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At least 235 records · Page 13

Multiphysics Modeling of Electrode Dissolution under Hydrodynamic Conditions in Low Conductivity Water

Efficient plug-flow electrochemical reactors are characterized by their ability to effectively convert species with significant ionic strength and/or with the assistance of a well-behaved electrolyte. Because of the classic electroconductivity requirement, electrochemical reactors are not particularly attractive options for applications with low-conductivity conditions, especially for low-pressure feeds. However, these reactors can still find application in dedicated processes such as ultra-clean water conditioning and biological-coupled separation systems. Consequently, a multi-physics model was developed using COMSOL Multiphysics to characterize different reactor-design conditions based on the Tertiary Current Distribution which accounts for the effects of expected variations in electrolyte composition and ionic strength on the electrochemical process, as well as solution resistance and electrode kinetics. The modelling framework presented here employs single-phase laminar fluid flow, the Nernst-Planck equation, the water-based electroneutrality condition, and concentration-dependent overpotentials. This investigation particularly explores the electrolysis process of “anodic dissolution,” in which elemental species dissociate from the solid matrix of the electrode and enter the liquid phase of the electrolyte as soluble ions. The reactor configuration of interest has a rectangular parallel-electrode design and is operated galvanostatically. A series of parametric studies are carried out to inspect the response of the system when hydrodynamic, kinetic, and geometric conditions are changed. The parametric sweep resulted in variable effluent concentrations and system voltage, which reveal underlaying optimization patterns for electrode dissolution in low conductivity water.

Multiphysics↗

Effective direct steam regeneration of bis-iminoguanidine solid sorbent used for carbon dioxide capture

A cost-effective, energy-efficient sorbent regeneration process for phase-changing guanidines used for CO 2 capture was developed based on direct-steam stripping. This approach enhances the regeneration rate, simplifies the overall CO 2 capture process, and reduces the energy cost compared to conventional conductive thermal regeneration. A direct-steam sorbent regeneration reactor was developed, demonstrating that aqueous bis(iminoguanidines) (BIG) sorbents, e.g., methylglyoxal-bis(iminoguanidine) (MGBIG) and glyoxal-bis(iminoguanidine) (GBIG), could be efficiently regenerated with up to ~ 99 % CO 2 recovery through direct-steam stripping. Using low-temperature steam at 100 °C, a 4.5 times faster regeneration rate for GBIG carbonate sorbent (e.g., 30 min for 10 g) was demonstrated compared to conductive-heating (e.g., 135 min for 10 g) at 130 °C. Additionally, fully regenerated MGBIG converts into an aqueous MGBIG solution when the steam condenses onto the sorbent surface. Condensed steam with the guanidine can be easily recycled as an aqueous solution into the gas–liquid contactor to achieve a continuous-flow CO 2 -capture process. Molecular dynamics simulation was employed to provide a better understanding of the process. Higher heat transfer rates from steam to guanidine carbonate, compared to air heating, were attributed to the vibration resonance of water molecules within MGBIG with that of vapor molecules and the effective transfer of kinetic energy from vapor to solid. Technoeconomic analysis demonstrated that direct-steam stripping significantly decreases the CO 2 capture cost by 50 % compared to traditional conductive heating methods. Further, enhanced mass transfer facilitated by low-temperature steam and subsequent condensation effectively heats up the H 2 O-containing BIG-carbonate crystals, facilitating the desorption of CO 2 from the solid crystals, thereby leading to fast, effective, and energy-efficient sorbent regeneration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Removing Background Noise with Phased Array Signal Processing

Preliminary results are presented from a test conducted to determine how well microphone phased array processing software could pull an acoustic signal out of background noise. The array consisted of 24 microphones in an aerodynamic fairing designed to be mounted in-flow. The processing was conducted using Functional Beam forming software developed by Optinav combined with cross spectral matrix subtraction. The test was conducted in the free-jet of the Nozzle Acoustic Test Rig at NASA GRC. The background noise was produced by the interaction of the free-jet flow with the solid surfaces in the flow. The acoustic signals were produced by acoustic drivers. The results show that the phased array processing was able to pull the acoustic signal out of the background noise provided the signal was no more than 20 dB below the background noise level measured using a conventional single microphone equipped with an aerodynamic forebody.

