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At least 469 records · Page 26

Investigation of Stress Field and Fracture Development During Shale Maturation Using Analog Rock Systems

The emergence of hydrocarbons within shale as a major recoverable resource has sparked interest in fluid transport through these tight mudstones. Recent studies suggest the importance to recovery of microfracture networks that connect localized zones with large organic content to the inorganic matrix. This paper presents a joint modeling and experimental study to examine the onset, formation, and evolution of microfracture networks as shale matures. Both the stress field and fractures are simulated and imaged. A novel laboratory-scale, phase-field fracture propagation model was developed to characterize the material failure mechanisms that play a significant role during the shale maturation process. The numerical model developed consists of coupled solid deformation, pore pressure, and fracture propagation mechanisms. Benchmark tests were conducted to validate model accuracy. Laboratory-grade gelatins with varying Young’s modulus were used as scaled-rock analogs in two dimensional Hele-Shaw cell apparatus. Yeast within the gelatin generates gas in a fashion analogous to hydrocarbon formation as shale matures. These setups allow study and visualization of host rock elastic-brittle fracture and fracture network propagation mechanisms. The experimental setup was fitted to utilize photoelasticity principles coupled with birefringence properties of gelatin to explore visually the stress field of the gelatin as the fracture network developed. Stress optics image analysis and Linear Elastic Fracture Mechanics (LEFM) principles for crack propagation were used to monitor fracture growth for each gelatin type. Observed and simulated responses suggest gas diffusion within and deformation of the gelatin matrix as predominant mechanisms for energy dissipation depending on gelatin strength. LEFM, an experimental estimation of principal stress development with fracture growth, at different stages was determined for each gelatin rheology. Here, the interplay of gas diffusion and material deformation determines the resulting frequency and pattern of fractures. Results correlate with Young’s modulus. Experimental and computed stress fields reveal that fractures resulting from internal gas generation are similar to, but not identical to, type 1 opening mode.

58 GEOSCIENCES↗

TiO 2 /TiN Interface Enables Integration of Ni 5 P 4 Electrocatalyst with a III–V Tandem Photoabsorber for Stable Unassisted Solar-Driven Water Splitting

H 2 production by direct photoelectrochemical (PEC) water splitting has remained unachievable commercially, mainly due to rapid failure at the interface between the photoabsorber(s) and catalyst(s). PEC devices made from multijunction III-V semiconductors with platinum group metal (PGM) catalysts have yielded impressive initial solar-to-H 2 (STH) efficiency >19%, which rapidly corrodes in aqueous electrolytes. Here, TiO 2 /TiN layers were fused to create a bifunctional interface between a GaInP 2 /GaAs III-V tandem photoabsorber and a polycrystalline Ni 5 P 4 HER catalyst. Here, the TiO 2 serves as a conducting corrosion barrier, while a thin layer of much denser TiN (1 nm) blocks interlayer diffusion during fabrication. This strategy allows the elevated temperatures needed to crystallize the Ni 5 P 4 nanoparticles and fuse to the TiO 2 /TiN junction to achieve minimal optical loss without damaging the sensitive photoasbsorber. The resulting photocathode exhibits an initial STH efficiency of 11.4%-13.2% in sodium phosphate electrolyte at neutral pH 7. It operated continuously for over 200 h without failure above 10% STH efficiency, exceeding all previous benchmarks. The earth-abundant Ni 5 P 4 catalyst replaces costly PGM catalysts at comparable HER activity in neutral, acidic, or basic pH electrolytes.

08 HYDROGEN↗

Planck intermediate results: XXXVII. Evidence of unbound gas from the kinetic Sunyaev-Zeldovich effect

