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At least 397 records · Page 22

Electrolysis on a Chip with Tunable Thin Film Nanostructured PGM Electrocatalysts Generated from Self-Assembled Block Copolymer Templates

Self-assembled block copolymers are promising templates for fabricating thin film materials with tuned periodic feature sizes and geometry at the nanoscale. Here, a series of nanostructured platinum and iridium oxide electrocatalysts templated from poly(styrene)-block-poly(vinyl pyridine) (PSbPVP) block copolymers via an incipient wetness impregnation (IWI) pathway is reported. Both nanowire and nanocylinder electrocatalysts of varying feature sizes are assessed and higher catalyst loadings are achieved by the alkylation of the pyridine moieties in the PVP block prior to IWI. Electrocatalyst evaluations featuring hydrogen pump and water electrolysis demonstrations are carried out on interdigitated electrode (IDE) chips flexible with liquid supporting electrolytes and thin film polymer electrolytes. Notably, the mass activities of the nanostructured electrocatalysts from alkylated block copolymer templates are 35%–94% higher than electrocatalysts from non-alkylated block copolymer templates. Standing cylinder nanostructures lead to higher mass activities than lamellar variants despite their not having the largest surface area per unit catalyst loading demonstrating that mesostructure architectures have a profound impact on reactivity. Overall, IDE chips with model thin film electrocatalysts prepared from self-assembled block copolymers offer a high-throughput experimental method for correlating electrocatalyst nanostructure and composition to electrochemical reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface-supported cluster catalysis: Ensembles of metastable states run the show

It has recently been demonstrated that the dynamic behaviour of surface-supported nanocluster catalysts in realistic reaction conditions defies conventional models used in catalysis. This opens new doors in catalysis by giving more leverage in catalyst design, but also requires a major revision of the understanding of how dynamic heterogeneous catalytic interfaces operate, as well as of the computational approaches of catalyst modelling, and experimental methods of catalyst characterization. Key aspects of the new paradigm include the collective action of many catalyst states that form a statistical ensemble in reacting conditions, the catalytic activity and selectivity being driven by rare and metastable catalyst states, reaction thermodynamics and kinetics being controlled by different states of the catalyst, broken scaling relationships, non-Arrhenius behaviours, and catalyst dynamic restructuring being an essential part of the reaction mechanism. For computation, this complexity means the departure from the standard DFT calculations of reaction mechanisms on a single catalyst structure. For experiment, it calls for the development of operando characterization tools with the per-site resolution and the ability to find the minority sites that govern the catalytic activity. For catalyst design, the goal becomes the creation of the catalyst state (geometric and electronic) that might not be present in the as-prepared catalyst, but would develop in the reaction conditions and would have the desired activity then. While cluster catalysts are the most dramatic in their dynamic fluxionality, other amorphous interfaces also exhibit some of it, and thus are also subject to similar paradigm revision.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laboratory Evaluation of the Thermal Breakout Method for Maximum Horizontal Stress Measurement

Measuring in situ stress is essential for many problems in geomechanics, and the maximum horizontal stress is the most difficult to constrain. We are developing an extension of the breakout method to measure maximum horizontal stress in regions where natural breakouts do not occur. In the novel thermal breakout method, additional compression which leads to breakout development is induced by heating the borehole wall. In the present study, we validated the method experimentally in a true-triaxial apparatus on samples with predrilled boreholes. Two rocks were selected for laboratory testing: high-porosity Berea sandstone and low-porosity Niagaran dolomite. Prior to main true-triaxial tests, we carried out standard testing to characterize the strength, elasticity and thermal properties. The true-triaxial experiments consisted of: (1) room-temperature tests where samples were first loaded mechanically until the breakout formed, and (2) elevated-temperature tests where samples were loaded mechanically within the elastic range with additional compression induced thermally. Breakout initiation was monitored by acoustic emission sensors mounted on the pistons that applied horizontal stresses. Furthermore, the magnitude of induced thermal stress was calculated from temperature measurements around the borehole wall. In both rock types, we created thermally induced breakouts and examined analytical expressions to constrain maximum horizontal stress based on strength, elastic and thermal properties of the rocks.