Background Noise↗

Observation of Hydrological Processes Using Remote Sensing: Volume 2: The Science of Hydrology - Chapter 2.14

Improving water management can make a significant contribution to achieving most of the Millennium Development Goals established by the UN General Assembly in 2000, especially those related to poverty, hunger, and major diseases. The World Summit on Sustainable Development (WSSD) in 2002 recognized this need. Water and sanitation in particular received great attention from the Summit. The Johannesburg Plan of Implementation recommended to improve water resources management and scientific understanding of the water cycle through joint cooperation and research. For this purpose, it is recommended to promote knowledge sharing, provide capacity building, and facilitate the transfer of technology including remote-sensing (RS) and satellite technologies, especially to developing countries and countries with economies in transition, and to support these countries in their efforts to monitor and assess the quantity and quality of water resources, for example, by establishing and/or further developing national monitoring networks and water resources databases and by developing relevant national indicators. The Johannesburg Plan also adopted integrated water resources management as the overarching concept in addressing and solving water-related issues. As a result of the commitments made in the Johannesburg Plan of Implementation, several global and regional initiatives have emerged. Current international initiatives such as the Global Monitoring for Environment and Security (GMES) program of the European Commission and the European Space Agency (ESA), and the Global Earth Observation System of Systems (GEOSS) 10-Year Implementation Plan, have all identified Earth observation (EO) of the water cycle as the key in helping to solve the world s water problems. The availability of spatial information on water quantity and quality will also enable closure of the water budget at river basin and continental scales to the point where effective water management is essential (e.g., as requested by the European Union s Water Framework Directive (WFD), as well as national policies). Geo-information science and EO are vital in achieving a better understanding of the water cycle and better monitoring, analysis, prediction, and management of the world s water resources. The major components of the water cycle of the Earth system and their possible observations are presented. Such observations are essential to understand the global water cycle and its variability, both spatially and temporally, and can only be achieved consistently by means of EOs. Additionally, such observations are essential to advance our understanding of coupling between the terrestrial, atmospheric, and oceanic branches of the water cycle, and how this coupling may influence climate variability and predictability. Water resources management directly interferes with the natural water cycle in the forms of building dams, reservoirs, water transfer systems, and irrigation systems that divert and redistribute part of the water storages and fluxes on land. The water cycle is mainly driven and coupled to the energy cycle in terms of phase changes of water (changes among liquid, water vapor, and solid phases) and transport of water by winds in addition to gravity and diffusion processes. The water-cycle components can be observed with in situ sensors as well as airborne and satellite sensors in terms of radiative quantities. Processing and conversion of these radiative signals are necessary to retrieve the water-cycle components.

Wilder, Peter↗

Facet-dependent growth and dissolution of hematite resulting from autocatalytic interactions with Fe(II) and oxalic acid

The ability to simultaneously monitor the flux of iron atoms within the solution and solid phases can provide considerable insight into mechanisms of iron oxide mineral transformations. The autocatalytic interaction between hematite and Fe(II)-oxalate has long been of interest for its environmental and industrial relevance. In this study we take advantage of iron isotopic labelling and mass-sensitive imaging at the single particle scale to determine how changes in solution composition correlate with the morphologic evolution of faceted, micrometer-sized hematite platelets. Net dissolution is confirmed through analyses of aqueous iron chemistry, as well as by quantitative atomic force microscopy. Isotopic mapping techniques show that Fe(II) readily adsorbs to (001) and (012) surfaces in the absence of oxalate, but when oxalate is present selective dissolution of the (001) surface prevails and 57Fe deposition via recrystallization is not observed. Comparison between particle microtopographies following reaction with Fe(II), oxalate, and Fe(II)-oxalate show substantially different behavior, consistent with distinct mechanisms of interaction with hematite surfaces. The extensive characterization conducted on the coupled solution/solid dynamics in this system provides new insight for distinguishing crystal growth, dissolution, and recrystallization processes.

