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At least 361 records · Page 20

Pulse-echo ultrasonic imaging method for eliminating sample thickness variation effects

A pulse-echo, immersion method for ultrasonic evaluation of a material is discussed. It accounts for and eliminates nonlevelness in the equipment set-up and sample thickness variation effects employs a single transducer, automatic scanning and digital imaging to obtain an image of a property of the material, such as pore fraction. The nonlevelness and thickness variation effects are accounted for by pre-scan adjusments of the time window to insure that the echoes received at each scan point are gated in the center of the window. This information is input into the scan file so that, during the automatic scanning for the material evaluation, each received echo is centered in its time window. A cross-correlation function calculates the velocity at each scan point, which is then proportionalized to a color or grey scale and displayed on a video screen.

Roth, Don J.↗

Pulse-Echo Ultrasonic Imaging Method for Eliminating Sample Thickness Variation Effects

A pulse-echo, immersion method for ultrasonic evaluation of a material which accounts for and eliminates nonlevelness in the equipment set-up and sample thickness variation effects employs a single transducer and automatic scanning and digital imaging to obtain an image of a property of the material, such as pore fraction. The nonlevelness and thickness variation effects are accounted for by pre-scan adjustments of the time window to insure that the echoes received at each scan point are gated in the center of the window. This information is input into the scan file so that, during the automatic scanning for the material evaluation, each received echo is centered in its time window. A cross-correlation function calculates the velocity at each scan point, which is then proportionalized to a color or grey scale and displayed on a video screen.

Roth, Don J.↗

Determination of Radiative Forcing of Saharan Dust using Combined TOMS and ERBE Data

The direct radiative forcing of Saharan dust aerosols has been determined by combining aerosol information derived from Nimbus-7 TOMS with radiation measurements observed at the top of atmosphere (TOA) by NOAA-9 ERBE made during February-July 1985. Cloud parameters and precipitable water derived from the NOAA-9 HIRS2 instrument were used to aid in screening for clouds and water vapor in the analyses. Our results indicate that under "cloud-free" and "dry" conditions there is a good correlation between the ERBE TOA outgoing longwave fluxes and the TOMS aerosol index measurements over both land and ocean in areas under the influence of airborne Saharan dust. The ERBE TOA outgoing shortwave fluxes were also found to correlate well with the dust loading derived from TOMS over ocean. However, the calculated shortwave forcing of Saharan dust aerosols is very weak and noisy over land for the range of solar zenith angle viewed by the NOAA-9 ERBE in 1985. Sensitivity factors of the TOA outgoing fluxes to changes in aerosol index were estimated using a linear regression fit to the ERBE and TOMS measurements. The ratio of the shortwave-to-longwave response to changes in dust loading over the ocean is found to be roughly 2 to 3, but opposite in sign. The monthly averaged "clear-sky" TOA direct forcing of airborne Saharan dust was also calculated by multiplying these sensitivity factors by the TOMS monthly averaged "clear-sky" aerosol index. Both the observational and theoretical analyses indicate that the dust layer height, ambient moisture content as well as the presence of cloud all play an important role in determining the TOA direct radiative forcing due to mineral aerosols.

