 bridgmanite at 5.57 g/cm3, i.e., they are the same within the uncertainty. Taking into account the partitioning of iron into the melt, we conclude that melts are denser than the surrounding solid phases in the lowermost mantle and that melts will be trapped above the CMB.

Constraints on the mobilization of Zr in magmatic-hydrothermal processes in subduction zones from in situ fluid-melt partitioning experiments

Abstract The partitioning of Zr between high P-T aqueous fluids and melts has been investigated in situ in the haplogranite-H2O and haplogranite-(F)-H2O systems to assess the mobilization of high field strength elements (HFSE) in magmatic-hydrothermal processes in subduction zones. The partition coefficients Df/Zmr were determined from Zr concentrations measured in situ by synchrotron X-ray fluorescence (SXRF) in both aqueous fluids and F-free or F-bearing hydrous haplogranite melts equilibrated in diamond-anvil cells at 575 to 800 °C and 0.3 to 2.4 GPa. This experimental approach eliminates the need for internal or external calibrations of the SXRF signal and/or post-mortem analysis of the melt phase, hence decreasing the total uncertainties on Df/Zmr below 16%. Above 0.6 GPa, Zr partitions favorably into the hydrous silicate melt in both F-free and F-bearing systems, with Df/Zmr that range between 0.19 ± 0.02 and 0.38 ± 0.03. However, the relatively high Df/Zmr values indicate that alkali-silica rich aqueous fluids generated by metamorphic devolatilization may contribute significantly to the recycling of HFSE in subduction zones. The efficient uptake of Zr (and likely other HFSE) by subduction zone fluids, regardless of their nature (aqueous fluid, hydrous melt, or supercritical fluid), supports the idea that the typical HFSE depletion recorded in arc magmas does not result from their incompatibility in water-rich slab-derived fluids but most probably originates from complex fluid-melt-rock interactions occurring at the slab interface and within the mantle wedge. At shallow crustal pressure conditions (800 °C and 0.3 GPa), Zr partitions reversely into the aqueous fluid in the presence of fluorine (Df/Zmr = 1.40 ± 0.10) as observed for Nb at similar conditions by Webster et al. (1989). The enrichment of the aqueous phase in HFSE (Zr, Nb) at shallow crustal conditions is likely related to the enhanced peralkalinity of low pressure, F-bearing aqueous fluid with temperature, that provides the favorable conditions for their mobilization via the formation of HFSE-O-Si/Na clusters. This mechanism may control the enrichment in HFSE (and plausibly other rare metals such as REE) in early magmatic fluids exsolved from granitic melts, leading to the formation of HFSE-enriched aggregates in shallow magmatic-hydrothermal environments (e.g., Strange Lake and Thor Lake Nechalacho deposit, Canada; Galineiro complex, Spain).

The partial 1H NMR spectra of Al–OH and molecular H2O in hydrous aluminosilicate glasses: Component-Resolved analysis of 27Al–1H cross polarization and 1H spin-echo MAS NMR spectra

The Component-Resolved methodology was applied to (1)H spin-echo and (27)Al-(1)H cross polarization (CP) MAS NMR data of aluminosilicate glasses. The method was able to resolve two components with different T2 relaxation rates, hydroxyl groups (OH) and molecular water (H(2)O(mol)), from the spin-echo data and to determine partial spectra and the relative abundances of OH and H(2)O(mol). The algorithm resolved two to three components with different (27)Al-(1)H CP dynamics from the (27)Al-(1)H cross polarization data; the obtained partial NMR spectra for Al-OH are in excellent agreement with those obtained previously from the difference spectra between spectra with various contact times and confirm previous quantitative results and models for the Al-OH, Si-OH and H(2)O(mol) speciation (Malfait and Xue, 2010).

Fast and Minimal‐Solvent Production of Superinsulating Silica Aerogel Granulate

With their low thermal conductivity (λ), silica aerogels can reduce carbon emissions from heating and cooling demands, but their widespread adoption is limited by the high production cost. A one-pot synthesis for silica aerogel granulate is presented that drastically reduces solvent use, production time, and global warming potential. The inclusion of the hydrophobization agent prior to gelation with a post-gelation activation step, enables a complete production cycle of less than four hours at the lab scale for a solvent use close to the theoretical minimum, and limits the global warming potential. Importantly, the one-pot aerogel granulate retains the exceptional properties associated with silica aerogel, mostly λ=14.4±1.0 mW m-1 ⋅K-1 for the pilot scale materials, about half that of standing air (26 mW m-1 ⋅K-1 ). The resource-, time-, and cost-effective production will allow silica aerogels to break out of its niche into the mainstream building and industrial insulation markets.

Densified glasses as structural proxies for high-pressure melts: Configurational compressibility of silicate melts retained in quenched and decompressed glasses

Abstract The structures of high-pressure magmatic liquids have often been inferred from spectroscopic studies on quenched and decompressed glasses. However, it has not been completely verified whether the structures of quenched and decompressed glasses are representative of the structure of their corresponding liquids at the glass transition temperature and synthesis pressure. Here, we provide quantitative evidence for the retention of pressure-induced configurational changes upon isobaric quench and isothermal decompression for synthesis pressures up to 3.5 GPa. We use the degree of densification and elastic compressibility of permanently densified glasses, together with thermo-elastic data from the literature, to calculate the density of the melt at the glass transition temperature and synthesis pressure. The derived densities agree with those derived directly from the thermal equations of state of the melts. This observation indicates that, at least up to 3.5 GPa, the densified structure of the melt is preserved in the glass upon quenching and decompression; this validates past and future structural studies of high-pressure melts based on studies of quenched and decompressed glasses.

Biopolymer Aerogels and Foams: Chemistry, Properties, and Applications

Biopolymer aerogels were among the first aerogels produced, but only in the last decade has research on biopolymer and biopolymer-composite aerogels become popular, motivated by sustainability arguments, their unique and tunable properties, and ease of functionalization. Biopolymer aerogels and open-cell foams have great potential for classical aerogel applications such as thermal insulation, as well as emerging applications in filtration, oil-water separation, CO2 capture, catalysis, and medicine. The biopolymer aerogel field today is driven forward by empirical materials discovery at the laboratory scale, but requires a firmer theoretical basis and pilot studies to close the gap to market. This Review includes a database with over 3800 biopolymer aerogel properties, evaluates the state of the biopolymer aerogel field, and critically discusses the scientific, technological, and commercial barriers to the commercialization of these exciting materials.

The nearly complete dissociation of water in glasses with strong aluminum avoidance

Abstract Water is dissolved in silicate glasses and melts as hydroxyl groups and molecular water, with mostly hydroxyl groups at low water contents and mostly molecular water at high water contents. However, we recently predicted that water will be dissociated nearly completely in potassium aluminosilicate glasses with more alumina than silica because of the strong aluminum avoidance and the strong tendency for Al-O-Al linkages to hydrolyze in such glasses. In the present study, I test this prediction on hydrous K2Al2SiO6 glasses: the Raman and infrared absorption spectra show that water is indeed predominantly present as hydroxyl groups, even for glasses with more than 7 wt% water. This observation validates the previously proposed speciation reactions, demonstrates that variations in water speciation are related to the nature of the cations to which the hydroxyl groups are bonded, and indicates that the classical picture of water dissolution, with predominantly molecular water at high water contents, may not apply near compositional extremes.