Taylor, Sandra D. [BATTELLE (PACIFIC NW LAB)]↗

Experiments on Nucleation in Different Flow Regimes

The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods. Dilatometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov. The advantage of these experiments is that the samples are directly observable. The nucleation temperature can be measured by noncontact optical pyrometry, the mass of the sample is known, and post processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions.

Bayuzick, R. J.↗

Experiments on Nucleation in Different Flow Regimes

The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods. Dilitometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov. The advantage of these experiments is that the samples are directly observable. The nucleation temperature can be measured by noncontact optical pyrometry, the mass of the sample is known, and post-processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions. Levitation processing of refractory materials in ultra high vacuum provides an avenue to conduct these kinetic studies on single samples. Two experimental methods have been identified where ultra high vacuum experiments are possible; electrostatic levitation in ground-based experiments and electromagnetic processing in low earth orbit on TEMPUS. Such experiments, reported here, were conducted on zirconium. Liquid zirconium is an excellent solvent and has a high solubility for contaminants contained in the bulk material as well as those contaminants found in the vacuum environment. Oxides, nitrides, and carbides do not exist in the melt, and do not form on the surface of molten zirconium, for the materials and vacuum levels used in this study. Ground-based experiments with electrostatic levitation have shown that the statistical nucleation kinetic experiments are viable and yield results which are consistent with classical nucleation theory. The advantage of low earth orbit experiments is the ability to vary the flow conditions in the liquid prior to nucleation. The put-pose of nucleation experiments in TEMPUS was to examine.

Bayuzick, R. J.↗

Experiments on Nucleation in Different Flow Regimes

The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods [1-6]. Dilitometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics [7]. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov [8]. The advantage of these experiments is that the samples are directly observable. The nucleation temperature can be measured by noncontact optical pyrometry, the mass of the sample is known, and post processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions.

Bayuzick, Robert J.↗

Mathematical Analysis and Optimization of Infiltration Processes

A variety of infiltration techniques can be used to fabricate solid materials, particularly composites. In general these processes can be described with at least one time dependent partial differential equation describing the evolution of the solid phase, coupled to one or more partial differential equations describing mass transport through a porous structure. This paper presents a detailed mathematical analysis of a relatively simple set of equations which is used to describe chemical vapor infiltration. The results demonstrate that the process is controlled by only two parameters, alpha and beta. The optimization problem associated with minimizing the infiltration time is also considered. Allowing alpha and beta to vary with time leads to significant reductions in the infiltration time, compared with the conventional case where alpha and beta are treated as constants.

Chang, H.-C.↗

Phase-Field Modeling of Materials Interfaces and Nanostructures

Nanostructured materials offer unique properties for a wide range of energy applications. Among various known processing methods, liquid metal dealloying (LMD)—the selective dissolution of a base alloy element into a metallic melt—has emerged as a powerful technique to produce a new class of nano-/meso-scale open porous and bicontinuous composite structures with ultra-high interfacial area. LMD has recently been complemented by the advent of vapor phase dealloying (VPD), a novel technique that exploits the selective evaporation of one element from a parent alloy containing elements with very different vapor pressures, thereby enabling to fabricate open nanoporous structures of various elements from less-noble metals to inorganic elements regardless of their chemical activity without requiring high LMD temperatures and chemical etching. Together LMD and VPD have greatly expanded the scope of dealloying techniques, limited by traditional electrochemical means to noble metals, and boosted the design of new functional and structural materials that combine a wide variety of elements. Topologically-connected open porous structures with ultra-high surface area allow mass transport within the structure while preserving structural integrity, enabling them to serve as catalysts, fuel cells, supercapacitors, or high-capacity battery materials. Bicontinuous composite structures in turn can display high strength and high ductility or superior radiation-damage resistance due to the ultra-high interface area between interpenetrating solid phases. This research program makes use of state-of-the-art computational methods to understand at a basic level the self-organizing dealloying process with main focus on dealloying kinetics and interfacial pattern formation at the dealloying front controlling initial structure size, topology, and phase compositions. Phase-field simulation studies of LMD focus on solid solutions, line compounds, and intermetallic systems that can form ternary composites by nucleation and growth of a new phase. Studies of VPD employ phase-field modeling and a hybrid method combining a kinetic Monte Carlo (KMC) model of evaporation and surface diffusion with molecular dynamics for vapor-phase transport inside nanopores. Simulations explore mechanisms of interface- and diffusion-controlled dealloying kinetics, both observed in VPD but not fundamentally understood. In addition, our newly developed multi-physics phase-field approach of large-volume-change phase transformations is being used to model novel 3D anode geometries based on dealloyed nanoporous structures including novel sandwiched graphene/Si/silica for highrate Li ion battery. Those studies are aimed at elucidating geometric design principles that improve mechanical stability. We expect this research to enhance the capability to tailor nano-/mesoscale structures for a wide range of energy-related materials applications and to yield further advances in computational methodologies that benefit a broad materials research community.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Infrared triggered dwell and active cooling thermal control effects on microstructural uniformity in DED

