Fundamentals of Energy Materials: A Theoretical Perspective
This report describes the fundamentals of material energy.
36 MATERIALS SCIENCE↗
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Fundamental Physical Mechanisms of Mitigation Approaches to Laser-Induced Damage on Ultraviolet Optics (FY08 LDRD Final Report)
The objective was to explore and further develop the concept that laser–induced damage on surfaces of an optic can be mitigated to extend its lifetime in high-fluence laser systems. The project scope explored mitigation processes utilizing laser, micro-machining, and chemical techniques including laser-induced damage testing of the mitigated site, and characterization of the size and shapes of the mitigation site with respect to downstream intensification of the high energy laser beam. Advanced materials processing and characterization tools, and computational tools were developed to investigate physical properties of the mitigated regions. The material focus of the mitigation effort was fused silica and potassium di-hydrogen phosphate (KDP) crystal optics. and to develop a fundamental understanding of the physical mechanisms of the mitigation processes is sought in order to extend their applicability to larger and deeper damage sites and to larger laser fluences. When successful, these mitigation processes will significantly extend the useful lifetime of the optic and drastically reduce the associated operating costs. For silica optics, mitigation processes utilizing mid-infrared (4.6 μm) and far infrared (10.6 μm) laser radiation from carbon dioxide lasers was used to ablate, evaporate, melt and anneal the damaged silica surface. By varying the laser parameters (power, pulse rate, spot size, etc.) these investigations evaluated the almost 100x difference in the optical absorption depth between these wavelengths in the efficacy in arresting damage growth, and controlling the end-state of the material in terms of shape morphology, residual stress and process by-products (vapor and re-condensed material). For crystal optics, micro-diamond tool machining and micro re-crystallization of KDP were investigated. A precision three-axis micro machine tool was developed, tested and shown capable of treating damage sites to 1 mm in size that were robust against re-initiation of damage and exhibited acceptable downstream intensification. Micro re-crystallization of KDP was accomplished through Gibbs-Thompson condensation at the tip of an Atomic Force Microscope stylus. By controlling the humidity at the tip and raster scanning of the stylus over damaged crystal surfaces, filling of scratched surfaces with re-crystallized material was demonstrated.
42 ENGINEERING↗
Fundamental studies of energy-and hole/electron- transfer in hydroporphyrin architectures
The long-term objective of the Bocian/Holten/Lindsey research program is to design, synthesize, and characterize tetrapyrrole-based molecular architectures that absorb sunlight, funnel energy, and separate charge with high efficiency and in a manner compatible with current and future solar-energy conversion schemes. The synthetic tetrapyrroles include porphyrins and hydroporphyrins; the latter classes of molecules encompass analogues of the naturally occurring chlorophylls and bacteriochlorophylls (e.g., chlorins, bacteriochlorins, and their derivatives). The attainment of the goals of the research program requires the close interplay of molecular design and synthesis (Lindsey group), static and time-resolved optical spectroscopic measurements (Holten group), and electrochemical, electron paramagnetic resonance, and resonance Raman studies, as well as density functional theory calculations (Bocian Group). The proposed research encompasses four interrelated themes: (1) Determination of the rates of ground-state hole/electron transfer between (hydro)porphyrins in multipigment arrays as a function of array size, distance between components, linker type, site of linker connection, and frontier molecular orbital composition. (2) Examination of excited-state energy transfer among hydroporphyrins in multipigment arrrays, including both pairwise and non-adjacent transfer, with a chief aim to identify the relative contributions of through-space (Förster) and through-bond (Dexter) mechanisms of energy transfer, including the roles of site of linker connection and frontier molecular orbital composition. (3) Elucidation of the role of substituents in tuning the spectral and electronic properties of bacteriochlorins, with a primary aim of learning how to shift the long-wavelength absorption band deeper into the near-infrared region. (4) Continued development of the software package PhotochemCAD for spectral manipulations and calculations through the compilation of a database of spectra for naturally occurring and synthetic hydroporphyrins. The availability of such data should augment efforts in the design of light-harvesting systems where spectral coverage in the red and near-infrared regions is desired. Collectively, the proposed studies will provide fundamental insights into molecular properties, interactions, and processes relevant to the design of molecular architectures for solar-energy conversion. The accomplishment of these goals is only possible through a highly synergistic program that encompasses molecular design, synthesis, and characterization.
