Showing papers by "Sandia National Laboratories published in 2010"

In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode

Abstract: We report the creation of a nanoscale electrochemical device inside a transmission electron microscope--consisting of a single tin dioxide (SnO(2)) nanowire anode, an ionic liquid electrolyte, and a bulk lithium cobalt dioxide (LiCoO(2)) cathode--and the in situ observation of the lithiation of the SnO(2) nanowire during electrochemical charging. Upon charging, a reaction front propagated progressively along the nanowire, causing the nanowire to swell, elongate, and spiral. The reaction front is a "Medusa zone" containing a high density of mobile dislocations, which are continuously nucleated and absorbed at the moving front. This dislocation cloud indicates large in-plane misfit stresses and is a structural precursor to electrochemically driven solid-state amorphization. Because lithiation-induced volume expansion, plasticity, and pulverization of electrode materials are the major mechanical effects that plague the performance and lifetime of high-capacity anodes in lithium-ion batteries, our observations provide important mechanistic insight for the design of advanced batteries.

DAKOTA : a multilevel parallel object-oriented framework for design optimization, parameter estimation, uncertainty quantification, and sensitivity analysis. Version 5.0, user's manual.

Abstract: The DAKOTA (Design Analysis Kit for Optimization and Terascale Applications) toolkit provides a flexible and extensible interface between simulation codes and iterative analysis methods. DAKOTA contains algorithms for optimization with gradient and nongradient-based methods; uncertainty quantification with sampling, reliability, and stochastic finite element methods; parameter estimation with nonlinear least squares methods; and sensitivity/variance analysis with design of experiments and parameter study methods. These capabilities may be used on their own or as components within advanced strategies such as surrogate-based optimization, mixed integer nonlinear programming, or optimization under uncertainty. By employing object-oriented design to implement abstractions of the key components required for iterative systems analyses, the DAKOTA toolkit provides a flexible and extensible problem-solving environment for design and performance analysis of computational models on high performance computers. This report serves as a reference manual for the commands specification for the DAKOTA software, providing input overviews, option descriptions, and example specifications. DAKOTA Version 5.0 Reference Manual generated on May 7, 2010

Peridynamic Theory of Solid Mechanics

Abstract: Publisher Summary The classical theory of solid mechanics is based on the assumption of a continuous distribution of mass within a body and all internal forces are contact forces that act across zero distance. The mathematical description of a solid that follows from these assumptions relies on PDEs that additionally assume sufficient smoothness of the deformation for the PDEs to make sense in their either strong or weak forms. The classical theory has been demonstrated to provide a good approximation to the response of real materials down to small length scales, particularly in single crystals, provided these assumptions are met. Nevertheless, technology increasingly involves the design and fabrication of devices at smaller and smaller length scales, even interatomic dimensions.

Biofuel combustion chemistry: from ethanol to biodiesel.

Abstract: Biofuels, such as bio-ethanol, bio-butanol, and biodiesel, are of increasing interest as alternatives to petroleum-based transportation fuels because they offer the long-term promise of fuel-source regenerability and reduced climatic impact. Current discussions emphasize the processes to make such alternative fuels and fuel additives, the compatibility of these substances with current fuel-delivery infrastructure and engine performance, and the competition between biofuel and food production. However, the combustion chemistry of the compounds that constitute typical biofuels, including alcohols, ethers, and esters, has not received similar public attention. Herein we highlight some characteristic aspects of the chemical pathways in the combustion of prototypical representatives of potential biofuels. The discussion focuses on the decomposition and oxidation mechanisms and the formation of undesired, harmful, or toxic emissions, with an emphasis on transportation fuels. New insights into the vastly diverse and complex chemical reaction networks of biofuel combustion are enabled by recent experimental investigations and complementary combustion modeling. Understanding key elements of this chemistry is an important step towards the intelligent selection of next-generation alternative fuels.