By looking at the kinetic Sunyaev-Zeldovich effect (kSZ) in Planck nominal mission data, we present in this paper a significant detection of baryons participating in large-scale bulk flows around central galaxies (CGs) at redshift z ≈ 0.1. We estimate the pairwise momentum of the kSZ temperature fluctuations at the positions of the Central Galaxy Catalogue (CGC) samples extracted from Sloan Digital Sky Survey (SDSS-DR7) data. For the foreground-cleaned SEVEM, SMICA, NILC, and COMMANDER maps, we find 1.8–2.5σ detections of the kSZ signal, which are consistent with the kSZ evidence found in individualPlanck raw frequency maps, although lower than found in the WMAP-9yr W-band (3.3σ). We further reconstruct the peculiar velocity field from the CG density field, and compute for the first time the cross-correlation function between kSZ temperature fluctuations and estimates of CG radial peculiar velocities. This correlation function yields a 3.0–3.7σ detection of the peculiar motion of extended gas on Mpc scales in flows correlated up to distances of 80–100 h -1 Mpc. Both the pairwise momentum estimates and the kSZ temperature-velocity field correlation find evidence for kSZ signatures out to apertures of 8 arcmin and beyond, corresponding to a physical radius of >1 Mpc, more than twice the mean virial radius of halos. This is consistent with the predictions from hydrodynamical simulations that most of the baryons are outside the virialized halos. We fit a simple model, in which the temperature-velocity cross-correlation is proportional to the signal seen in a semi-analytic model built upon N-body simulations, and interpret the proportionality constant as an effective optical depth to Thomson scattering. Finally, we find τ T = (1.4 ± 0.5) × 10 -4 ; the simplest interpretation of this measurement is that much of the gas is in a diffuse phase, which contributes little signal to X-ray or thermal Sunyaev-Zeldovich observations.

79 ASTRONOMY AND ASTROPHYSICS↗

Defect-mediated metastability and carrier lifetimes in polycrystalline (Ag,Cu)(In,Ga)Se 2 absorber materials

Using a combination of optical and electrical measurements, we develop a model for metastable defects in Ag-alloyed Cu(In,Ga)Se 2 , one of the leading thin film photovoltaic materials. By controlling the pre-selenization conditions of the back contact prior to the growth of polycrystalline (Ag,Cu)(In,Ga)Se 2 absorbers and subsequently exposing them to various stresses (light soaking and dark-heat), we explore in this paper the nature and role of metastable defects on the electro-optical and photovoltaic performance of high-efficiency solar cell materials and devices. Positron annihilation spectroscopy indicates that dark-heat exposure results in an increase in the concentration of the selenium–copper divacancy complex (V Se –V Cu ), attributed to depassivation of donor defects. Deep-level optical spectroscopy finds a corresponding increase of a defect at Ev+0.98 eV, and deep-level transient spectroscopy suggests that this increase is accompanied by a decrease in the concentration of mid-bandgap recombination centers. Time-resolved photoluminescence excitation spectroscopy data are consistent with the presence of the V Se –V Cu divacancy complex, which may act as a shallow trap for the minority carriers. Light-soaking experiments are consistent with the V Se –V Cu optical cycle proposed by Lany and Zunger, resulting in the conversion of shallow traps into recombination states that limit the effective minority carrier recombination time (and the associated carrier diffusion length) and an increase in the doping density that limits carrier extraction in photovoltaic devices.

14 SOLAR ENERGY↗

Localization of fluorescent targets in deep tissue with expanded beam illumination for studies of cancer and the brain

Imaging fluorescence through millimeters or centimeters of tissue has important in vivo applications, such as guiding surgery and studying the brain. Often, the important information is the location of one of more optical reporters, rather than the specifics of the local geometry, motivating the need for a localization method that provides this information. We present an optimization approach based on a diffusion model for the fast localization of fluorescent inhomogeneities in deep tissue with expanded beam illumination that simplifies the experiment and the reconstruction. We show that the position of a fluorescent inhomogeneity can be estimated while assuming homogeneous tissue parameters and without having to model the excitation profile, reducing the computational burden and improving the utility of the method. We perform two experiments as a demonstration. First, a tumor in a mouse is localized using a near infrared folate-targeted fluorescent agent (OTL38). This result shows that localization can quickly provide tumor depth information, which could reduce damage to healthy tissue during fluorescence-guided surgery. Second, another near infrared fluorescent agent (ATTO647N) is injected into the brain of a rat, and localized through the intact skull and surface tissue. This result will enable studies of protein aggregation and neuron signaling.

