Show Abstract ▼

Abstract: Bubble nucleation and growth dynamics exert a primary control on the explosivity of volcanic eruptions. Numerous theoretical and experimental studies aim to capture the complex process of melt vesiculation, whereas textural studies use vesicle populations to reconstruct magma behaviour. However, post-fragmentation vesiculation in rhyolitic bombs can create final quenched bubble (vesicle) textures that are not representative of the nature of fragmenting magma within the conduit. To examine bubble growth in hydrous rhyolitic bombs, we have used heated stage microscopy to directly observe vesiculation of a Chaitén rhyolite melt (with an initial dissolved water content of ∼0.95 wt %) at atmospheric pressure and magmatic temperatures upon reheating. Thin wafers of obsidian were held from 5 min up to two days in the heated stage at temperatures between 575 °C and 875 °C. We found that bubble growth rates, measured through changes in bubble diameter, increased with both temperature and bubble size. The average growth rate at the highest temperature of 875 °C is ∼1.27 μm s−1, which is substantially faster than the lowest detected growth rate of ∼0.02 μm s−1 at 725 °C; below this temperature no growth was observed. Average growth rate Vr follows an exponential relationship with temperature, T and inferred melt viscosity η, where Vr = 5.57 10−7e0.016 and Vr = 3270.26e−1.117η. Several stages of evolving bubble morphology were directly observed, including initial relaxation of deformed bubbles into spheres, extensive growth of spheres, and, at higher temperatures, close packing and foam formation. Bubble deformation due to bubble-bubble interaction and coalescence was observed in most experiments. We use our simple, experimentally-determined relationship between melt viscosity and bubble growth rates to model post-fragmentation vesicle growth in a cooling 1 m-diameter rhyolitic bomb. The results, which indicate negligible vesicle growth within 2–3 cm of the bomb surface, correspond well with the observed dense margin thickness of a Chaitén bomb of comparable dimensions. The experiments described can be used to effectively reconstruct the post-fragmentation vesiculation history of bombs through simple analytical expressions which provide a useful tool for aiding in the interpretation of pumiceous endmember textures in hydrous rhyolitic bombs.

Open Access

Show Abstract ▼

Abstract: The demand for xylenes is projected to increase over the coming decades. The separation of xylene isomers, particularly p- and m-xylenes, is vital for the production of numerous polymers and materials. However, current state-of-the-art separation is based upon fractional crystallisation at 220 K which is highly energy intensive. Here, we report the discrimination of xylene isomers via refinement of the pore size in a series of porous metal–organic frameworks, MFM-300, at sub-angstrom precision leading to the optimal kinetic separation of all three xylene isomers at room temperature. The exceptional performance of MFM-300 for xylene separation is confirmed by dynamic ternary breakthrough experiments. In-depth structural and vibrational investigations using synchrotron X-ray diffraction and terahertz spectroscopy define the underlying host–guest interactions that give rise to the observed selectivity (p-xylene < o-xylene < m-xylene) and separation factors of 4.6–18 for p- and m-xylenes.

Open Access

Show Abstract ▼

Abstract: Vibrational microspectroscopy via Fourier transform infrared (FTIR) faces an experimental trade-off among the signal to noise ratio (SNR), acquisition time, spatial resolution, and sample coverage. This is mainly associated with broadband source type: e.g. low brightness thermal sources with high flux for large field of view imaging at low resolution, or low ´etendue of synchrotron radiation infrared (SRIR) for diffraction-limited scanning mi- croanalysis at high magnification.1 Adaptive optics (AO), in this case deformable mirror (DM), is a potent tool in tackling the problem by modulating the intensity of high brightness structured SRIR beam toward a homo- geneous field illumination for IR imaging at high magnification. The latter is required for an efficient coupling of SRIR source to a multi-pixel detector such as focal plane array (FPA).2 Additionally, DM enables to achieve different shapes, optimized for different Cassegrain IR objective. Regardless, the quality of the generated beam relies upon the performance of the adaptive elements, i.e. actuators and their linear and reproducible response to the applied voltage. Moreover, the beam shaping capability of a single DM in controlling light beam position and angle is limited by its actuators influence function. In this work, we implemented two DMs for intensity shaping for the complex SRIR beam. A variation of multi-conjugate AO is implemented to characterize the performance of DMs and their actuators transfer function at multiple locations. An IR sensitive microbolometer array has been optically conjugated to the focal plane of individual actuators and the far-field of DM, in order to probe the corresponding actuating response. By analysing each actuator’s response individually, a measure of linear independence, uniformity in response, and cross-coupling can be obtained in a spectral range, from visible to near and mid IR. Additionally, by assembling the vectorized version of each actuator response, the transfer matrix can be formed. This matrix describes the relationship between the actuation effect on the beam and the response of the IR microbolometer, at the given conjugate planes. Based on such discussion, we assess the stability of the deformable mirror for open-loop (i.e. without feedback) operation.

Open Access

Show Abstract ▼

Abstract: Metal–organic frameworks (MOFs) functionalised with amine, amide and hydroxyl groups show great promise for CO2 binding due to their ability to form hydrogen bonds to CO2. Herein we report the adsorption and selectivity of CO2 in four iso-reticular MOFs adopting the NbO topology. Functionalisation of the parent MOF, MFM-102, with –NO2, –NH2 and alkyl groups leads to an enhancement of CO2 adsorption of up to 36% for the NO2-decorated MOF and with raised selectivity. MFM-102-NO2 shows the highest adsorption capacity for CO2 (184 cm3 g−1 at 273 K and 1.0 bar) within this series, comparable to the best-behaving iso-reticular MOFs. At 298 K and 1.0 bar, MFM-102-NO2 shows a CO2/CH4 selectivity of 5.0. In situ inelastic neutron scattering and synchrotron FT-IR micro-spectroscopy were employed to elucidate the host–guest interaction dynamics within CO2-loaded MFM-102-NO2. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-102-NO2, and, to the best of our knowledge, we report the first example of CO2 binding to a –NO2 group in a porous MOF. Synergistic effects between the –NO2 group and the open metal sites lead to optimal binding of CO2 molecules within MFM-102-NO2 via hydrogen bonding to C–H groups.

Show Abstract ▼

Abstract: Operando synchrotron infrared microspectroscopy (OIMS) was used to study the conversion of methanol over coffin-shaped HZSM-5 crystals of different sizes: large (∼250 × 80 × 85 μm3), medium (∼160 × 60 × 60 μm3) and small (∼55 × 30 × 30 μm3). The induction period, for direct alkene formation by deprotonation of surface methoxy groups, was found to decrease with decreasing crystal size and with increasing reaction temperature. Experiments with a continuous flow of dimethylether showed that evolution of the hydrocarbon pool and indirect alkene formation is also strongly dependent on crystal size. These measurements suggest that the hydrocarbon pool formation and indirect alkene generation should be almost instantaneous at reaction temperatures used in practical catalysis with crystal sizes typically ∼1 μm3.