14 SOLAR ENERGY↗
Fundamental Study of Micro-Defects in Electropolished EB-Welded and Hydroformed SRF Accelerating Structures
In the area of niobium elecropolishing fundamentals, we focused on understanding the influence of the surface topology, and geometry (with effects from gravity included. The formation of a viscous film is essential for the electropolishing process to take place. The exact nature and composition of the film formed on niobium is still unknown because of its solubility in the electrolyte. Extensive pitting may take place at surface where a stable film cannot form. This has to be taken into consideration while determining the speed with which the SRF cavities are rotated while EP. Hydrodynamic aspects must be taken into consideration while optimizing the polishing parameters. There is improvement in surface finish with polishing time. There is a huge change in surface quality when the EP time is increased from 2 hours to 4 hours but not much change takes place when the time is further increased to 6 hours. So keeping the economic points in view, about 100 um defect layer removal may be sufficient to get the desired performance. In the area of Electropolishing of untreated and treated niobium with Weld Joints we studied untreated and treated Nb, especially for the heat affected areas next to welded bumps, electropolished for different durations. The electropolishing of the untreated Nb caused the formation of pits on the surface at about 15 min but they disappeared when the electropolishing duration was more than 15 min. Electropolishing for 120 min smoothened the surface of untreated Nb by levelling the surface, but the severe formation of pits on the whole surface was found after 240 min. The treatment of Nb significantly changed the Nb surface morphology which was covered by grains of different size that looked light or dark in the optical microscope. The treated Nb was susceptible to pitting during the entire electropolishing starting from 15 min and the dark grains had more susceptibility to pitting than the light grains. In addition, electropolishing for 240 min again resulted in severe pit formation. In the area of Bulge test and microstructure studies, we worked to create a useful constitutive relationship for the complex stress state that accompanies SRF cavity formation. To do so, bulge tests were performed on Cu and Nb tube samples that exhibited the greatest degrees of uniaxial elongation after HT. The data from the bulge tests and an accompanying set of tensile tests provided input to a finite-element model that recreated the bulge tests numerically. As expected the model based on the bulge test results fit the experimental data well at least at low stress levels safely below the bursting pressure. Not so for that based on the tensile results. The results of the study emphasize the importance of for bulge testing rather than tensile testing when deriving the constitutional relationships eventually needed for modelling the hydroforming of Nb SRF cavities.
43 PARTICLE ACCELERATORS↗
Final Report of “Collaborative research: Fundamental science of low temperature plasma-biological material interactions” (Award# DE-SC0005105)
Low temperature plasma (LTP) treatment of biological tissue is a promising path toward sterilization of bacteria due to its versatility and ability to operate under well-controlled and relatively mild conditions. The present collaborative research of an interdisciplinary team of investigators at University of Maryland, College Park (UMD), and University of California, Berkeley (UCB) focused on establishing our knowledge on low temperature plasma-induced chemical modifications in biomolecules that result in inactivation due to various plasma species, including ions, reactive radicals, and UV/VUV photons. The overall goals of the project were to identify the mechanisms by which low and atmospheric pressure plasma (APP) deactivates endotoxic biomolecules. Additionally, we wanted to understand how deactivation processes depend on the interaction of APP with the environment. Various low pressure plasma sources, a vacuum beam system and several atmospheric pressure plasma sources were used to accomplish these objectives. In our work we elucidated for the first time the role of ions, VUV photons and radicals in biological deactivation of model endotoxic biomolecules, both in a UHV beam system and an inductively coupled, low pressure plasma system, and established the associated atomistic modifications in biomolecules. While we showed that both ions and VUV photons can be very efficient in deactivation of biomolecules, significant etching and/or deep modification (~200 nm) were accompanied by these biological effects. One of the most important findings in this work is that the significant deactivation and surface modification can occur with minimal etching using radical species. However, if radical fluxes and corresponding etch rates are relatively high, for example, at atmospheric pressure, inactivation of endotoxic biomolecule film may require near-complete removal of the film. These findings motivated further work at atmospheric pressure using several types of low temperature plasma sources with modified geometry where radical induced interactions generally dominate due to short mean free paths of ions and VUV photons. In these conditions we demonstrated the importance of environmental interactions of plasma species when APP sources are used to modify biomolecules. This is evident from both gas phase characterization data and in-situ surface characterization of treated biomolecules. Environmental interactions can produce unexpected outcomes due to the complex reactions of reactive species with the atmosphere which determine the composition of reactive fluxes and atomistic changes in biomolecules. Overall, this work elucidated a richer spectrum of scientific opportunities and challenges for the field of low temperature plasma-biomolecule surface interactions than initially anticipated, in particular, for plasma sources operating at atmospheric pressure. The insights produced in this work, e.g. demonstration of the importance of environmental interactions, are generally important for applications of APP to materials modifications. Thus one major contributions of this research has been the establishment of methodologies to study the interaction of plasma with bio-molecules in a systemic and rigorous manner. In particular, our studies of atmospheric pressure plasma sources using very well-defined experimental conditions enabled us to correlate atomistic surface modifications of biomolecules with changes in their biological function. The clarification of the role of ions, VUV photons and radicals in deactivation of biomolecules during low pressure and atmospheric pressure plasma-biomolecule interaction has broad implications, e.g. for the emerging field of plasma medicine. The development of methods to detect the effects of plasma treatment on immune-active biomolecules will lay a fundamental foundation to enhance our understanding of the effect of plasma on biological systems. be helpful in many future studies.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Fundamental studies on initiation and evolution of multi-channel discharges and their application to next generation pulsed power machines.