Pulsed-power-driven cylindrical liner implosions of laser preheated fuel magnetized with an axial field

Abstract: The radial convergence required to reach fusion conditions is considerably higher for cylindrical than for spherical implosions since the volume is proportional to r2 versus r3, respectively. Fuel magnetization and preheat significantly lowers the required radial convergence enabling cylindrical implosions to become an attractive path toward generating fusion conditions. Numerical simulations are presented indicating that significant fusion yields may be obtained by pulsed-power-driven implosions of cylindrical metal liners onto magnetized (>10 T) and preheated (100–500 eV) deuterium-tritium (DT) fuel. Yields exceeding 100 kJ could be possible on Z at 25 MA, while yields exceeding 50 MJ could be possible with a more advanced pulsed power machine delivering 60 MA. These implosions occur on a much shorter time scale than previously proposed implosions, about 100 ns as compared to about 10 μs for magnetic target fusion (MTF) [I. R. Lindemuth and R. C. Kirkpatrick, Nucl. Fusion 23, 263 (1983)]. Consequently t...

Radioactive Iodine Capture in Silver-Containing Mordenites through Nanoscale Silver Iodide Formation

Abstract: The effective capture and storage of radiological iodine (129I) remains a strong concern for safe nuclear waste storage and safe nuclear energy. Silver-containing mordenite (MOR) is a longstanding benchmark for iodine capture; however, the molecular level understanding of this process needed to develop more effective iodine getters has remained elusive. Here we probe the structure and distribution of iodine sorbed by silver-containing MOR using differential pair distribution function analysis. While iodine is distributed between γ-AgI nanoparticles on the zeolite surface and subnanometer α-AgI clusters within the pores for reduced silver MOR, in the case of unreduced silver-exchanged MOR, iodine is exclusively confined to the pores as subnanometer α-AgI. Consequently, unreduced silver-containing zeolites may offer a more secure route for radioactive iodine capture, with the potential to more effectively trap the iodine for long-term storage.

Cold welding of ultrathin gold nanowires

Abstract: The welding of metals at the nanoscale is likely to have an important role in the bottom-up fabrication of electrical and mechanical nanodevices. Existing welding techniques use local heating, requiring precise control of the heating mechanism and introducing the possibility of damage. The welding of metals without heating (or cold welding) has been demonstrated, but only at macroscopic length scales and under large applied pressures. Here, we demonstrate that single-crystalline gold nanowires with diameters between 3 and 10 nm can be cold-welded together within seconds by mechanical contact alone, and under relatively low applied pressures. High-resolution transmission electron microscopy and in situ measurements reveal that the welds are nearly perfect, with the same crystal orientation, strength and electrical conductivity as the rest of the nanowire. The high quality of the welds is attributed to the nanoscale sample dimensions, oriented-attachment mechanisms and mechanically assisted fast surface-atom diffusion. Welds are also demonstrated between gold and silver, and silver and silver, indicating that the technique may be generally applicable.

Conductivity, Doping, and Redox Chemistry of a Microporous Dithiolene-Based Metal−Organic Framework

Abstract: The new microporous metal−organic framework Cu[Ni(pdt)2] (pdt2− = pyrazine-2,3-dithiolate) is demonstrated to have an optical bandgap, p-type semiconductivity, and redox activity. The compound can be doped by using I2 as an oxidant, leading to an increase in conductivity by 4 orders of magnitude with retention of porosity.

Temporal Link Prediction using Matrix and Tensor Factorizations

Abstract: The data in many disciplines such as social networks, web analysis, etc. is link-based, and the link structure can be exploited for many different data mining tasks. In this paper, we consider the problem of temporal link prediction: Given link data for times 1 through T, can we predict the links at time T+1? If our data has underlying periodic structure, can we predict out even further in time, i.e., links at time T+2, T+3, etc.? In this paper, we consider bipartite graphs that evolve over time and consider matrix- and tensor-based methods for predicting future links. We present a weight-based method for collapsing multi-year data into a single matrix. We show how the well-known Katz method for link prediction can be extended to bipartite graphs and, moreover, approximated in a scalable way using a truncated singular value decomposition. Using a CANDECOMP/PARAFAC tensor decomposition of the data, we illustrate the usefulness of exploiting the natural three-dimensional structure of temporal link data. Through several numerical experiments, we demonstrate that both matrix- and tensor-based techniques are effective for temporal link prediction despite the inherent difficulty of the problem. Additionally, we show that tensor-based techniques are particularly effective for temporal data with varying periodic patterns.

