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At least 451 records · Page 25

Ionization of HCCI Neutral and Cations by Strong Laser Fields Simulated With Time Dependent Configuration Interaction

Strong field ionization of neutral iodoacetylene (HCCI) can produce a coherent superposition of the X and A cations. This superposition results in charge migration between the CC π orbital and the iodine π-type lone pair which can be monitored by strong field ionization with short, intense probe pulses. Strong field ionization of the X and A states of HCCI cation was simulated with time-dependent configuration interaction using singly ionized configurations and singly excited, singly ionized configurations (TD-CISD-IP) and an absorbing boundary. Studies with static fields were used to obtain the 3-dimensional angular dependence of instantaneous ionization rates by strong fields and the orbitals involved in producing the cations and dications. The frequency of charge oscillation is determined by the energy separation of the X and A states; this separation can change depending on the direction and strength of the field. Furthermore, fields along the molecular axis can cause extensive mixing between the field-free X and A configurations. For coherent superpositions of the X and A states, the charge oscillations are characterized by two frequencies–the driving frequency of the laser field of the probe pulse and the intrinsic frequency due to the energy separation between the X and A states. For linear and circularly polarized pulses, the ionization rates show marked differences that depend on the polarization direction of the pulse, the carrier envelope phase and initial phase of the superposition. Varying the initial phase of the superposition at the beginning of the probe pulse is analogous to changing the delay between the pump and probe pulses. The charge oscillation in the coherent superposition of the X and A states results in maxima and minima in the ionization yield as a function of the superposition phase

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular dynamics simulations of radiation response of $\mathrm{LiAlO_2}$ and $\mathrm{LiAl_5O_8}$

Here, we report the findings of a computational investigation of defect production and migration in two lithium aluminate ceramics: LiAlO 2 and LiAl 5 O 8 . Although the first ceramic, LiAlO 2 has been widely investigated computationally, especially via molecular dynamics (MD), there have been no MD studies done on LiAl 5 O 8 up to date, due to the lack of interatomic potentials for this system. This work implemented an existing set of Li-Al-O coulombic and Buckingham potential parameters for the LiAl 5 O 8 system from the literature, followed by validating it based on experimental values of density, crystallinity, bond lengths and melting point. The Li + diffusion in the two ceramics was examined and was found to be one order of magnitude slower in LiAl 5 O 8 (D 0 = 3.17 x 10 -11 m 2 /s) as compared to that in LiAlO 2 (D 0 = 4.02 x 10 -10 m 2 /s) at 600 K. The lithium vacancy migration barrier of 4.15 eV in LiAl 5 O 8 was more than three times that in LiAlO 2 (1.31 eV) possibly due to stronger ordering in the Li-O 6 octahedra of LiAl 5 O 8 than in Li-O 4 tetrahedra of LiAlO 2 . The Li displacement threshold energy (E d ) in LiAl 5 O 8 was found to have a median value of 68 eV which is much higher than that in LiAlO 2 (40 eV). The greater E d for Li signifies a lower likelihood for defect formation and clustering and thus lower tendency for amorphization in LiAl 5 O 8 . The presented results show the difference in defect dynamics in the two ceramics that may help us understand the susceptibility of the two ceramics to amorphization caused by irradiation.

36 MATERIALS SCIENCE↗

FOXK1 plays an oncogenic role in the development of esophageal cancer

Forkhead box k1 (FOXK1) is a member of the FOX class of transcription factors and it is dysregulated in many solid tumors including hepatocellular carcinoma, gastric cancer, colorectal cancer and prostate cancer. However, the expression status of FOXK1 and its clinical significance in esophageal cancer (EC) is still uncertain. Our study aimed at investigating the significance of FOXK1 expression in human EC and its biological function in the development of EC. We found that FOXK1 was overexpressed in EC tissues compared with corresponding non-tumor tissues using immunohistochemistry. And high FOXK1 expression was related to poor differentiation of EC. The Kaplan-Meier curve indicated that high FOXK1 expression may result in poor prognosis of EC patients. Furthermore, overexpression of FOXK1 in EC9706 cell inhibited cell apoptosis and promoted cell proliferation and migration, and suppression of FOXK1 in EC109 cell obtained reverse results. Our data suggest that FOXK1 plays an oncogenic role in EC pathogenesis and can serve as a therapeutic target for patients with EC. - Highlights: • It's the first time investigating the relationship between FOXK1 and esophageal cancer (EC). • FOXK1 could inhibit cell apoptosis and promote cell proliferation and migration of EC in vitro. • FOXK1 plays an oncogenic role in EC pathogenesis and can serve as a therapeutic target for patients with EC.