Future pulsed power systems may rely on linear transformer driver (LTD) technology. The LTD's will be the building blocks for a driver that can deliver higher current than the Z-Machine. The LTD's would require tens of thousands of low inductance ( %3C 85nH), high voltage (200 kV DC) switches with high reliability and long lifetime ( 10 4 shots). Sandia's Z-Machine employs 36 megavolt class switches that are laser triggered by a single channel discharge. This is feasible for tens of switches but the high inductance and short switch life- time associated with the single channel discharge are undesirable for future machines. Thus the fundamental problem is how to lower inductance and losses while increasing switch life- time and reliability. These goals can be achieved by increasing the number of current-carrying channels. The rail gap switch is ideal for this purpose. Although those switches have been extensively studied during the past decades, each effort has only characterized a particular switch. There is no comprehensive understanding of the underlying physics that would allow predictive capability for arbitrary switch geometry. We have studied rail gap switches via an extensive suite of advanced diagnostics in synergy with theoretical physics and advanced modeling capability. Design and topology of multichannel switches as they relate to discharge dynamics are investigated. This involves electrically and optically triggered rail gaps, as well as discrete multi-site switch concepts.
Schwarz, Jens↗
Fundamental Studies of Hydroporphyrin Architectures for Solar-Energy Applications
The long-term objective of the Bocian/Holten&Kirmaier/Lindsey research program is to design, synthesize, and characterize tetrapyrrole-based molecular architectures that absorb sunlight, funnel energy, and separate charge with high efficiency and in a manner compatible with current and future solar-energy conversion schemes. The synthetic tetrapyrroles include porphyrins and hydroporphyrins; the latter classes of molecules encompass analogues of the naturally occurring chlorophylls and bacteriochlorophylls (e.g., chlorins, bacteriochlorins, and their derivatives). The attainment of the goals of the research program requires the close interplay of molecular design and synthesis (Lindsey group), static and time-resolved optical spectroscopic measurements (Holten&Kirmaier group), and electrochemical, electron paramagnetic resonance, resonance Raman, and infrared studies, as well as density functional theory calculations (Bocian Group). The proposed research encompasses four interrelated themes: (i) Gain a deeper understanding of the spectral and electronic properties of bacteriochlorins, with a subsidiary aim of learning how to shift the long-wavelength absorption band deeper into the NIR region. Bacteriochlorins bearing diverse substituents, including annulated rings, will be prepared and examined. A set of bacteriochlorins with site-specific isotopic (13C, 2H) substitution patterns about the macrocycle perimeter will be prepared for studies of vibrational and electronic properties. (ii) Examine the underlying electronic origin of panchromatic absorption and excited-state behavior of strongly coupled rylene–tetrapyrrole arrays. The rylene constituents include a perylene-monoimide and a terrylene-monoimide. The tetrapyrroles include porphyrins (meso- or β-linked) and bacteriochlorins (β-linked). The objective is to achieve panchromatic absorption while preserving a viable, long-lived excited singlet state. (iii) Determine the rates of ground-state hole/electron transfer between (hydro)porphyrins as a function of array size, distance between components, linker type, site of linker connection, and frontier molecular orbital composition. (iv) Build upon the results of the aforementioned studies to design, synthesize, and characterize integrated architectures that incorporate a panchromatic absorber and other molecular components that that afford efficient hole/electron migration and long-lived charge separation. Such architectures will be examined on solid substrates to explore the viability of the component parts and processes under application-oriented conditions. Such architectures or successors may prove directly useful for solar-energy conversion systems. An equally important attribute is to serve as a test-bed for successful integration of the requisite properties and processes, some of which require rather weak coupling between constituents, some of which require very strong electronic interactions to elicit the desired behavior, and all of which should be tunable under molecular design control to the extent possible. Collectively, the proposed studies will provide fundamental insights into molecular properties, interactions, and processes relevant to the design of molecular architectures for solar-energy conversion. The accomplishment of these goals is only possible through a highly synergistic program that encompasses molecular design, synthesis, and in-depth characterization.