Exascale computing technology challenges

Abstract: High Performance Computing architectures are expected to change dramatically in the next decade as power and cooling constraints limit increases in microprocessor clock speeds. Consequently computer companies are dramatically increasing on-chip parallelism to improve performance. The traditional doubling of clock speeds every 18-24 months is being replaced by a doubling of cores or other parallelism mechanisms. During the next decade the amount of parallelism on a single microprocessor will rival the number of nodes in early massively parallel supercomputers that were built in the 1980s. Applications and algorithms will need to change and adapt as node architectures evolve. In particular, they will need to manage locality to achieve performance. A key element of the strategy as we move forward is the co-design of applications, architectures and programming environments. There is an unprecedented opportunity for application and algorithm developers to influence the direction of future architectures so that they meet DOE mission needs. This article will describe the technology challenges on the road to exascale, their underlying causes, and their effect on the future of HPC system design.

Graphene Islands on Cu Foils: The Interplay between Shape, Orientation, and Defects

Abstract: We have observed the growth of monolayer graphene on Cu foils using low-energy electron microscopy. On the (100)-textured surface of the foils, four-lobed, 4-fold-symmetric islands nucleate and grow. The graphene in each of the four lobes has a different crystallographic alignment with respect to the underlying Cu substrate. These “polycrystalline” islands arise from complex heterogeneous nucleation events at surface imperfections. The shape evolution of the lobes is well explained by an angularly dependent growth velocity. Well-ordered graphene forms only above ∼790 °C. Sublimation-induced motion of Cu steps during growth at this temperature creates a rough surface, where large Cu mounds form under the graphene islands. Strategies for improving the quality of monolayer graphene grown on Cu foils must address these fundamental defect-generating processes.

Introducing the Graph 500

Abstract: In the words of Lord Kelvin, “if you cannot measure it, you cannot improve it”. One of the longlasting successes of the Top 500 list is sustained, community-wide floating point performance improvement. Emerging large-data problems, either resulting from measured real-world phenomena or as further processing of data generated by simulation, have radically different performance characteristics and architectural requirements. As the community contemplates scaling to large-scale HPC resources to solve these problems, we are challenged by the reality that supercomputers are typically optimized for the 3D simulation of physics, not large-scale, data-driven analysis. Consequently, the community contemplating this kind of analysis requires a new yard stick for evaluating future platforms. Since the invention of the von Neumann architecture, the physics simulation has largely driven the development and evolution of High Performance Computing. This allows scientists and engineers to test hypotheses, designs, and ask “what if” questions. Emerging informatics and analytics applications are different both in purpose and structure. While physics simulations typically are core-memory sized, floating point intensive, and well-structured, informatics applications tend to be out of core, integer oriented, and unstructured. (It could be argued that physics simulations are moving in this direction.) The graph abstraction is a powerful model in com-

Long Range Interactions in Nanoscale Science.

Abstract: Our understanding of the ``long range'' electrodynamic, electrostatic, and polar interactions that dominate the organization of small objects at separations beyond an interatomic bond length is reviewed From this basic-forces perspective, a large number of systems are described from which one can learn about these organizing forces and how to modulate them The many practical systems that harness these nanoscale forces are then surveyed The survey reveals not only the promise of new devices and materials, but also the possibility of designing them more effectively

A statistical, physical-based, micro-mechanical model of hydrogen-induced intergranular fracture in steel

Abstract: Intergranular cracking associated with hydrogen embrittlement represents a particularly severe degradation mechanism in metallic structures which can lead to sudden and unexpected catastrophic fractures. As a basis for a strategy for the prognosis of such failures, here we present a comprehensive physical-based statistical micro-mechanical model of such embrittlement which we use to quantitatively predict the degradation in fracture strength of a high-strength steel with increasing hydrogen concentration, with the predictions verified by experiment. The mechanistic role of dissolved hydrogen is identified by the transition to a locally stress-controlled fracture, which is modeled as being initiated by a dislocation pile-up against a grain-boundary carbide which in turn leads to interface decohesion and intergranular fracture. Akin to cleavage fracture in steel, the “strength” of these carbides is modeled using weakest-link statistics. We associate the dominant role of hydrogen with trapping at dislocations; this trapped hydrogen reduces the stress that impedes dislocation motion and also lowers the reversible work of decohesion at the tip of dislocation pile-up at the carbide/matrix interface. Mechanistically, the model advocates the synergistic action of both the hydrogen-enhanced local plasticity and decohesion mechanisms in dictating failure.