Hsu, N. Christina↗

Conservation laws, vertex corrections, and screening in Raman spectroscopy

We present a microscopic theory for the Raman response of a clean multiband superconductor, with emphasis on the effects of vertex corrections and long-range Coulomb interaction. The measured Raman intensity, R⁡(Ω), is proportional to the imaginary part of the fully renormalized particle-hole correlator with Raman form factors γ⁡( ⃗ k). In a BCS superconductor, a bare Raman bubble is nonzero for any γ⁡( ⃗ k) and diverges at Ω = 2⁢Δ max , where Δ max is the largest gap along the Fermi surface. However, for γ( ⃗ k) = constant, the full R⁡(Ω) is expected to vanish due to particle number conservation. It was sometimes stated that this vanishing is due to the singular screening by long-range Coulomb interaction. In our general approach, we show diagrammatically that this vanishing actually holds due to vertex corrections from the same short-range interaction that gives rise to superconductivity. We further argue that long-range Coulomb interaction does not affect the Raman signal for any γ( ⃗ k). We argue that vertex corrections eliminate the divergence at 2⁢Δ max . Here, we also argue that vertex corrections give rise to sharp peaks in R(Ω) at Ω < 2⁢Δ min (the minimum gap along the Fermi surface), when Ω coincides with the frequency of one of the collective modes in a superconductor, e.g., Leggett and Bardasis-Schrieffer modes in the particle-particle channel, and an excitonic mode in the particle-hole channel.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High Throughput In-Line Coating Metrology Development for Solid Oxide Fuel Cell Manufacturing

Coatings play key roles in solid oxide fuel cell (SOFC) stack durability. For example, diffusion barrier coatings on Cr-containing interconnect and balance of plant (BOP) components protect electrodes from Cr poisoning over the long operational lifetimes (>10,000 hours) of the fuel cell stack. Common defects in coatings, such as cracks, pinholes, and porosity, result in a failure to protect the electrodes, resulting in shorter operational lifetime and thus higher cost. It is very unlikely, even in the best coating process, that all these defects can be mitigated, hence identifying critical defects in parts, and removing defective parts from production before they can damage the stack, becomes paramount. Furthermore, these quality control techniques must be operational in the production/assembly line (in-line), i.e., high throughput and non-destructive, and cost effective. Redox Power Systems, LLC (Redox) together with the National Renewable Energy Laboratory (NREL) developed much needed high throughput, in-line metrology techniques for protective coatings. The overall goal of the project is to lower cost while increasing robustness, reliability, and endurance of SOFC stacks. To accomplish this, we had several objectives, including: to identify key coating and substrate defects that lead to coating failure through the use of detailed characterization methods (e.g., microscopy, XRD, EDS, electrochemistry); to assess capabilities of in-line metrology techniques, e.g., optical profilometry (Redox) and thermography (NREL), to probe these defects, or evidence thereof; demonstrate long-term performance of “defect-free” protective coatings, as identified by in-line metrology, in solid oxide fuel cell (SOFC) stack operation. In the first part of this project, the ability to identify key defects expected to lead to coating and SOFC degradation using in-line metrology tools were evaluated. Coated interconnect samples with controlled defect types and populations were tested under conditions similar to SOFC operation, followed by detailed post-test analysis to reveal the defects responsible for observed degradation. In the second part of the project, the optimal in-line metrology techniques and methodologies were used to map the defect distribution in full-size interconnects with critical defects intentionally allowed to exist in some cases. These interconnects underwent SOFC testing for extended periods (up to ~3,000 hours) followed by post-test analysis to evaluate the effectiveness of in-line metrology techniques in mitigating MCO coating related degradation. Key accomplishments in this project included the following: Demonstrated ASR of < 0.05 ohm-cm 2 at 650 °C for 1,000 hours with low defect (determined by in-line metrology) interconnect samples (average ASR=37 milliohms-cm 2 after over 1,000 hours). Demonstrated that low defect coatings on interconnects (as screened using in-line metrology) have low volatilization of chromium at ~650 °C for 1,000 hours as detected using Cr-getter material (< 5 at% increase above baseline); 1022 hour duration tests under humidified, elevated temperature (750 °C rather than 650 °C) compared a base case against different coating thicknesses. Demonstrated capability to identify initial key defects of interest with in-line metrology techniques using up to 8 cm by 10 cm having coatings with and without intentional defects of interest using thermal imaging and optical profilometry. Correlated key defects identified using metrology techniques with observed coating performance (e.g., ASR and Cr volatility). Conducted several 4 cm by 4 cm cell tests using MCO-interconnects that were pre-screened using some of the metrology techniques developed in the project (e.g., optical profilometry). An analysis of ASR measurements were able to show that defect-free coatings resulted in the anticipated performance in the cell tests.