58 GEOSCIENCES↗

Confirmation of the seismic resistance of nuclear power plant equipment after assembly

It is shown that the natural frequencies and damping decrements of nuclear power plant equipment can only be determined experimentally and directly at the power generation units (reactors) of nuclear power plants under real disassembly conditions for the equipment, piping network, thermal insulation, etc. A computational experimental method is described in which the natural frequencies and damping decrements are determined in the field and the seismic resistance is reevaluated using these values. This method is the basis of the standards document 'Methods for confirming the dynamic characteristics of systems and components of the generating units of nuclear power plants which are important for safety' prepared and introduced in 2012.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Effect of microalgae cell composition and size on responsiveness to ultrasonic harvesting

Ultrasonic harvesting could reduce the energy consumption and costs associated with separating microalgae from growth media. The responsiveness of microalgae cells to an ultrasonic standing wave depends on the cell radius and acoustic contrast factor (ACF). The ACF can vary as cell composition (e.g. lipid, protein, carbohydrate content) varies depending on the algae strain, cultivation conditions, and growth stage. Here, two independent experimental methods were used to characterize the ACF of three algae ;strains—Nannochloropsis salina, Chlamydomonas reinhardtii, and Tetraselmis chuii—as a function of dynamic cellular composition over 9- to 14-day growth periods. For N. salina, lipid content increased from 25 ± 1% to 33 ± 1% ash-free dry weight (AFDW) and ACF decreased by 46% (from 0.041 ± 0.002 to 0.022 ± 0.002) between growth days 3 and 10. For C. reinhardtii, lipid content increased from 26 ± 1% to 40 ± 1% AFDW and ACF decreased by 33% (from 0.051 ± 0.013 to 0.034 ± 0.006) between growth days 3 and 9. For T. chuii, lipid content and ACF remained stable (~ 10% AFDW and ~ 0.3) over the growth period. ACF decreased as lipid content increased because lipids have a negative ACF in the growth media; however, cell size had a greater impact on cell responsiveness because the ratio of the acoustic radiation force to the drag force is proportional to cell radius squared.

09 BIOMASS FUELS↗

Porous Media Characterization Using Minkowski Functionals: Theories, Applications and Future Directions

Porous materials are ubiquitous, from biological tissues (skin, cartilage, bones, heart tissue), to manufactured materials (paper, functional porous materials, batteries, drug delivery systems, diapers), to environmental materials (rocks, soils, plants). Because these materials are composed of multiple phases, the effects of flow, heat transfer, chemical reactions, and deformations including swelling and shrinking are more complex than that for a single phase such as a gas, liquid, or solid. The realization that porous materials, regardless of the application, have commonalities in modeling approaches, experimental methods, and numerical methods was the impetus of this journal, Transport in Porous Media (founded by Jacob Bear in 1986) and of the International Society for Porous Media (InterPore, interpore.org), which at its roots, originated in 2006. The growth of TIPM and of InterPore mirrors the explosive interest in porous media research that is now recognized as a field of research in and of itself. It is in the honor of InterPore’s 10th anniversary, celebrated at the InterPore 10th Annual Meeting and Jubilee in 2018 in New Orleans, USA, that this special issue was conceived.

Armstrong, Ryan T. (ORCID:0000000164317902)↗

Contact Angle Measurements Using Sessile Drop and Micro-CT Data from Six Sandstones

Numerous sessile drop and micro-computed tomography (micro-CT) studies have been conducted to quantify Geologic Carbon Storage formation wettability by measuring static contact angles (θ); however, the influence of pore geometry remains unknown. In this work, six sandstones (Bandera Brown, Berea, Bentheimer, Mt. Simon, Navajo, and Nugget) are used to measure θ using the two aforementioned experimental methods at identical testing conditions (45°C and 12.41 MPa). The range of θ measured at in situ conditions (micro-CT) exceeds those the range at ex situ (sessile drop method) conditions for all sandstones. However, when droplets with more representative in situ diameters are analyzed, θ averages show ex situ θ exceed those of in situ θ. Pore geometry does influence local θ, but the size of ex situ droplets relative to pore size appears to influence θ. This is an important to consider for future sessile drop studies used for analysis of CO 2 behavior in carbon storage reservoirs.