60 APPLIED LIFE SCIENCES↗

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multi-Dimensional Calibration of Impact Dynamic Models

NASA Langley, under the Subsonic Rotary Wing Program, recently completed two helicopter tests in support of an in-house effort to study crashworthiness. As part of this effort, work is on-going to investigate model calibration approaches and calibration metrics for impact dynamics models. Model calibration of impact dynamics problems has traditionally assessed model adequacy by comparing time histories from analytical predictions to test at only a few critical locations. Although this approach provides for a direct measure of the model predictive capability, overall system behavior is only qualitatively assessed using full vehicle animations. In order to understand the spatial and temporal relationships of impact loads as they migrate throughout the structure, a more quantitative approach is needed. In this work impact shapes derived from simulated time history data are used to recommend sensor placement and to assess model adequacy using time based metrics and orthogonality multi-dimensional metrics. An approach for model calibration is presented that includes metric definitions, uncertainty bounds, parameter sensitivity, and numerical optimization to estimate parameters to reconcile test with analysis. The process is illustrated using simulated experiment data.

Horta, Lucas G.↗

A study of thermal properties of sodium titanate nanotubes synthesized by microwave-assisted hydrothermal method

Highlights: • The microwave-assisted hydrothermal route was used for titanate nanotubes synthesis. • Conversion to single-phase nanotube morphology completes after 8 h reaction time. • The nanotube morphology is stable up to 600 °C, as determined by in-situ XRD and SEM. • Sodium ions migrate to the surface due to thermal motion and structure condensation. - Abstract: Sodium titanate nanotubes (NaTiNTs) were synthesized by microwave-assisted hydrothermal treatment of commercial TiO{sub 2}, at constant temperature (135 °C) and different irradiation times (15 min, 1, 4, 8 and 16 h). The products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, differential scanning calorimetry and specific surface area measurements. The irradiation time turned out to be the key parameter for morphological control of the material. Nanotubes were observed already after 15 min of microwave irradiation. The analyses of the products irradiated for 8 and 16 h confirm the complete transformation of the starting TiO{sub 2} powder to NaTiNTs. The nanotubes are open ended with multi-wall structures, with the average outer diameter of 8 nm and specific surface area up to 210 m{sup 2}/g. The morphology, surface area and crystal structure of the sodium titanate nanotubes synthesized by microwave-assisted hydrothermal method were similar to those obtained by conventional hydrothermal method.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Validation of the ERO2.0 code using W7-X and JET experiments and predictions for ITER operation

Abstract The paper provides an overview of recent modelling of global material erosion and deposition in the fusion devices Wendelstein 7-X (W7-X), JET and ITER using the Monte-Carlo code ERO2.0. For validating the modelling tool in a three-dimensional environment, W7-X simulations are performed to describe carbon erosion from the graphite test divertor units, which were equipped in operational phase OP 1.2 and analysed post-mortem. Synthetic spectroscopy of carbon line emission is compared with experimental results from the divertor spectrometer measurement system, showing a good agreement in the e-folding lengths in the radial intensity profiles of carbon. In the case of metallic wall materials, earlier modelling of the Be/W environment in JET and ITER is revisited and extended with an updated set of sputtering and reflection data, as well as including the mixing model for describing the Be/W dynamics in the divertor. Motivated by recent H/D/T isotope experiments in JET, limited and diverted configuration pulses are modelled, showing the expected trend of both Be and W erosion increasing with isotope mass. For the JET diverted configuration pulses, it is shown that Be migrates predominantly to the upper part of the inner divertor where it initially leads to strong W erosion. With longer exposure time, the growth of a Be deposited layer leads to a reduction of W erosion in that region. A similar trend is observed in simulations of the ITER baseline Q = 10 scenario, however with a more symmetric Be migration pattern leading to deposition also on the outer divertor.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Electronic Structure Calculations of Oxygen Atom Transport Energetics in the Presence of Screw Dislocations in Tungsten