60 APPLIED LIFE SCIENCES↗

CROSS-CORRELATION BETWEEN X-RAY AND OPTICAL/NEAR-INFRARED BACKGROUND INTENSITY FLUCTUATIONS

Angular power spectra of optical and infrared background anisotropies at wavelengths between 0.5 and 5 μ m are a useful probe of faint sources present during reionization, in addition to faint galaxies and diffuse signals at low redshift. The cross-correlation of these fluctuations with backgrounds at other wavelengths can be used to separate some of these signals. A previous study on the cross-correlation between X-ray and Spitzer fluctuations at 3.6 μ m and 4.5 μ m has been interpreted as evidence for direct collapse black holes present at z > 12. Here we return to this cross-correlation and study its wavelength dependence from 0.5 to 4.5 μ m using Hubble and Spitzer data in combination with a subset of the 4 Ms Chandra observations in GOODS-S/ECDFS. Our study involves five Hubble bands at 0.6, 0.7, 0.85, 1.25, and 1.6 μ m, and two Spitzer -IRAC bands at 3.6 μ m and 4.5 μ m. We confirm the previously seen cross-correlation between 3.6 μ m (4.5 μ m) and X-rays with 3.7 σ (4.2 σ ) and 2.7 σ (3.7 σ ) detections in the soft [0.5–2] keV and hard [2–8] keV X-ray bands, respectively, at angular scales above 20 arcsec. The cross-correlation of X-rays with Hubble is largely anticorrelated, ranging between the levels of 1.4 σ –3.5 σ for all the Hubble and X-ray bands. This lack of correlation in the shorter optical/NIR bands implies the sources responsible for the cosmic infrared background at 3.6 and 4.5 μ m are at least partly dissimilar to those at 1.6 μ m and shorter.

79 ASTRONOMY AND ASTROPHYSICS↗

Method and system for gas flow mitigation of molecular contamination of optics

A computer-implemented method for determining an optimized purge gas flow in a semi-conductor inspection metrology or lithography apparatus, comprising receiving a permissible contaminant mole fraction, a contaminant outgassing flow rate associated with a contaminant, a contaminant mass diffusivity, an outgassing surface length, a pressure, a temperature, a channel height, and a molecular weight of a purge gas, calculating a flow factor based on the permissible contaminant mole fraction, the contaminant outgassing flow rate, the channel height, and the outgassing surface length, comparing the flow factor to a predefined maximum flow factor value, calculating a minimum purge gas velocity and a purge gas mass flow rate from the flow factor, the contaminant mass diffusivity, the pressure, the temperature, and the molecular weight of the purge gas, and introducing the purge gas into the semi-conductor inspection metrology or lithography apparatus with the minimum purge gas velocity and the purge gas flow rate.

42 ENGINEERING↗

Dark matter and H i in ultra-diffuse galaxy UGC 2162

ABSTRACT Our GMRT (Giant Metrewave Radio Telescope) H i observations of the ultra-diffuse galaxy (UDG) UGC 2162, projected ∼ 300 kpc from the centre of the M 77 group, reveal it to a have an extended H i disc ($R_{\rm H\,{\small I}}/R_{25}$ ∼ 3.3) with a moderate rotational velocity (Vrot ∼ 31 km s−1). This Vrotis in line with that of dwarf galaxies with similar H i mass. We estimate an Mdyn of ∼1.14 × 109 M⊙ within the galaxy’s $R_ \rm {H\,{\small I}}$ ∼ 5.2 kpc. Additionally, our estimates of M200 for the galaxy from NFW models are in the range of 5.0–8.8 × 1010 M⊙. Comparing UGC 2162 to samples of UDGs with H i detections show it to have amongst the smallest Re with its MH i/M* being distinctly higher and g – icolour slightly bluer than typical values in those samples. We also compared H i and dark matter (DM) halo properties of UGC 2162 with dwarf galaxies in the LITTLE THINGS sample and find its DM halo mass and profile are within the range expected for a dwarf galaxy. While we were unable to determine the origin of the galaxy’s present-day optical form from our study, its normal H i rotation velocity in relation to its H i mass, H i morphology, environment, and dwarf mass DM halo ruled out some of the proposed ultra-diffuse galaxy formation scenarios for this galaxy.