Understanding the interactions of cellulose with ionic liquids: a molecular dynamics study.

Abstract: Ionic liquids (ILs) have recently been demonstrated to be highly effective solvents for the dissolution of cellulose and lignocellulosic biomass. To date, there is no definitive rationale for selecting ionic liquids that are capable of dissolving these biopolymers. In this work, an all-atom force field for the IL 1-ethyl-3-methylimidazolium acetate [C2mim][OAc] was developed and the behavior of cellulose in this IL was examined using molecular dynamics simulations of a series of (1−4) linked β-d-glucose oligomers with a degree of polymerization n = 5, 6, 10, and 20. Molecular dynamics simulations were also carried out on cellulose oligomers in two common solvents, water and methanol, which are known to precipitate cellulose from IL solutions, to determine the extent and energetics of the interactions between these solvents and the cellulosic oligomers. Thermodynamic properties, such as density and solubility, as well as the two-body solute−solvent interaction energy terms, were calculated. The structural ...

Current and Future Challenges in Radiation Effects on CMOS Electronics

Abstract: Advances in microelectronics performance and density continue to be fueled by the engine of Moore's law. Although lately this engine appears to be running out of steam, recent developments in advanced technologies have brought about a number of challenges and opportunities for their use in radiation environments. For example, while many advanced CMOS technologies have generally shown improving total dose tolerance, single-event effects continue to be a serious concern for highly scaled technologies. In this paper, we examine the impact of recent developments and the challenges they present to the radiation effects community. Topics covered include the impact of technology scaling on radiation response and technology challenges for both total dose and single-event effects. We include challenges for hardening and mitigation techniques at the nanometer scale. Recent developments leading to hardness assurance challenges are covered. Finally, we discuss future radiation effects challenges as the electronics industry looks beyond Moore's law to alternatives to traditional CMOS technologies.

Discrete plasticity in sub-10-nm-sized gold crystals

Abstract: Although deformation processes in submicron-sized metallic crystals are well documented, the direct observation of deformation mechanisms in crystals with dimensions below the sub-10-nm range is currently lacking. Here, through in situ high-resolution transmission electron microscopy (HRTEM) observations, we show that (1) in sharp contrast to what happens in bulk materials, in which plasticity is mediated by dislocation emission from Frank-Read sources and multiplication, partial dislocations emitted from free surfaces dominate the deformation of gold (Au) nanocrystals; (2) the crystallographic orientation (Schmid factor) is not the only factor in determining the deformation mechanism of nanometre-sized Au; and (3) the Au nanocrystal exhibits a phase transformation from a face-centered cubic to a body-centered tetragonal structure after failure. These findings provide direct experimental evidence for the vast amount of theoretical modelling on the deformation mechanisms of nanomaterials that have appeared in recent years.

Three-dimensional direct numerical simulation of a turbulent lifted hydrogen jet flame in heated coflow: a chemical explosive mode analysis

Abstract: A chemical explosive mode analysis (CEMA) was developed as a new diagnostic to identify flame and ignition structure in complex flows. CEMA was then used to analyse the near-field structure of the stabilization region of a turbulent lifted hydrogen–air slot jet flame in a heated air coflow computed with three-dimensional direct numerical simulation. The simulation was performed with a detailed hydrogen–air mechanism and mixture-averaged transport properties at a jet Reynolds number of 11000 with over 900 million grid points. Explosive chemical modes and their characteristic time scales, as well as the species involved, were identified from the Jacobian matrix of the chemical source terms for species and temperature. An explosion index was defined for explosive modes, indicating the contribution of species and temperature in the explosion process. Radical and thermal runaway can consequently be distinguished. CEMA of the lifted flame shows the existence of two premixed flame fronts, which are difficult to detect with conventional methods. The upstream fork preceding the two flame fronts thereby identifies the stabilization point. A Damkohler number was defined based on the time scale of the chemical explosive mode and the local instantaneous scalar dissipation rate to highlight the role of auto-ignition in affecting the stabilization points in the lifted jet flame.