01 COAL, LIGNITE, AND PEAT↗

Relaxing Kondo-screened Kramers doublets in CeRhSi 3

${\mathrm{CeRhSi}}_{3}$ is a superconductor under pressure coexisting with a weakly antiferromagnetic phase characterized by a Bragg peak at q → 0 = (~ 0.2,0,0.5) [N. Aso et al., J. Magn. Magn. Mater. 310, 602 (2007)]. The compound is also a heavy-fermion material with a large specific heat coefficient ${\gamma}=110$ mJ ${\mathrm{mol}}^{{-}1}{\mathrm{K}}^{{-}2}$ and a high Kondo temperature of ${T}_{K}=50$ K, indicating ${\mathrm{CeRhSi}}_{3}$ is in a strongly Kondo screened state. We apply high-resolution neutron spectroscopy to investigate the magnetic fluctuations in the normal phase, at ambient pressures, and at low temperatures. We measure a commensurate dynamic response centered around the Q → = (0,0,2) position that gradually evolves to $H{\sim}0.2$ with decreasing temperature and/or energy transfers. The response is broadened both in momentum and energy and is not reminiscent of sharp spin wave excitations found in insulating magnets where the electrons are localized. We parametrize the excitation spectrum and temperature dependence using a heuristic model utilizing the random-phase approximation to couple relaxing ${\mathrm{Ce}}^{3+}$ ground-state Kramers doublets with a Kondo-like dynamic response. With a Ruderman-Kittel-Kasuya-Yosida exchange interaction within the $ab$ plane and an increasing single-site susceptibility, we can qualitatively reproduce the neutron spectroscopic results in ${\mathrm{CeRhSi}}_{3}$ and, namely, the trade-off between scattering at commensurate and incommensurate positions. We suggest that the antiferromagnetic phase in ${\mathrm{CeRhSi}}_{3}$ is driven by weakly correlated relaxing localized Kramers doublets and that ${\mathrm{CeRhSi}}_{3}$ at ambient pressures is on the border between a Rudderman-Kittel-Yosida antiferromagnetic state and a Kondo-screened phase where static magnetism is predominately absent.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Tuning Film Stresses for Open-Air Processing of Stable Metal Halide Perovskites

Challenges to upscaling metal halide perovskites (MHPs) include mechanical film stresses that accelerate degradation, dominate at the module scale, and can lead to delamination or fracture. In this work, we demonstrate open-air blade coating of single-step coated perovskite as a scalable method to control residual film stress after processing and introduce beneficial compression in the thin film with the use of polymer additives such as gellan gum and corn starch. The optoelectronic properties of MHP films with compression are improved with higher photoluminescence yields. MHP film stability is significantly improved under compression, under humidity, heat, and thermal cycling. By measuring the evolution of film stresses, we demonstrate for the first time that stress relaxation occurs in MHP films with tensile stress that correlates with film degradation. Finally, this discovery of a new mechanism underpinning MHP degradation shows that film stress can be used as a parameter to screen MHP devices and modules for quality control before deployment as a design for reliability criterion.

14 SOLAR ENERGY↗

Structural dynamics in proteins induced by and probed with X-ray free-electron laser pulses

X-ray free-electron lasers (XFELs) enable crystallographic structure determination beyond the limitations imposed upon synchrotron measurements by radiation damage. The need for very short XFEL pulses is relieved through gating of Bragg diffraction by loss of crystalline order as damage progresses, but not if ionization events are spatially non-uniform due to underlying elemental distributions, as in biological samples. Indeed, correlated movements of iron and sulfur ions were observed in XFEL-irradiated ferredoxin microcrystals using unusually long pulses of 80 fs. Here, we report a femtosecond time-resolved X-ray pump/X-ray probe experiment on protein nanocrystals. We observe changes in the protein backbone and aromatic residues as well as disulfide bridges. Simulations show that the latter’s correlated structural dynamics are much slower than expected for the predicted high atomic charge states due to significant impact of ion caging and plasma electron screening. This indicates that dense-environment effects can strongly affect local radiation damage-induced structural dynamics.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Excitonic effects in absorption spectra of carbon dioxide reduction photocatalysts