36 MATERIALS SCIENCE↗

Preface to Special Issue on Neutron Scattering for Catalysis

In the pursuit of understanding the chemical transformations of catalytic reactions and the structural evolution of catalysts at the molecular level, a suite of advanced experimental methods has been developed in the studies of catalysis science. Furthermore, among these methods, neutron scattering not only gives catalytic information that is highly complementary to other microscopic scattering techniques such as electrons (microscopy and diffraction) and photons from visible light to synchrotron X-rays, but also frequently provides unique insights into catalysis regarding the structure and chemical nature of light elements such as hydrogen and oxygen that are either not possible or difficult to study with other approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Application of Differential Scanning Calorimetry to Investigate Precipitation Behavior in Nickel-Base Superalloys Under Continuous Cooling and Heating Conditions

In this study, a suite of experimental tools and fast-acting, numerical-simulation techniques was used to quantify the precipitation behavior of three nickel-base superalloys: IN-100, LSHR, and 718. Experimental methods comprised differential scanning calorimetry (DSC) to establish the specific heat as a function of temperature and selected direct-resistance heating trials (using a Gleeble ® machine) to obtain samples for microstructural analysis. For the DSC experiments, each alloy was cooled at a prescribed constant rate (between 5 and 20 K/min) after an initial soak/equilibration in the high-temperature, single-phase (supersolvus) temperature regime. On-heating DSC trials beginning at ambient temperature were also performed on alloy 718 in three different starting conditions: super- δ -solvus solution treated and water quenched (denoted as ST), solution treated and aged (STA), and solution treated and overaged (STOA). DSC results, revealing the thermal signatures associated with the kinetics of precipitation of γ ' (IN-100, LSHR) or γ ' and γ " (718), were interpreted using a previously-developed fast-acting routine that treats concurrent nucleation, growth, coarsening, and dissolution. For these simulations, special attention was paid to various thermo-kinetic input parameters including equilibrium solvus-approach curves, bulk free energies of transformation, matrix-precipitate interface energies, and effective diffusivities. For the γ - γ ' superalloys (IN-100 and LSHR), estimates of precipitate volume fraction as a function of temperature from the specific-heat data revealed semi-quantitative agreement with simulation predictions. For the γ - γ '- γ " superalloy (718), simulation predictions of precipitate volume fractions were converted to specific heat as a function of temperature and showed semi-quantitative agreement with the direct measurements.

36 MATERIALS SCIENCE↗

Effect of Si Content on Oxide Formation on Surface of Molten Fe-Cr-C Alloy Bath During Oxygen Top Blowing

Using a direct observation experimental method, the oxide formation behavior on the surface of Fe-Cr-5 mass pct C-Si alloy baths during decarburization by a top-blown Ar-O 2 mixture was studied. The effects of the initial Si and Cr content of the alloy, temperature, and oxygen feed ratio on oxide formation were investigated. The results showed that, for alloys without Si, oxide particles, unstable oxide films, and stable oxide films formed sequentially. The presence of Si in the alloy changed the formation behavior of stable oxide film, and increased the crucial C content when stable oxide film started to form. Increasing the temperature, decreasing the initial Cr content, and increasing the ratio of the diluting gas decreased the critical C content at which a stable oxide film started to form. In addition, the P CO and a Cr 2O 3 values at which oxides started to form were estimated using Hilty’s equation and the equilibrium relation to understand the formation conditions and the role of each parameter in oxide formation.