Directed Energy Deposition (DED) offers rapid large scale fabrication, but difficulty in delivering consistent microstructures and properties hinders the use of DED fabricated components in safety or performance critical applications. Variability stems from the complex thermal cycles generated by the toolpath used to print the required geometry. Several practical methods have become established in DED to regulate overheating, such as active cooling of the baseplate structure or the use of an infrared camera to inject interlayer pauses to ensure the top layer of the component cools to a set temperature, which have been shown to affect microstructure. However, no critical assessment has been performed as to how effective these controls are in promoting microstructural uniformity in the context of complex layer timing commonly generated by non-prismatic geometries. Here we show how controls influence the thermal field, phase transformations, and dynamic annealing of a low-temperature transformation steel using infrared imaging and operando neutron diffraction. Counterintuitively, common thermal homogenization process controls can reduce microstructural uniformity because these approaches stabilize peak temperature while overlooking temperatures near the solid-state phase transformation fronts. Instead, the cyclic reheating induces spatially-variant dynamically annealed regions which can be modulated via control parameters. We show that these controls have spatially linked effects centimeters away from the active weld, which implies that microstructure control must co-optimize thermal input across many subsequent layers. In conclusion, our results demonstrate the pressing need for higher order controls that integrate predictive elements of simulation data to stabilize printed properties for future qualification of DED components.

Directed energy deposition↗

An Overview of the Electrostatic Levitation Facility at Nasa's Marshall Space Flight Center

Containerless processing represents an important area of research in microgravity materials science. This method provides access to the metastable state of an undercooled melt. Containerless processing provides a high-purity environment for the study of reactive, high-temperature materials. Reduced gravity affords several benefits for containerless processing; for example, greatly reduced positioning forces are required and therefore samples of greater mass can be studied. Additionally, in reduced gravity larger specimens will maintain spherical shape which will facilitate modeling efforts. Space Systems/LORAL developed an Electrostatic Containerless Processing System (ESCAPES) as a materials science research tool for investigations of refractory solids and melts. ESCAPES is designed for the investigation of thermophysical properties, phase equilibria, metastable phase formation, undercooling and nucleation, time-temperature-transformation diagrams, and other aspects of materials processing. These capabilities are critical to the research programs of several Principal Investigators supported by the Microgravity Materials Science Program of NASA. NASA's Marshall Space Flight Center (MSFC) recently acquired the ESCAPES system from LORAL. MSFC is now developing a levitation facility in order to provide a critical resource to the microgravity materials science research community and to continue and enhance ground-based research in the support of the development of flight experiments during the transition to Space Station.

Rogers, Jan R.↗

An Overview of the Electrostatic Levitation Facility at NASA's Marshall Space Flight Center

Containerless processing represents an important area of research in microgravity materials science. This method provides access to the metastable state of an undercooled melt. Containerless processing provides a high-purity environment for the study of reactive, high-temperature materials. Reduced gravity affords several benefits for containerless processing, for example greatly reduced positioning forces are required and therefore samples of greater mass can be studied. Additionally in reduced gravity, larger specimens will maintain spherical shape which will facilitate modeling efforts. Space Systems/LORAL developed an Electrostatic Containerless Processing System (ESCAPES) as a materials science research tool for investigations of refractory solids and melts. ESCAPES is designed for the investigation of thermophysical properties, phase equilibria, metastable phase formation, undercooling and nucleation, time-temperature- transformation diagrams and other aspects of materials processing. These capabilities are critical to the research programs of several Principal Investigators supported by the Microgravity Materials Science Program of NASA. NASA's Marshall Space Flight Center (MSFC) recently acquired the ESCAPES system from LORAL. MSFC is now developing a levitation facility to provide a critical resource to the microgravity materials science research community to continue and enhance ground-based research in the support of the development of flight experiments during the transition to Space Station.