Plastic flow in body-centered cubic (bcc) alloys is governed by the thermally-activated motion of screw dislocations in close-packed planes. In bcc interstitial solid solutions, solute diffusion can occur at very fast rates owing to low migration energies and solute concentrations. Under mechanical loading, solutes may move on the same or similar time scale as dislocations glide, even at low temperatures, potentially resulting in very rich co-evolution processes that may have important effects in the overall material response. It is therefore important to accurately quantify the coupling between interstitial impurities and dislocations, so that larger-scale models can correctly account for their interactions. In this paper, we use electronic structure calculations to obtain the energetics of oxygen diffusion under stress and its interaction energy with screw dislocation cores in bcc tungsten. We find that oxygen atoms preferentially migrate from tetrahedral to tetrahedral site with an energy of 0.2 eV. This energy couples only weakly to hydrostatic and deviatoric deformations, with activation volumes of less than 0.02 and 0.02 b 3 , respectively. The strongest effect is found for the inelastic interaction between O atoms and screw dislocation cores, which leads to attractive energies between 1.2 and 1.9 eV and sometimes triggers a transformation of the screw dislocation core from an easy core configuration to a hard core configuration.

36 MATERIALS SCIENCE↗

Insulation Resistance Degradation in Ni-BaTiO3 Multilayer Ceramic Capacitors

Insulation resistance (IR) degradation in Ni-BaTiO3 multilayer ceramic capacitors has been characterized by the measurement of both time to failure and direct-current (DC) leakage current as a function of stress time under highly accelerated life test conditions. The measured leakage current-time dependence data fit well to an exponential form, and a characteristic growth time SD can be determined. A greater value of tau(sub SD) represents a slower IR degradation process. Oxygen vacancy migration and localization at the grain boundary region results in the reduction of the Schottky barrier height and has been found to be the main reason for IR degradation in Ni-BaTiO3 capacitors. The reduction of barrier height as a function of time follows an exponential relation of phi (𝑡)=phi (0)e(exp -2Κt), where the degradation rate constant 𝐾=𝐾o𝑒(𝐸𝑘/𝑘𝑇) is inversely proportional to the mean time to failure (MTTF) and can be determined using an Arrhenius plot. For oxygen vacancy electromigration, a lower barrier height phi(0) will favor a slow IR degradation process, but a lower phi(0) will also promote electronic carrier conduction across the barrier and decrease the insulation resistance. As a result, a moderate barrier height phi(0) (and therefore a moderate IR value) with a longer MTTF (smaller degradation rate constant 𝐾) will result in a minimized IR degradation process and the most improved reliability in Ni-BaTiO3 multilayer ceramic capacitors.

dielectric degradation↗

Effect of alloying elements on defect evolution in Ni-20X binary alloys

The effect of alloying elements on radiation-induced microstructural evolution in Ni and Ni-20X (X = Fe, Cr, Mn and Pd) binary alloys was investigated using ion irradiation and cross-sectional transmission electron microscopy. The three-dimensional migration mode is identified to be the dominating migration mechanism for interstitial clusters in these binary alloys, contrary to the one-dimensional mode that dominates in the well-studied dilute alloys. The results reveal that: (1) the average size of defect clusters decreases as the solute atomic volume size factor increases. Smaller void size in Ni-20Cr is attributed to faster vacancy mobility in the near surface region, and weaker vacancy binding energy beyond the irradiation peak than Ni-20Fe. The smaller voids observed in Ni-20Mn and Ni-20Pd beyond the damage peak are due to the stronger Mn/Pd-vacancy binding effect of largely oversized solute atoms. (2) Oversized solutes can act as strong trapping sites for interstitials. The larger the solute atomic volume factor, the stronger the trapping force. This leads to a more significantly sluggish interstitial migration and smaller dislocation loop size. The average dislocation loop size in Ni-20Fe was four times larger than Ni-20Pd (atomic volume factor being 10.6% and 41.3%) but an order of magnitude lower in density. The smaller dislocation loop size in Ni-20Cr is attributed to stronger interstitial binding of Cr-Ni. In conclusion, overall, the alloying effect on defects is more significant in concentrated binary alloys than in dilute binary alloys, due to the concentration difference of alloying atoms and the interstitial dominant migration mechanisms in the main irradiated region.