14 SOLAR ENERGY↗
Fundamentals of figure control and fracture-'free' finishing for high aspect ratio laser optics
The high level objectives of the this work were to: 1) scientifically understand critical phenomena affecting the surface figure during full aperture finishing; 2) utilize these fundamentals to more deterministically control the surface figure during finishing; 3) successfully polish under rogue particle-‘free’ environments during polishing by understanding/preventing key sources of rogue particles.
42 ENGINEERING↗
From Fundamental Understanding To Predicting New Nanomaterials For High Capacity Hydrogen/Methane Storage and Carbon Capture
On-board hydrogen/methane storage in fuel cell-powered vehicles is a major component of the national need to achieve energy independence and protect the environment. The main obstacles in hydrogen storage are slow kinetics, poor reversibility and high dehydrogenation temperatures for the chemical hydrides; and very low desorption temperatures/energies for the physisorption materials (MOF’s, porous carbons). Similarly, the current methane storage technologies are mainly based on physisorption in porous materials but the gravimetric and volumetric storage capacities are below the target values. Finally, carbon capture, a critical component of the mitigation of CO 2 emissions from industrial plants, also suffers from similar problems. The solid-absorbers such as MOFs are either not stable against real flue-gas conditions and/or do not have large enough CO 2 capture capacity to be practical and cost effective. In this project, we addressed these challenges using a unique combination of computational, synthetic and experimental methods. The main scope of our research was to achieve fundamental understanding of the chemical and structural interactions governing the storage and release of hydrogen/methane and carbon capture in a wide spectrum of candidate materials. We studied the effect of scaffolding and doping of the candidate materials on their storage and dynamics properties. We reviewed current progress, challenges and prospect in closely related fields of hydrogen/methane storage and carbon capture. For example, for physisorption based storage materials, we show that tap-densities or simply pressing MOFs into pellet forms reduce the uptake capacities by half and therefore packing MOFs is one of the most important challenges going forward. For room temperature hydrogen storage application of MOFs, we argue that MOFs are the most promising scaffold materials for Ammonia-Borane (AB) because of their unique interior active metal-centers for AB binding and well defined and ordered pores. Here the main challenge is to find a chemically stable MOF required for regeneration of the AB-spent fuel. Finally, for carbon capture application of MOFs, we investigate the performance of a number of metal–organic frameworks with particular focus on their behavior at the low pressures commonly used in swing adsorption. This comparison clearly shows that it is the process that determines which MOF is optimal rather than there being one best MOF, though MOFs that possess enhanced binding at open metal sites generally perform better than those with high surface area.
03 NATURAL GAS↗
Experimental Investigations of Fundamental Processes in Dusty Plasmas
This is the final technical report for DOE Grant #DE-FG02-04ER54795-Experimental Investigations of Fundamental Processes in Dusty Plasmas. A plasma is an ionized gas, and a dusty plasmas is a plasma that contains, in addition to electrons and ions, micron-sized dust particles. The dust particles acquire and electric charge in the plasma by collecting electrons and ions. The electrons move more rapidly than the ions, so the dust charge is negative. A 1 micron dust particle in a typical low temperature plasma has a charge corresponding to approximately 2000 electrons. Dusty plasmas are naturally found in astrophysical plasmas, planetary rings, technological plasmas, and magnetic fusion plasmas. The goal of this project was to study in the laboratory, the basic physical processes that occur in dusty plasmas. This report provides a summary of the major scientific products and activities of this award.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Fundamental Understanding of Methane-Carbon Dioxide-Water (CH 4 -CO 2 - H 2 O) Interactions in Shale Nanopores under Reservoir Conditions
Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO 2 and H 2 O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4 ) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested as an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH 4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4 -CO 2 -H 2 O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4 -CO 2 -H 2 O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.