36 MATERIALS SCIENCE↗

Self-diffusion Measurements of Liquid Sn Using the Shear Cell Technique and Stable Density Layering

By utilizing the shear cell technique and achieving stable density layering with the addition of an alloying element Bi, the self-diffusion coefficients of liquid Sn were measured on the ground at 573 K, 773 K, and 973 K (300 °C, 500 °C, and 700 °C). Moreover, the impurity diffusion coefficients of Bi in the liquid Sn were simultaneously measured, to confirm the suppression of natural convection. From the experimental results, natural convection was confirmed to be suppressed, given that the impurity diffusion coefficients of Bi were in good agreement with the microgravity reference data. Upon changing the amounts of added Bi within 5 at. pct Bi, the self-diffusion coefficients of liquid Sn did not vary significantly. Moreover, the SnBi system within 5 at. pct Bi can be regarded as a dilute solution by calculating the activity of Sn in the SnBi system beforehand. The self-diffusion coefficients of the liquid Sn were in good agreement with the power law of temperature dependence from the microgravity reference data. After confirming the suppression of natural convection and that the SnBi system is a dilute solution, the self-diffusion coefficient of liquid Sn was determined as 5.00 ± 0.16 × 10{sup −9} m{sup 2} s{sup −1} at 773 K (500 °C). The effectiveness of the experimental method used in this study for the measurement of the self-diffusion coefficients was confirmed, under the condition that the liquid system could be regarded as a dilute solution.

36 MATERIALS SCIENCE↗

Geometric Limitation and Tensile Properties of Wire and Arc Additive Manufacturing 5A06 Aluminum Alloy Parts

Wire and arc additive manufacture (WAAM), as an emerging and promising technology of metal additive manufacturing, it lacks of experimental works to clarify the feature of geometrical configuration, microstructure and tensile properties, which can be used for further evaluating whether the as-deposited part can be used directly, and providing design reference for structure optimization. Taking 5A06 aluminum alloy additive manufacturing for example, in this paper, the geometric limitation and tensile property criteria are characterized using experimental method. The minimum angle and curvature radius that can be made by WAAM are 20° and 10 mm when the layer width is 7.2 mm. It shows isotropy when loading in build direction and perpendicular one. When loading in the direction of parallel and perpendicular to texture orientation, the tensile properties are anisotropic. The difference between them is 22 MPa.

36 MATERIALS SCIENCE↗

Experimental Determination of Power Losses and Heat Generation in Solar Cells for Photovoltaic-Thermal Applications

Solar cell thermal recovery has recently attracted more and more attention as a viable solution to increase photovoltaic efficiency. However, the convenience of the implementation of such a strategy is bound to the precise evaluation of the recoverable thermal power and to a proper definition of the losses occurring within the solar device. In this work, we establish a framework in which all solar cell losses are defined and described. The aim is to determine the components of the thermal fraction. We therefore describe an experimental method to precisely compute these components from the measurement of the external quantum efficiency, the current–voltage characteristics, and the reflectivity of the solar cell. Applying this method to three different types of devices (bulk, thin film, and multi-junction), we could exploit the relationships among losses for the main three generations of PV cells available nowadays. In addition, since the model is explicitly wavelength dependent, we could show how thermal losses in all cells occur over the whole solar spectrum, and not only in the infrared region. This demonstrates that profitable thermal harvesting technologies should enable heat recovery over the whole solar spectral range.

36 MATERIALS SCIENCE↗

Study of Thermomechanical Behavior of Zirconium-0.3 Tin Alloy

Zirconium-based alloys are used in the manufacturing of nuclear fuel tubes. These tubes need to be clad with zirconium-tin (Zr-0.3 wt.% Sn) alloy to enhance the lives of tubes. Manufacturing of such clad tubes is a challenging task, due to work hardening and dynamic softening phenomenon. In this study, hot deformation behavior of Zr-0.3Sn alloy is investigated at different temperatures and strain rates. It is found that fully recrystallized microstructure can be obtained by working at around 900 °C and high strain rate of 10 s{sup −1}. Further, constitutive equations are developed for the entire domain of deformation range and fitted into standard FEM-based simulation model for extrusion. The simulation results are validated with experimental data. The difference in flow stresses values obtained from numerical and experimental methods was around 14%.