Abstract The formation and disassociation of excitons play a crucial role in any photovoltaic or photocatalytic application. However, excitonic effects are seldom considered in materials discovery studies due to the monumental computational cost associated with the examination of these properties. Here, we study the excitonic properties of nearly 50 photocatalysts using state-of-the-art Bethe–Salpeter formalism. These ~50 materials were recently recognized as promising photocatalysts for CO 2 reduction through a data-driven screening of 68,860 materials. Here, we propose three screening criteria based on the optical properties of these materials, taking excitonic effects into account, to further down select six materials. Furthermore, we study the correlation between the exciton binding energies obtained from the Bethe–Salpeter formalism and those obtained from the computationally much less-expensive Wannier–Mott model for these chemically diverse ~50 materials. This work presents a paradigm towards the inclusion of excitonic effects in future materials discovery for solar-energy harvesting applications.

36 MATERIALS SCIENCE↗

Understanding the Kondo resonance in the d-CoPc/Au(111) adsorption system

By combining the density functional theory (DFT) and a hierarchical equations of motion (HEOM) approach, we investigate the Kondo phenomena in a composite system consisting of a dehydrogenated cobalt phthalocyanine molecule (d-CoPc) adsorbed on an Au(111) surface. DFT calculations are performed to determine the ground-state geometric and electronic structures of the adsorption system. It is found that the singly occupied d{sub z{sup 2}} orbital of Co forms a localized spin, which could be screened by the substrate conduction electrons. This screening leads to the prominent Kondo features as observed in the scanning tunneling microscopy experiments. We then employ the HEOM approach to characterize the Kondo correlations of the adsorption system. The calculated temperature-dependent differential conductance spectra and the predicted Kondo temperature agree well with the experiments, and the universal Kondo scaling behavior is correctly reproduced. This work thus provides important insights into the relevant experiments, and it also highlights the applicability of the combined DFT+HEOM approach to the studies of strongly correlated condensed matter systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Simple Computational Proxy for Screening Magnetocaloric Compounds

Alternating cycles of isothermal magnetization and adiabatic demagnetization applied to a magnetocaloric material can drive refrigeration in very much the same manner as cycles of gas compression and expansion. The material property of interest in finding candidate magnetocaloric materials is ΔS M , their gravimetric entropy change upon application of a magnetic field under isothermal conditions. There is, however, no general method for screening materials for such an entropy change without actually performing the relevant, time- and effort-intensive magnetic measurements. Here we propose a simple computational proxy based on performing nonmagnetic and magnetic density functional theory calculations on magnetic materials. This proxy, which we term the magnetic deformation Σ M , is a measure of how much the unit cell deforms comparing with the relaxed structures with and without the inclusion of spin polarization. Σ M appears to correlate very well with experimentally measured magnetic entropy change values. Here, the proxy has been tested against 33 ferromagnetic materials with known ΔS M , including nine materials newly measured for this study. It has then been used to screen 134 ferromagnetic materials for which the magnetic entropy has not yet been reported, identifying 30 compounds as being promising for further study. As a demonstration of the effectiveness of our approach, we have prepared one of these compounds and measured its isothermal entropy change. MnCoP, with a T C of 575 K, shows a maximal ΔS M of –6.0 J kg –1 K –1 for an H = 5 T applied field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A high throughput assay to detect enzymatic polyethylene oxidation