36 MATERIALS SCIENCE↗

Hemispherically Asymmetric Volcanic Forcing of Tropical Hydroclimate During the Last Millennium

Volcanic aerosols exert the most important natural radiative forcing of the last millennium. State-of-the-art paleoclimate simulations of this interval are typically forced with diverse spatial patterns of volcanic forcing, leading to different responses in tropical hydroclimate. Recently, theoretical considerations relating the intertropical convergence zone (ITCZ) position to the demands of global energy balance have emerged in the literature, allowing for a connection to be made between the paleoclimate simulations and recent developments in the understanding of ITCZ dynamics. These energetic considerations aid in explaining the well-known historical, paleoclimatic, and modeling evidence that the ITCZ migrates away from the hemisphere that is energetically deficient in response to asymmetric forcing. Here we use two separate general circulation model (GCM) suites of experiments for the last millennium to relate the ITCZ position to asymmetries in prescribed volcanic sulfate aerosols in the stratosphere and related asymmetric radiative forcing. We discuss the ITCZ shift in the context of atmospheric energetics and discuss the ramifications of transient ITCZ migrations for other sensitive indicators of changes in the tropical hydrologic cycle, including global streamflow. For the first time, we also offer insight into the large-scale fingerprint of water isotopologues in precipitation (delta sup 18 Op) in response to asymmetries in radiative forcing. The ITCZ shifts away from the hemisphere with greater volcanic forcing. Since the isotopic composition of precipitation in the ITCZ is relatively depleted compared to areas outside this zone, this meridional precipitation migration results in a large-scale enrichment (depletion) in the isotopic composition of tropical precipitation in regions the ITCZ moves away from (toward). Our results highlight the need for careful consideration of the spatial structure of volcanic forcing for interpreting volcanic signals in proxy records and therefore in evaluating the skill of Common Era climate model output.

Radiative forcing↗

Long-range interactions between chiral molecules

Results of molecular quantum electrodynamics calculations of discriminatory interactions between two chiral molecules undergoing resonance energy transfer, van der Waals dispersion, and optical binding are presented. A characteristic feature of the theory is that the radiation field is quantized with signals consequently propagating between centres at the speed of light. In order to correctly describe optically active chromophores, it is necessary to include magnetic as well as electric dipole coupling terms in the time-dependent perturbation theory computations. Recent work investigating the effect of an absorptive and dispersive chiral medium on the rate of migration of energy will also be discussed.

74 ATOMIC AND MOLECULAR PHYSICS↗

Al(0.3)Ga(0.7)As / Al(0.05)Ga(0.95)As light-emitting diodes on GaAs-coated Si substrates grown by liquid phase epitaxy

Al(0.3)Ga(0.7)As/Al(0.05)Ga(0.95)As double-heterostructure light-emitting diodes (LEDs) were successfully grown for the first time by liquid phase epitaxy on a GaAs-coated Si substrate that was prepared by a sequential process of migration-enhanced epitaxy and molecular beam epitaxy. The edge-emitting LEDs had diode ideality factors of 1.54 at a forward-biased voltage higher than 0.9 V and external quantum efficiencies of 0.0033 W/A per facet. This efficiency is 50 times higher than the previously reported value, and is on the same order as that of AlGaAs homojunction LEDs fabricated on the GaAs substrates by liquid phase epitaxy.

Sakai, Shiro↗

Production of Star-Grazing and Star-Impacting Planetestimals via Orbital Migration of Extrasolar Planets

During the orbital migration of a giant extrasolar planet via ejection of planetesimals (as studied by Murray et al. in 1998), inner mean-motion resonances can be strong enough to cause planetesimals to graze or impact the star. We integrate numerically the motions of particles which pass through the 3:1 or 4:1 mean-motion resonances of a migrating Jupiter-mass planet. We find that many particles can be trapped in the 3:1 or 4:1 resonances and pumped to high enough eccentricities that they impact the star. This implies that for a planet migrating a substantial fraction of its semimajor axis, a fraction of its mass in planetesimals could impact the star. This process may be capable of enriching the metallicity of the star at a time when the star is no longer fully convective. Upon close approaches to the star, the surfaces of these planetesimals will be sublimated. Orbital migration should cause continuing production of evaporating bodies, suggesting that this process should be detectable with searches for transient absorption lines in young stars. The remainder of the particles will not impact the star but can be ejected subsequently by the planet as it migrates further inward. This allows the planet to migrate a substantial fraction of its initial semimajor axis by ejecting planetesimals.