Sengupta, Chandreyee↗

Growth of lattice-matched GaInAsP grown on vicinal GaAs(001) substrates within the miscibility gap for solar cells

The growth of quaternary Ga 0.68 In 0.32 As 0.35 P 0.65 by metal-organic vapor phase epitaxy is very sensitive to growth conditions because the composition is within a miscibility gap. In this investigation, we fabricated 1 um-thick lattice-matched GaInAsP films grown on GaAs(001) for application to solar cells. In order to characterize the effect of the surface diffusion of adatoms on the material quality of alloys, the growth temperature and substrate miscut are varied. Transmission electron microscopy and two-dimensional in-situ multi-beam optical stress determine that growth temperatures of 650 degrees C and below enhance the formation of the CuPtB atomic ordering and suppress material decomposition, which is found to occur at the growth surface. The root-mean-square (RMS) roughness is reduced from 33.6 nm for 750 degrees C to 1.62 nm for 650 degrees C, determined by atomic force microscopy. Our initial investigations show that the RMS roughness can be further reduced using increased miscut angle, and substrates miscut toward (111)A, leading to an RMS roughness of 0.56 nm for the sample grown at 600 degrees C on GaAs miscut 6 degrees toward (111)A. Using these conditions, we fabricate an inverted hetero-junction 1.62 eV Ga 0.68 In 0.32 As 0.35 P 0.65 solar cell without an anti-reflection coating with a short-circuit current density, open-circuit voltage, fill factor, and efficiency of 12.23 mA/cm2, 1.12 V, 86.18%, and 11.80%, respectively.

14 SOLAR ENERGY↗

Isotope tracer investigation and ab-initio simulation of anisotropic hydrogen transport and possible multi-hydrogen centers in tin dioxide

Hydrogen as an impurity in single crystals of tin dioxide was investigated through diffusivity and vibrational-mode analyses performed using isotope tracers and density functional theory calculations. It was found that hydrogen diffusion along the 〈001〉 axis is very fast, even at relatively low temperatures (400 °C), but is considerably slower within the (001) plane. Using transitional state calculations, this diffusion behavior was determined to be the result of anisotropy in the migration barrier for interstitial hydrogen (H{sub i}). In addition, the two distinct vibrational modes observed in the optical spectrum were identified as the O-H stretching modes of Hi and the substitutional hydrogen at the tin sites.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Fugitive methane detection using open-path stand-off chirped laser dispersion spectroscopy

We report an open-path chirped laser dispersion spectrometer capable of detecting the atmospheric methane concentration above the background using both specular and diffusive reflective surfaces via two distinct operation modes in a stand-off detection configuration. The system is integrated with simultaneous ranging functionality, which enables average concentration measurements for varying optical pathlengths. The system was first tested for accuracy and characterized to achieve sensitivity of 2.9 p p m - m / H z 1 / 2 and pathlength precision of 0.2 m / H z 1 / 2 with a controlled release of methane outside the laboratory. The instrument was subsequently field-deployed in the proximity of a natural gas compressor station for fugitive methane detection. The instrument successfully detected methane plumes and narrowed down the location of the plume through multi-path measurement. The field measurements were verified by a co-located reference mobile methane sensor.

Chen, Yifeng↗

Disk and circumsolar radiances in the presence of ice clouds

The impact of ice clouds on solar disk and circumsolar radiances is investigated using a Monte Carlo radiative transfer model. The monochromatic direct and diffuse radiances are simulated at angles of 0 to 8° from the center of the sun. Input data for the model are derived from measurements conducted during the 2010 Small Particles in Cirrus (SPARTICUS) campaign together with state-of-the-art databases of optical properties of ice crystals and aerosols. For selected cases, the simulated radiances are compared with ground-based radiance measurements obtained by the Sun and Aureole Measurements (SAM) instrument. First, the sensitivity of the radiances to the ice cloud properties and aerosol optical thickness is addressed. The angular dependence of the disk and circumsolar radiances is found to be most sensitive to assumptions about ice crystal roughness (or, more generally, non-ideal features of ice crystals) and size distribution, with ice crystal habit playing a somewhat smaller role. Second, in comparisons with SAM data, the ice cloud optical thickness is adjusted for each case so that the simulated radiances agree closely (i.e., within 3 %) with the measured disk radiances. Circumsolar radiances at angles larger than ≈ 3° are systematically underestimated when assuming smooth ice crystals, whereas the agreement with the measurements is better when rough ice crystals are assumed. In conclusion, our results suggest that it may well be possible to infer the particle roughness directly from ground-based SAM measurements. In addition, the results show the necessity of correcting the ground-based measurements of direct radiation for the presence of diffuse radiation in the instrument's field of view, in particular in the presence of ice clouds.