Biological plastics deconstruction and upcycling have emerged as sustainable alternatives to traditional recycling technologies for plastics waste. The discovery and engineering of efficient thermostable poly(ethylene terephthalate) (PET) hydrolases have made biological PET recycling possible at scale; however, enzymes for non-PET plastics, which account for approximately 70% of all plastics produced, remain largely undiscovered. To accelerate the discovery of such enzymes, we develop a high-throughput screen to detect initial polymer oxidation, specifically that of the C-H bond to an aldehyde. We test 4-hydrazino-7-nitro-2,1,3-benxoxadiozole hydrazine (NBD-H), which reacts with generated aldehydes to form a fluorescent hydrazone on plasma oxidized low-density polyethylene (LDPE) films. Hydrazone generation correlated well with the area of aldehyde peaks as measured by Fourier Transform Infrared Spectroscopy (FTIR) (R2 = 0.92). Moreover, we demonstrate that the probe reliably identifies LDPE-active dye decolorizing peroxidases (DyPs) that generate aldehydes on LDPE films (1.7 – 3.0 fold change relative to background), serving as an effective screen as demonstrated by receiver operating characteristic area under the curve of 0.95. Furthermore, this assay offers an LDPE oxidation screening platform that can be readily parallelized and automated for accelerated discovery of enzymes involved in polyolefin deconstruction.

biocatalysis↗

Robust validation of approximate 1-matrix functionals with few-electron harmonium atoms

A simple comparison between the exact and approximate correlation components U of the electron-electron repulsion energy of several states of few-electron harmonium atoms with varying confinement strengths provides a stringent validation tool for 1-matrix functionals. The robustness of this tool is clearly demonstrated in a survey of 14 known functionals, which reveals their substandard performance within different electron correlation regimes. Unlike spot-testing that employs dissociation curves of diatomic molecules or more extensive benchmarking against experimental atomization energies of molecules comprising some standard set, the present approach not only uncovers the flaws and patent failures of the functionals but, even more importantly, also allows for pinpointing their root causes. Since the approximate values of U are computed at exact 1-densities, the testing requires minimal programming and thus is particularly suitable for rapid screening of new functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting chemically-induced skin reactions. Part II: QSAR models of skin permeability and the relationships between skin permeability and skin sensitization

Skin permeability is widely considered to be mechanistically implicated in chemically-induced skin sensitization. Although many chemicals have been identified as skin sensitizers, there have been very few reports analyzing the relationships between molecular structure and skin permeability of sensitizers and non-sensitizers. The goals of this study were to: (i) compile, curate, and integrate the largest publicly available dataset of chemicals studied for their skin permeability; (ii) develop and rigorously validate QSAR models to predict skin permeability; and (iii) explore the complex relationships between skin sensitization and skin permeability. Based on the largest publicly available dataset compiled in this study, we found no overall correlation between skin permeability and skin sensitization. In addition, cross-species correlation coefficient between human and rodent permeability data was found to be as low as R{sup 2} = 0.44. Human skin permeability models based on the random forest method have been developed and validated using OECD-compliant QSAR modeling workflow. Their external accuracy was high (Q{sup 2}{sub ext} = 0.73 for 63% of external compounds inside the applicability domain). The extended analysis using both experimentally-measured and QSAR-imputed data still confirmed the absence of any overall concordance between skin permeability and skin sensitization. This observation suggests that chemical modifications that affect skin permeability should not be presumed a priori to modulate the sensitization potential of chemicals. The models reported herein as well as those developed in the companion paper on skin sensitization suggest that it may be possible to rationally design compounds with the desired high skin permeability but low sensitization potential. - Highlights: • It was compiled the largest publicly-available skin permeability dataset. • Predictive QSAR models were developed for skin permeability. • No concordance between skin sensitization and skin permeability has been found. • Structural rules for optimizing sensitization and penetration were established.