Comparison of Diesel Spray Combustion in Different High-Temperature, High-Pressure Facilities

Abstract: Diesel spray experiments at controlled high-temperature and high-pressure conditions offer the potential for an improved understanding of diesel combustion, and for the development of more accurate CFD models that will ultimately be used to improve engine design. Several spray chamber facilities capable of high-temperature, high-pressure conditions typical of engine combustion have been developed, but uncertainties about their operation exist because of the uniqueness of each facility. For the IMEM meeting, we describe results from comparative studies using constant-volume vessels at Sandia National Laboratories and IFP. Targeting the same ambient gas conditions (900 K, 60 bar, 22.8 kg/m{sup 3}, 15% oxygen) and sharing the same injector (common rail, 1500 bar, KS1.5/86 nozzle, 0.090 mm orifice diameter, n-dodecane, 363 K), we describe detailed measurements of the temperature and pressure boundary conditions at each facility, followed by observations of spray penetration, ignition, and combustion using high-speed imaging. Performing experiments at the same high-temperature, high-pressure operating conditions is an objective of the Engine Combustion Network (http://www.ca.sandia.gov/ECN/), which seeks to leverage the research capabilities and advanced diagnostics of all participants in the ECN. We expect that this effort will generate a high-quality dataset to be used for advanced computational model development at engine conditions.

Boosted HCCI for High Power without Engine Knock and with Ultra-Low NOx Emissions - using Conventional Gasoline

Abstract: The potential of boosted HCCI for achieving high loads has been investigated for intake pressures (P in) from 100 kPa (naturally aspirated) to 325 kPa absolute. Experiments were conducted in a single-cylinder HCCI research engine (0.98 liters) equipped with a compression-ratio 14 piston at 1200 rpm. The intake charge was fully premixed well upstream of the intake, and the fuel was a research-grade (R+M)/2 = 87-octane gasoline with a composition typical of commercial gasolines. Beginning with P in = 100 kPa, the intake pressure was systematically increased in steps of 20 - 40 kPa, and for each P in, the fueling was incrementally increased up to the knock/stability limit, beyond which slight changes in combustion conditions can lead to strong knocking or misfire. A combination of reduced intake temperature and cooled EGR was used to compensate for the pressure-induced enhancement of autoignition and to provide sufficient combustion-phasing retard to control knock. The maximum attainable load increased progressively with boost from a gross indicated mean effective pressure (IMEP g) of about 5 bar for naturally aspirated conditions up to 16.34 bar for P in = 325 kPa. For this high-load point, combustion and indicated thermal efficiencies were 99% and 47%, respectively, and NOx emissions were < 0.1 g/kg-fuel. Maximum pressure-rise rates were kept sufficiently low to prevent knock, and the COV of the IMEP g was < 1.5%. Central to achieving these results was the ability to retard combustion phasing (CA50) as late as 19°after TDC with good stability under boosted conditions. Detailed examination of the heat release rates shows that this substantial CA50 retard was possible because intake boosting significantly enhances the early autoignition reactions, keeping the charge temperature rising toward the hot-ignition point despite the high rate of expansion at these late crank angles. Overall, the investigation showed that well-controlled boosted HCCI has a strong potential for achieving power levels close to those of turbo-charged diesel engines. Copyright © 2010 SAE International.

A Framework for Assessing the Resilience of Infrastructure and Economic Systems

Abstract: Recent U.S. national mandates are shifting the country’s homeland security policy from one of asset-level critical infrastructure protection (CIP) to allhazards critical infrastructure resilience, creating the need for a unifying framework for assessing the resilience of critical infrastructure systems and the economies that rely on them. Resilience has been defined and applied in many disciplines; consequently, many disparate approaches exist. We propose a general framework for assessing the resilience of infrastructure and economic systems. The framework consists of three primary components: (1) a definition of resilience that is specific to infrastructure systems; (2) a quantitative model for measuring the resilience of systems to disruptive events through the evaluation of both impacts to system performance and the cost of recovery; and (3) a qualitative method for assessing the system properties that inherently determine system resilience, providing insight and direction for potential improvements in these systems.