Rogers, Jan R.↗

An Overview of the MSFC Electrostatic Levitation Facility

Containerless processing represents an important area of research in microgravity materials science. This method provides access to the metastable state of an undercooled melt. Containerless processing provides a high-purity environment for the study of reactive, high-temperature materials. Reduced gravity affords several benefits for containerless processing, for example greatly reduced positioning forces are required and therefore samples of greater mass can be studied. Additionally in reduced gravity, larger specimens will maintain spherical shape which will facilitate modeling efforts. Space Systems/LORAL developed an Electrostatic Containerless Processing System (ESCAPES) as a materials science research tool for investigations of refractory solids and melts. ESCAPES is designed for the investigation of thermophysical properties, phase equilibria, metastable phase formation, undercooling and nucleation, time-temperature- transformation diagrams and other aspects of materials processing. These capabilities are critical to the research programs of several Principal Investigators supported by the Microgravity Materials Science Program of NASA.

Rogers, J. R.↗

Optimization of Lithium Content and Sintering Additives in Tape Cast Lithium Garnet Electrolyte Sheets

The lithium garnet (LLZO) remains one of the most promising electrolyte materials for producing solid state batteries. Tape casting is one method for producing the thin ceramic electrolyte layer required for a high-performance solid state battery. Processing of LLZO is complicated by several factors including lithium volatilization, abnormal grain growth and phase instability. Many of these issues are exacerbated in tape cast sheets by the sheets' higher surface area to volume ratio, when compared to pellet processing methods. Here, we report on an environmentally friendly aqueous tape casting process for LLZO using methylcellulose as a binder and compare final sheet properties to other, solvent-based, options. Solids loading, binder content, dispersant composition, and wetting agent type are varied to improve ease of casting and enhance properties of the as-cast tape. Lithium content in sintered LLZO sheets is controlled by the inclusion of excess Li 2 CO 3 as lithium source in the ceramic tape itself and by a novel method of producing a lithium-saturated furnace atmosphere. Sintering time and temperature are optimized, and rapid thermal processing is investigated as a method of reducing lithium loss. Al 2 O 3 and MgO are examined for use as sintering additives. Characterization of LLZO sheets is performed with XRD, EIS and SEM. Li 2 CO 3 and sintering additive levels are optimized for ionic conductivity and density. The optimization effort improved the conductivity and density of 100µm thick sintered sheets to greater than 3x10 -4 S/cm conductivity and 90% density.

36 MATERIALS SCIENCE↗

Insulator–metal transition in CrSiTe 3 triggered by structural distortion under pressure

van der Waals solids are well known to host remarkable phase diagrams with competing phases, unusual energy transfer processes, and elusive states of matter. Among this class of materials, chalcogenides have emerged as the most flexible and relevant platforms for unraveling charge–structure–function relationships. In order to explore the properties of complex chalcogenides under external stimuli, we measured the far infrared spectroscopic response of CrSiTe 3 under extreme pressure–temperature conditions. Analysis of the 368 cm –1 Si–Te stretching mode and the manner in which it is screened by the closure of the indirect gap reveals that the insulator–metal transition takes place immediately after the structural phase transition—once the mixed phase aspect of the lattice distortion is resolved. At the same time, the two-phase region associated with the structural transition widens with decreasing temperature, and the slope of the insulator–metal transition under pressure is consistent with increasing entropy. These trends completely revise the character of the temperature–pressure phase diagram as well as the relationship between the structural and insulator–metal transitions, leading to a critical nexus of activity that may hide a quantum critical point and allow superconductivity to emerge.

36 MATERIALS SCIENCE↗