60 APPLIED LIFE SCIENCES↗

From Organized High-Throughput Data to Phenomenological Theory using Machine Learning: The Example of Dielectric Breakdown

Understanding the behavior (and failure) of dielectric insulators experiencing extreme electric fields is critical to the operation of present and emerging electrical and electronic devices. Despite its importance, the development of a predictive theory of dielectric breakdown has remained a challenge, owing to the complex multiscale nature of this process. We focus on the intrinsic dielectric breakdown field of insulators—the theoretical limit of breakdown determined purely by the chemistry of the material, i.e., the elements the material is composed of, the atomic-level structure, and the bonding. Starting from a benchmark dataset (generated from laborious first principles computations) of the intrinsic dielectric breakdown field of a variety of model insulators, simple predictive phenomenological models of dielectric breakdown are distilled using advanced statistical or machine learning schemes, revealing key correlations and analytical relationships between the breakdown field and easily accessible material properties. Lastly, the models are shown to be general, and can hence guide the screening and systematic identification of high electric field tolerant materials.

36 MATERIALS SCIENCE↗

Polarity compensation in ultra-thin films of complex oxides: The case of a perovskite nickelate

We address the fundamental issue of growth of perovskite ultra-thin films under the condition of a strong polar mismatch at the heterointerface exemplified by the growth of a correlated metal LaNiO 3 on the band insulator SrTiO 3 along the pseudo cubic [111] direction. While in general the metallic LaNiO 3 film can effectively screen this polarity mismatch, we establish that in the ultra-thin limit, films are insulating in nature and require additional chemical and structural reconstruction to compensate for such mismatch. A combination of in-situ reflection high-energy electron diffraction recorded during the growth, X-ray diffraction, and synchrotron based resonant X-ray spectroscopy reveal the formation of a chemical phase La 2 Ni 2 O 5 (Ni 2+ ) for a few unit-cell thick films. First-principles layer-resolved calculations of the potential energy across the nominal LaNiO 3 /SrTiO 3 interface confirm that the oxygen vacancies can efficiently reduce the electric field at the interface.

36 MATERIALS SCIENCE↗

Effect of extended strain fields on point defect phonon scattering in thermoelectric materials

The design of thermoelectric materials often involves the integration of point defects (alloying) as a route to reduce the lattice thermal conductivity. Classically, the point defect scattering strength follows from simple considerations such as mass contrast and the presence of induced strain fields (e.g. radius contrast, coordination changes). While the mass contrast can be easily calculated, the associated strain fields induced by defect chemistry are not readily predicted and are poorly understood. In this work, we use classical and first principles calculations to provide insight into the strain field component of phonon scattering from isoelectronic point defects. Our results also integrate experimental measurements on bulk samples of SnSe and associated alloys with S, Te, Ge, Sr and Ba. These efforts highlight that the strength and extent of the resulting strain field depends strongly on defect chemistry. Strain fields can have a profound impact on the local structure. For example, in alloys containing Ba, the strain fields have significant spatial extent (1 nm in diameter) and produce large shifts in the atomic equilibrium positions (up to 0.5 A). Such chemical complexity suggests that computational assessment of point defects for thermal conductivity depression should be hindered. However, in this work, we present and verify several computational descriptors that correlate well with the experimentally measured strain fields. Furthermore, these descriptors are conceptually transparent and computationally inexpensive, allowing computation to provide a pivotal role in the screening of effective alloys. The further development of point defect engineering could complement or replace nanostructuring when optimizing the thermal conductivity, offering the benefits of thermodynamic stability, and providing more clearly defined defect chemistry.

30 DIRECT ENERGY CONVERSION↗

Dynamical cluster approximation study of electron localization in the extended Hubbard model

We perform a detailed study of the phase transitions and mechanisms of electron localization in the extended Hubbard model using the dynamical cluster approximation on a 2×2 cluster. We explore the interplay of charge order and Mott physics. We find that a nearest-neighbor Coulomb interaction V causes “screening” effects close to the Mott phase transition, pushing the phase boundary to larger values of U. We also demonstrate the different effects of V on correlations in metallic and insulating regimes, and document the different correlation aspects of charge order and Mott states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