54 ENVIRONMENTAL SCIENCES↗

Mechanical and optical response of [100] lithium fluoride to multi-megabar dynamic pressures

An understanding of the mechanical and optical properties of lithium fluoride (LiF) is essential to its use as a transparent tamper and window for dynamic materials experiments. In order to improve models for this material, we applied iterative Lagrangian analysis to ten independent sets of data from magnetically driven planar shockless compression experiments on single crystal [100] LiF to pressures as high as 350 GPa. We found that the compression response disagreed with a prevalent tabular equation of state for LiF that is commonly used to interpret shockless compression experiments. We also present complementary data from ab initio calculations performed using the diffusion quantum Monte Carlo method. The agreement between these two data sets lends confidence to our interpretation. In order to aid in future experimental analysis, we have modified the tabular equation of state to match the new data. We have also extended knowledge of the optical properties of LiF via shock-compression and shockless compression experiments, refining the transmissibility limit, measuring the refractive index to ~300 GPa, and confirming the nonlinear dependence of the refractive index on density. Lastly, we present a new model for the refractive index of LiF that includes temperature dependence and describe a procedure for correcting apparent velocity to true velocity for dynamic compression experiments.

36 MATERIALS SCIENCE↗

Advancing Enhanced Raman Spectroscopy to Detect and Measure NOW Pheromones (CPRB 2022 proposal)

Insect sex pheromones are chemical compounds that insects release to attract their partners over distances of hundreds of meters or even kilometers, in complete darkness and without any audible signals. Use of synthetic forms of key compounds have in some cases become an essential component of monitoring and/or managing key pests of agricultural crops, including navel orangeworm (Amyelois transitella) (NOW) in California tree nuts. These pheromone-based strategies can include monitoring, mating disruption, mass trapping, attract-and-kill and push-pull. There are currently multiple commercially available mating disruption products available for NOW and recent studies have demonstrated that they can be effectively used to reduce crop damage by this pest. Just how mating disruption works is not fully established and likely varies across products and target species. For instance, the extent to which synthetic pheromones compete with natural pheromone is not well understood, or in the case of monitoring, how efficaciously the insect follows the diffusing plumes, especially across large blocks and at plot borders. Furthermore, there may be specific conditions under which poor or impeded diffusion of synthetic pheromone diminishes the disruption effect, which could result in some males effectively locating females for reproduction. At the same time, many commercially available synthetic lures are also available, and growers have been effectively using them to track population development – although the attractive range of these lures remains unclear. That is, while pheromone lures can attract many moths, the relationship between trap capture and local populations, much less crop damage, remains unclear. Regardless of the emission source (aerosol puffers, meso emitters, lures etc.), we currently lack the ability to fully understand how these synthetic pheromone compounds diffuse away from their point-source of emission – and subsequently how this might affect the efficacy of mating disruption and/or the accuracy of monitoring efforts. Raman spectroscopy (RS) may offer a means to detect synthetic pheromone because of its analytical properties and recent technological advancements. In combination with nanostructured probes, RS has a demonstrated capability to detect volatiles at extremely low concentrations. While other methods for detecting pheromones have proven to be successful, such analytical methods like mass spectrometry (MS) gas chromatography (GC) require sampling in the fields and are not real-time. Other methods such as EAG/ EAD are also invasive (use antennas) but are of course valuable. Opto-electronic, micro and nano sensors just recently enticed interest. We fall in this latter category, proposing the use of optical spectroscopy (Raman) in a fiber aided by nanostructures to provide a chemical fingerprint without transductions and in real-time (i.e. no sampling). To date, we have been able to generate Raman signatures for the main chemicals in synthetic pheromones (a first for science, to the best of our knowledge), observe their trends at different concentrations, and also provide a clear distinction of such signatures in mixed samples via Principal Component Analysis (PCA) – all of which strengthens our conclusions on the ability of RS to detect emissions in more realistic conditions. We also established processes to enhance the detection sensitivity via preconcentration with Solid Phase Micro Extraction (SPME) fibers and Surface Enhanced Raman Spectroscopy (SERS) to increase the overall optical signals. Furthermore, we explored limitations and requirements for detecting from dispensers, lures, or live moths, including Dept. of Energy and CA State regulatory approvals. Finally, we setup some of our first “orchard in a box” experiments to measure pheromone diffusion along with developing appropriate models.