First-principles and classical molecular dynamics simulation of shocked polymers

Abstract: Density functional theory (DFT) molecular dynamics (MD) and classical MD simulations of the principal shock Hugoniot are presented for two hydrocarbon polymers, polyethylene (PE) and poly(4-methyl-1-pentene) (PMP). DFT results are in excellent agreement with experimental data, which is currently available up to 80 GPa. Further, we predict the PE and PMP Hugoniots up to 350 and 200 GPa, respectively. For comparison, we studied two reactive and two nonreactive interaction potentials. For the latter, the exp-6 interaction of Borodin et al. showed much better agreement with experiment than OPLS. For the reactive force fields, ReaxFF displayed decidedly better agreement than AIREBO. For shocks above 50 GPa, only the DFT results are of high fidelity, establishing DFT as a reliable method for shocked macromolecular systems.

Viscoplasticity using peridynamics

Abstract: Peridynamics is a continuum reformulation of the standard theory of solid mechanics. Unlike the partial differential equations of the standard theory, the basic equations of peridynamics are applicable even when cracks and other singularities appear in the deformation field. The assumptions in the original peridynamic theory resulted in severe restrictions on the types of material response that could be modeled, including a limitation on the Poisson ratio. Recent theoretical developments have shown promise for overcoming these limitations, but have not previously incorporated rate dependence and have not been demonstrated in realistic applications. In this paper, a new method for implementing a rate-dependent plastic material within a peridynamic numerical model is proposed and demonstrated. The resulting material model implementation is fitted to rate-dependent test data on 6061-T6 aluminum alloy. It is shown that with this material model, the peridynamic method accurately reproduces the experimental results for Taylor impact tests over a wide range of impact velocities. The resulting model retains the advantages of the peridynamic formulation regarding discontinuities while allowing greater generality in material response than was previously possible. Copyright © 2009 John Wiley & Sons, Ltd.

Measuring fundamental properties in operating solid oxide electrochemical cells by using in situ X-ray photoelectron spectroscopy

Abstract: Photoelectron spectroscopic measurements have the potential to provide detailed mechanistic insight by resolving chemical states, electrochemically active regions and local potentials or potential losses in operating solid oxide electrochemical cells (SOCs), such as fuel cells. However, high-vacuum requirements have limited X-ray photoelectron spectroscopy (XPS) analysis of electrochemical cells to ex situ investigations. Using a combination of ambient-pressure XPS and CeO2-x/YSZ/Pt single-chamber cells, we carry out in situ spectroscopy to probe oxidation states of all exposed surfaces in operational SOCs at 750 °C in 1 mbar reactant gases H2 and H 2O. Kinetic energy shifts of core-level photoelectron spectra provide a direct measure of the local surface potentials and a basis for calculating local overpotentials across exposed interfaces. The mixed ionic/electronic conducting CeO2-x electrodes undergo Ce3+/Ce4+ oxidation-reduction changes with applied bias. The simultaneous measurements of local surface Ce oxidation states and electric potentials reveal the active ceria regions during H2 electro-oxidation and H2O electrolysis. The active regions extend ∼150 μm from the current collectors and are not limited by the three-phase-boundary interfaces associated with other SOC materials. The persistence of the Ce3+/Ce 4+ shifts in the ∼150 μm active region suggests that the surface reaction kinetics and lateral electron transport on the thin ceria electrodes are co-limiting processes.

Nature's neutron probe: Land surface hydrology at an elusive scale with cosmic rays

Abstract: [1] Fast neutrons are generated naturally at the land surface by energetic cosmic rays. These “background” neutrons respond strongly to the presence of water at or near the land surface and represent a hitherto elusive intermediate spatial scale of observation that is ideal for land surface studies and modeling. Soil moisture, snow, and biomass each have a distinct influence on the spectrum, height profile, and directional intensity of neutron fluxes above the ground, suggesting that different sources of water at the land surface can be distinguished with neutron data alone. Measurements can be taken at fixed sites for long-term monitoring or in a moving vehicle for mapping over large areas. We anticipate applications in many previously problematic contexts, including saline environments, wetlands and peat bogs, rocky soils, the active layer of permafrost, and water and snow intercepted by vegetation, as well as calibration and validation of data from spaceborne sensors.

Multimaterial piezoelectric fibres

Abstract: Fibres are typically used as passive devices, whether in fibre-optical cables used in telecommunciations or as yarns for clothing. The demonstration of polymer-based piezoelectric fibres that can be drawn to tens of metres in length, and whose acoustic response can be actively controlled, suggests possible applications in, for example, medical imaging or acoustic sensing.