03 NATURAL GAS↗
Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts
The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron microcopy (STEM) to measure size and structure, energy dispersive X-ray spectroscopy (EDS) to measure atomic composition, X-ray absorption spectroscopy (XAS) to measure oxidation state and metal coordination, Fourier transform infrared spectroscopy (FTIR) to study adsorbed species, laser Raman spectroscopy to probe metal oxide promoters, and temperature programmed reaction/desorption to study the energetics of adsorption and desorption processes. We have studied our bimetallic catalysts for the selective cleavage of carbon-oxygen bonds, and we have studied the effects of adding metal oxide promoters to supported platinum and gold catalysts for water-gas shift (i.e., the production of hydrogen by reaction of carbon monoxide with water). We anticipate that the knowledge obtained from our studies will allow us to identify promising directions for new catalysts that show high activity, selectivity, and stability for important reactions, such as the conversion of biomass-derived oxygenated hydrocarbons to fuels and chemicals.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Workshop on Fundamental Science using Pulsed Power
The project objective was to fund travel to a workshop organized by the Institute for High Energy Density Science (IHEDS) at the University of Texas at Austin. In so doing the intent was to a) Grow the national academic High Energy Density Science (HEDS) community, b) Expand high impact, discovery driven fundamental HEDS, and c) Facilitate user-oriented research
99 GENERAL AND MISCELLANEOUS↗
Fundamental Mechanisms of Roughening and Smoothing During Thin Film Deposition
In this research program, we have explored the fundamental limits for thin film deposition in both crystalline and amorphous (i.e. non-crystalline) materials systems. For vacuum-based physical deposition processes such as sputter deposition, the background gas pressure of the inert gas (usually argon) used as the process gas has been found to be a key variable. Both a roughness transition and stress transition as a function of pressure have been linked to a common mechanism involving collisions of energetic particles from the deposition source with the process inert gas. As energetic particles collide with gas molecules in the deposition process they lose their energy rapidly if the pressure (and background gas density) is above a critical value. Both roughness and stress limit important properties of thin films for applications. In the area of epitaxial growth we have also discovered a related effect; there is a critical pressure below which highly crystalline layers grow in a layer-by-layer mode. This effect is also though to be due to energetic particle thermalization and scattering. Several other important effects such as the observation of coalescence dominated growth has been observed. This mode can be likened to the behavior of two-dimensional water droplets on the hood of a car during a rain storm; as the droplets grow and touch each other they tend to coalesce rapidly into new larger circular puddles, and this process proceeds exponentially as larger puddles overtake smaller ones and also merge with other large puddles. This discovery will enable more accurate simulations and modeling of epitaxial growth processes. We have also observed that epitaxial films undergo a roughening transition as a function of thickness, which is attributed to strain induced by the crystalline lattice mismatch with the substrate crystal. In addition, we have studied another physical deposition process called pulsed laser deposition. It differs from sputter deposition due to the pulsed nature of the deposition where particles arrive at the growth surface in an interval of a few microseconds. We have observed effects such as transient formation of two dimensional islands on elemental crystalline surfaces. Pulsed deposition may also lead to non-equilibrium phases in some cases, such as the observation anomalously high tetragonality for ferroelectric thin films. All of the results described above feature in-situ synchrotron X-ray scattering as the main experimental method, which has become an indispensable technique for observing the kinetics of structures forming in real-time. We have also investigated in-situ coherent X-ray scattering and have developed methods to characterize temporal correlations that are not possible to observe with low-coherence X-rays. A high profile result of this work is a new technique to monitor defect propagation velocities in thin films. This has practical significance since defects limit the properties of thin films and it is desirable to understand their properties and origin in order to control them for practical applications. More broadly, amorphous thin films and multilayers have applications in optical devices, including mirrors and filters. Epitaxial thin films and multilayers have applications in electronic devices such as ferroelectric multilayers for non-volatile data storage, and thermoelectric nanostructures for energy conversion. Our progress in this project points the way for improved deposition methods and for improved simulation and modeling of thin film deposition processes for nanoscale control of materials with novel applications in these areas.