42 ENGINEERING↗

Ultrafast Metal Electrodeposition Revealed by In Situ Optical Imaging and Theoretical Modeling towards Fast–Charging Zn Battery Chemistry

Metallic Zn is a preferred anode material for rechargeable aqueous batteries towards a smart grid and renewable energy storage. Importantly, understanding how the metal nucleates and grows at the aqueous Zn anode is a critical and challenging step to achieve full reversibility of Zn battery chemistry, especially under fast-charging conditions. Here, by combining in situ optical imaging and theoretical modeling, we uncover the critical parameters governing the electrodeposition stability of the metallic Zn electrode, that is, the competition among crystallographic thermodynamics, kinetics, and Zn 2+ -ion diffusion. Moreover, steady-state Zn metal plating/ stripping with Coulombic efficiency above 99 % is achieved at 10-100 mA cm -2 in a reasonably high concentration (3 M) ZnSO 4 electrolyte. Significantly, a long-term cycling-stable Zn metal electrode is realized with a depth of discharge of 66.7% under 50 mA cm -2 in both Zn || Zn symmetrical cells and MnO 2 || Zn full cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance and durability of electrically conductive tape for shingled Si heterojunction technology cells

We report electrically conductive tape (ECT) was characterized and used to assemble shingled cell strings at low temperature to achieve high reliability Pb- and Ag-free interconnections. The volume resistivity for two considered ECTs are 0.13 ± 0.06 mΩ·cm and 0.47 ± 0.20 mΩ·cm and specific contact resistances, 6.85± 2.00 mΩ·cm 2 and 6.30 ± 0.37 mΩ·cm 2 using the emerging IEC 62788-8-1 Technical Specification for assessment of electrically conductive adhesives (ECA). Durability and performance of the technology in glass–glass mini modules were evaluated with temperature cycling, damp heat testing, and combined-accelerated stress testing (CAST). Through temperature cycling (-40°C to 85°C) applying five times the mini module short-circuit current in forward bias and in the multi climate CAST protocol, there was negligible degradation of fill factor after replacing connectors at the modules' cable leads; however, CAST resulted in short circuit current loss attributed to degradation in light collection by the cells, not the ECT. The IEC 61215-2 85°C, 85% relative humidity damp heat testing showed susceptibility of the HJT cells to effects of humidity in the electroluminescence intensity around the module perimeter that degraded power performance by 4% (relative). Contrasting the IEC 61215-2 qualification testing-based damp heat testing with CAST, factors such as the optical stress of CAST may precipitate the degradation of the modules whereas the humidity levels and duration of IEC 61215-2 damp heat testing may lead to excessive levels of humidity diffused into the modules, potentially resulting in degradation that is unrepresentative of the field.

14 SOLAR ENERGY↗

The Effect of Monomer Size on Fusion and Coupling in Colloidal Quantum Dot Molecules

The fusion step in the formation of colloidal quantum dot molecules, constructed from two core/shell quantum dots, dictates the coupling strength and hence their properties and enriched functionalities compared to monomers. Herein, studying the monomer size effect on fusion and coupling, we observe a linear relation of the fusion temperature with the inverse nanocrystal radius. This trend, similar to that in nanocrystal melting, emphasizes the role of the surface energy. The suggested fusion mechanism involves intraparticle ripening where atoms diffuse to the reactive connecting neck region. Moreover, the effect of monomer size and neck filling on the degree of electronic coupling is studied by combined atomistic-pseudopotential calculations and optical measurements, uncovering strong coupling effects in small QD dimers, leading to significant optical changes. Understanding and controlling the fusion and hence coupling effect allows tailoring the optical properties of these nanoscale structures, with potential applications in photonic and quantum technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