36 MATERIALS SCIENCE↗

Advanced Real-Time Optical Imaging: Part I

Materials research is significantly assisted by information gathered from imaging. Images may be macroscopic or microscopic; different imaging techniques ranging from conventional microscopes to synchrotron tomography are selected for various research purposes and goals. While most materials imaging is performed in static environments at room temperature because of its appropriateness (or due to device limitations), simple optical imaging may transform into a powerful tool if it is dynamically captured during materials treatments, processing, or physical/chemical exposures. Real-time observations this way provide researchers with vital information on materials behaviors under controlled but various conditions. In the field of energy materials, it is not uncommon to require materials studies under high-temperature, high-pressure, and/or corrosive conditions. In gasifiers, for example, investigations of sensor alloy degradation, slag-refractory reactions, and coal agglomeration require samples to undergo severe environments where direct imaging would be difficult using conventional experimental methods. Finally, while post mortem analysis often provides critical information, interpretation may sometimes be complicated without confirming such occurrences under those conditions.

36 MATERIALS SCIENCE↗

In situ observation of atomic movement in a ferroelectric film under an external electric field and stress

Atomic movement under application of external stimuli (i.e., electric field or mechanical stress) in oxide materials has not been observed due to a lack of experimental methods but has been well known to determine the electric polarization. Here, we investigated atomic movement arising from the ferroelectric response of BiFeO 3 thin films under the effect of an electric field and stress in real time using a combination of switching spectroscopy, time-resolved X-ray microdiffraction, and in situ stress engineering. Under an electric field applied to a BiFeO 3 film, the hysteresis loop of the reflected X-ray intensity was found to result from the opposing directions of displaced atoms between the up and down polarization states. An additional shift of atoms arising from the linearly increased dielectric component of the polarization in BiFeO 3 was confirmed through gradual reduction of the diffracted X-ray intensity. The electric-fieldinduced displacement of oxygen atoms was found to be larger than that of Fe atom for both ferroelectric switching and increase of the polarization. In conclusion, the effect of external stress on the BiFeO 3 thin film, which was controlled by applying an electric field to the highly piezoelectric substrate, showed smaller atomic shifts than for the case of applying an electric field to the film, despite the similar tetragonality.

74 ATOMIC AND MOLECULAR PHYSICS↗

Inferring Strength of Tantalum from Hydrodynamic Instability Recovery Experiments

Hydrodynamic instability experiments allow access to material properties at extreme conditions, where strain rates exceed 105 s -1 and pressures reach 100 GPa. Current hydrodynamic instability experimental methods require in-flight radiography to image the instability growth at high pressure and high strain rate, limiting the facilities where these experiments can be performed. An alternate approach, recovering the sample after loading, allows measurement of the instability growth with profilometry. Tantalum samples were manufactured with different 2D and 3D initial perturbation patterns and dynamically compressed by a blast wave generated by laser ablation. The samples were recovered from peak pressures between 30 and 120 GPa and strain rates on the order of 107 s -1 , providing a record of the growth of the perturbations due to hydrodynamic instability. These records are useful validation points for hydrocode simulations using models of material strength at high strain rate. Recovered tantalum samples were analyzed, providing an estimate of the strength of the material at high pressure and strain rate.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Determining heterogeneous slip activity on multiple slip systems from single crystal orientation pole figures

A new experimental method to determine heterogeneity of shear strains associated with crystallographic slip in the bulk of ductile, crystalline materials is outlined. The method quantifies the time resolved evolution of misorientation within plastically deforming crystals using single crystal orientation pole figures (SCPFs) measured in-situ with X-ray diffraction. A multiplicative decomposition of the crystal kinematics is used to interpret the distributions of lattice plane orientation observed on the SCPFs in terms of heterogeneous slip activity (shear strains) on multiple slip systems. Here, to show the method’s utility, the evolution of heterogeneous slip is quantified in a silicon single crystal plastically deformed at high temperature at multiple load steps, with slip activity in sub-volumes of the crystal analyzed simultaneously.

36 MATERIALS SCIENCE↗