36 MATERIALS SCIENCE↗
Fundamentals of Monte Carlo
This is a powerpoint presentation which serves as lecture material for the Parallel Computing summer school. It goes over the fundamentals of the Monte Carlo calculation method. The material is presented according to the following outline: Introduction (background, a simple example: estimating π), Why does this even work? (The Law of Large Numbers, The Central Limit Theorem), How to sample (inverse transform sampling, rejection), and An example from particle transport.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Fundamental Studies of the Role of Grain Boundaries on Uniform Corrosion of Advanced Nuclear Reactor Materials
The main objective of this proposal is to develop fundamental understanding of the role of grain boundaries in stable oxide growth. To understand the process of oxide layer destabilization, it is necessary to observe the early stages of corrosion. During conventional studies in which a sample is exposed and examined after removal from the autoclave, the destabilization process will normally have already taken place, and is only examined post facto. To capture the instants of oxide destabilization, it is necessary to observe it in situ; however, significant questions always arise as to the influence of the corrosion geometry and conditions on the corrosion process. Thus, a combination of post facto examinations and in situ studies is proposed, which also combines state-of-the-art characterization techniques to derive a complete understanding of the destabilization process and the role of grain boundaries.
22 GENERAL STUDIES OF NUCLEAR REACTORS↗
Fundamental Investigations and Rational Design of Durable High-Performance SOFC Cathodes
The main objective of this project is to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminants, aiming towards the rational design of cathodes with high-performance and enhanced durability by combining a porous backbone (such as LSCF) with a thin catalyst coating. The mechanistic understanding will help us to optimize the composition and morphology of the catalyst layer and microstructure of the LSCF backbone for better performance and durability. More specifically, the technical objectives include: (1) to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminants using in situ and ex situ measurements performed on specially-designed cathodes; (2) to examine the microstructural and compositional evolution of LSCF cathodes as well as the cathode/electrolyte interfaces under realistic operating conditions; (3) to correlate the fuel cell performance instability and degradation with the microstructural and morphological evolution and surface chemistry change of the cathode under realistic operating conditions; (4) to explore new catalyst materials and electrode structures to enhance the stability of the LSCF cathode under realistic operating conditions; and (5) to validate the long term stability of the modified LSCF cathode in commercially available cells under realistic operating conditions. We have systematically evaluated LSCF cathodes in symmetrical cells and anode supported cells under realistic conditions with different types of contaminants such as humidity, CO 2 , and Cr. Electrochemical models for the design of test cells and understanding of mechanisms have been developed for the exploration of fundamental properties of electrode materials. It is demonstrated that the activity and stability of LSCF cathodes can be degraded by the introduction of contaminants. The microstructural and compositional evolution of LSCF cathodes as well as the cathode/electrolyte interfaces under realistic operating conditions has been studied. It is found that SrO readily segregated/enriched on the LSCF surface. More severe contamination conditions cause more SrO on surface. Novel catalyst coatings through particle depositions (PrOx) or continuous thin films (PNM) were successfully developed to improve the activity and stability of LSCF cathodes. Finally, we have demonstrated enhanced activity and stability of LSCF cathodes over longer periods of time in homemade and commercially available cells by an optimized PNM (dense film and particles) infiltration process, under clean air and realistic operating conditions (3% H 2 O, 5% CO 2 and direct Crofer contact). Both performance and durability of single cells with PNM coating has been enhanced compared with those without coating. Raman analysis of cathodes surface indicated that the intensity of SrCrO 4 was significantly decreased.
30 DIRECT ENERGY CONVERSION↗
Fundamental Aspects of Selective Melting Additive Manufacturing Processes
Certain details of the additive manufacturing process known as selective laser melting (SLM) affect the performance of the final metal part. To unleash the full potential of SLM it is crucial that the process engineer in the field receives guidance about how to select values for a multitude of process variables employed in the building process. These include, for example, the type of powder (e.g., size distribution, shape, type of alloy), orientation of the build axis, the beam scan rate, the beam power density, the scan pattern and scan rate. The science-based selection of these settings con- stitutes an intrinsically challenging multi-physics problem involving heating and melting a metal alloy, reactive, dynamic wetting followed by re-solidification. In addition, inherent to the process is its considerable variability that stems from the powder packing. Each time a limited number of powder particles are placed, the stacking is intrinsically different from the previous, possessing a different geometry, and having a different set of contact areas with the surrounding particles. As a result, even if all other process parameters (scan rate, etc) are exactly the same, the shape and contact geometry and area of the final melt pool will be unique to that particular configuration. This report identifies the most important issues facing SLM, discusses the fundamental physics associated with it and points out how modeling can support the additive manufacturing efforts.
36 MATERIALS SCIENCE↗