Quillen, A. C.↗

Structural and Stratigraphic Controls on Methane Hydrate occurrence and distribution: Gulf of Mexico, Walker Ridge 313 and Green Canyon 955: Final Report

The goal of this project was to determine structural and stratigraphic controls on hydrate occurrence and distribution in Green Canyon (GC) 955 and Walker Ridge (WR) 313 blocks using seismic and well data. Gas hydrate was discovered in these blocks in coarse- and fine-grained sediments during the 2009 Joint Industrial project (JIP) Leg 11 drilling expedition. Although the immediate interest of the exploration community is exclusively hydrate which is present in coarse–grained sediments, factors that control hydrate and free gas distribution in the two blocks and whether coarse and fine-grained hydrate-bearing units are related in any manner, formed the core of this research. The project spanned from 10/01/2012 to 07/31/2016. In the project, in both the leased blocks, the interval spanning the gas hydrate stability zone (GHSZ) was characterized using a joint analysis of sparse Ocean Bottom Seismic (OBS) and dense, surface–towed multichannel seismic (MCS) data. The project team had the luxury of calibrating their results with two well logs. Advance processing methods such as depth migration and full-waveform inversion (FWI) were used for seismic data analysis. Hydrate quantification was achieved through interpretation of the FWI velocity field using appropriate rock physics models at both blocks. The seismic modeling/inversion methodology (common to both GC955 and WR313 blocks) was as follows. First, the MCS data were depth migrated using a P-wave velocity (VP) model constructed using inversion of reflection arrival times of a few (four in both cases) key horizons carefully picked in the OBS data to farthest possible offsets. Then, the resolution of the traveltime VP model was improved to wavelength scale by inverting OBS gathers up to the highest frequency possible (21.75 Hz for GC955 and 17.5 for WR313) using FWI. Finally, the hydrate saturation (or the volume fraction) was estimated at the well location assuming one of the other hydrate morphology (filling the primary or the secondary porosity) was extrapolated out from the wells using the FWI VP as a guide. General outcomes were as follows. First and foremost, an imaging methodology using sparse seismic data, which is easily replicable at other sites with similar datasets, has been demonstrated. The end product of this methodology at both the leased blocks is quantitative estimates of hydrate distribution. Second, at both locations there is strong evidence that the base of the GHSZ, which does not appear as a clear Bottom Simulating Reflection (BSR), manifests in the VP perturbations created by FWI, suggesting that FWI is sensitive to subtle compositional changes in shallow sediments and establishes it as a valuable tool for investigations of hydrate-bearing basins. Third, through joint interpretation of the depth migrated image and the FWI VP model, how structure and stratigraphy jointly determine hydrate and free gas distribution in both blocks could be clearly visualized. The joint interpretation also suggests that the coarse and fine grained hydrate-bearing sediments at both leased are connected. Site specific results, in addition to general results, are as follows. At GC955 the overlying fine-grained hydrate-bearing unit could have been sourced from the underlying hydrate coarse-grained channel-levee complex through a chimney feature. The channel-levee system at GC955 is compartmentalized by faults, of which only a few may be impermeable. Although compartmentalized, the channel-levee system in the GC955 as a whole might be in communication except selected zones. At WR313 the overlying fine-grained fracture-filled hydrate unit appears to be sourced from below the GHSZ. The reason that only a particular fine-grained unit has hydrate, despite having lower porosity that the bounding units, could be the presence of secondary porosity (such as those formed from clay dewatering under compaction). In conclusion, the project was a pioneering effort in in joint analysis of OBS and MCS datasets for advancing the knowledge about a hydrate and free–gas system dynamics using advanced processing methods such as FWI and depth migration. Results obtained in this project can greatly advance the tools and techniques used for delineating specific hydrate prospects. Results obtained in this project can also be seamlessly incorporated into other DOE funded project on modeling the potential productivity and commercial viability of hydrate from sand-dominated reservoirs. The OBS and MCS data in this project were acquired in 2012 (after the JIP II drilling) by the USGS and therefore the results are a posteriori. Nonetheless, the seismic inversion workflow established through this project can be used to generate various what-if quantification scenarios even in absence of logs and serve as a valuable tool for guiding drilling operations. Results from this project can augment other DOE sponsored projects on determining the commercial viability of methane production from the Gulf of Mexico.

03 NATURAL GAS↗

Silicon nanocrystals in SiN{sub x}/SiO{sub 2} hetero-superlattices: The loss of size control after thermal annealing

Superlattices containing 3 nm thick silicon rich silicon nitride sublayers and 3 nm and 10 nm thick SiO{sub 2} barriers were prepared by plasma enhanced chemical vapor deposition. Despite the as-prepared samples represented a well-kept multilayer structure with smooth interfaces, the high temperature annealing resulted in the total destruction of multilayer structure in the samples containing 3 nm SiO{sub 2} barriers. Energy-filtered transmission electron microscopy images of these samples indicated a silicon nanoclusters formation with sizes of 2.5–12.5 nm, which were randomly distributed within the structure. Although in the sample with 10 nm SiO{sub 2} barriers some fragments of the multilayer structure could be still observed after thermal annealing, nevertheless, the formation of large nanocrystals with diameters up to 10 nm was confirmed by dark field transmission electron microscopy. Thus, in contrast to the previously published results, the expected size control of silicon nanocrystals was lost. According to the FTIR results, the thermal annealing of SiN{sub x}/SiO{sub 2} superlattices led to the formation of silicon nanocrystals in mostly oxynitride matrix. Annealed samples demonstrated a photoluminescence peak at 885 nm related to the luminescence of silicon nanocrystals, as confirmed by time-resolved photoluminescence measurements. The loss of nanocrystals size control is discussed in terms of the migration of oxygen atoms from the SiO{sub 2} barriers into the silicon rich silicon nitride sublayers. A thermodynamic mechanism responsible for this process is proposed. According to this mechanism, the driving force for the oxygen migration is the gain in the configuration entropy related to the relative arrangements of oxygen and nitrogen atoms.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Conversion of Ethanol to Hydrocarbons on Hierarchical HZSM-5 Zeolites

This study reports synthesis, characterization, and catalytic activity of the nano-size hierarchical HZSM-5 zeolite with high mesoporosity produced via a solvent evaporation procedure. Further, this study compares hierarchical zeolites with conventional HZSM-5 zeolite with similar Si/Al ratios for the ethanol-to-hydrocarbon conversion process. The catalytic performance of the hierarchical and conventional zeolites was evaluated using a fixed-bed reactor at 360 °C, 300 psig, and a weight hourly space velocity of 7.9 h-1. For the low Si/Al ratio zeolite (~40), the catalytic life-time for the hierarchical HZSM-5 was approximately 2 times greater than the conventional HZSM-5 despite its coking amount deposited 1.6 times higher than conventional HZSM-5. For the high Si/Al ratio zeolite (~140), the catalytic life-time for the hierarchical zeolite was approximately 5 times greater than the conventional zeolite and the amount of coking deposited was 2.1 times higher. Correlation was observed between catalyst life time, porosity, and the crystal size of the zeolite. The nano-size hierarchical HZSM-5 zeolites containing mesoporosity demonstrated improved catalyst life-time compared to the conventional catalyst due to faster removal of products, shorter diffusion path length, and the migration of the coke deposits to the external surface from the pore structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impacts on mechanical strength of chemical reactions induced by hydrous supercritical CO2 in Boise Sandstone

Geomechanics experiments were used to assess mechanical alteration of Boise Sandstone promoted by reactions with supercritical carbon dioxide (scCO 2 ) and water vapor. During geologic carbon storage, scCO 2 is injected into subsurface reservoirs, forming buoyant plumes. At brine-plume interfaces, scCO 2 can dissolve into native brines, and water from brines can partition into scCO 2 , forming hydrous scCO 2 . This study investigates the effect of hydrous scCO 2 on the strength of Boise Sandstone. Samples are first exposed to recirculating hydrous scCO 2 for 24 h at 70 °C and 13.8 MPa scCO 2 pressure. Samples are reacted with scCO 2 with added water contents up to 500 mL. After scCO 2 exposure, samples are deformed at room temperature under confining pressures of 3.4, 6.9, and 10.3 MPa. The results demonstrate that hydrous scCO 2 induces chemical reactions in Boise Sandstone, with ions migrating from the solid into the hydrous scCO 2 phase. At the longer time-scales, these reactions could lead to mechanical weakening in the samples; however, on the scale of our experiments, the strength changes are within sample variability. Because the solubility of water in scCO 2 is extremely low (0.008 mol H 2 O per 1 mol CO 2 ), the mineral dissolution of Boise Sandstone was under 0.002 wt.%. Additionally, mineral grains and pore throats in Boise Sandstone are cemented with quartz, which is not susceptible to dissolution at these conditions. Our results indicate that humidity in scCO 2 plumes is unlikely to sustain chemical reactions and induce long term strength changes in quartz cemented sandstones due to resistant mineralogies and low water solubility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