Depression is a major workplace concern with significant impact on employee productivity, attendance and “presenteeism” and often affects the company bottom line in areas such as cost impact, employee morale, worker turnover and affected families. However, despite the frequent challenge of depression in the workplace, EAPs are often not well-equipped to fully address these employees. Often, the individual will either be directed to a 24 hour call center or seen briefly onsite by an EAP professional and referred to a treating provider without a full assessment or comprehensive approach. Diagnostic practices may be informal without use of validated tools and without a full assessment of risk or identification of appropriate level of care. However, the EAP may be ideally placed within an organization to have a significant positive impact on this condition. This article will summarize my recommendations regarding EAP strategies for optimizing assessment and care for employees who are struggling with depression. I will also briefly review a working model for the assessment and treatment of depression that we have developed at my company using best practices and a collaborative model for tracking outcomes.
The accelerated aging behavior and aging state of a 30 year old field retrieved polysulfide elastomer was examined. The material is used as an environmental thread sealant for a stainless steel bolt in a steel threaded insert in an aluminum assembly. It is a two component curable polysulfide elastomer that is commercially available in a similar formulation as was applied 30 years ago. The primary goal of this study was to establish if aging over 30 years under moderate aging conditions (mostly ambient temperature and humidity) resulted in significant property changes, or if accelerated aging could identify developing aging pathways which would prevent the extended use of this material. The aging behavior of this material was examined in three ways: A traditional accelerated thermo-oxidative aging study between 95 to 140°C which focused on physical and chemical properties changes, an evaluation of the underlying oxidation rates between RT and 125°C, and an assessment of the aging state of a small 30 year old sample. All three data sets were used to establish aging characteristics, their time evolution, and to extrapolate the observed behavior to predict performance limits at RT. The accelerated aging study revealed a relatively high average activation energy of ~130 kJ/mol which gives overconfident performance predictions. Oxidation rates showed a decreasing behavior with aging time and a lower E a of ~84 kJ/mol from time - temperature superposition , but also predicted sufficient additional performance at RT. Consistent with these projections for extended RT performance, only small changes were observed for the 30 year old material. Extrapolations using this partially aged material also predict ongoing use as a viable option. Unexpected RT degradation could only develop into a concern should the oxidation rate not trend lower over time as was observed at elevated temperature. Considering all data acquired in this limited aging study , there are no immediately apparent concerns with this material for ongoing use. ACKNOWLEDGEMENTS We thank Lisa Deibler for providing us with a small sample of field aged and new commercial material.
In coded aperture imaging, one of the most important factors determining the quality of reconstructed images is the choice of mask/aperture pattern. In many applications, uniformly redundant arrays (URAs) are widely accepted as the optimal mask pattern. Under ideal conditions, thin and highly opaque masks, URA patterns are mathematically constructed to provide artifact-free reconstruction however, the number of URAs for a chosen number of mask elements is limited and when highly penetrating particles such as fast neutrons and high-energy gamma-rays are being imaged, the optimum is seldom achieved. In this case more robust mask patterns that provide better reconstructed image quality may exist. Through the use of heuristic optimization methods and maximum likelihood expectation maximization (MLEM) image reconstruction, we show that for both point and extended neutron sources a random mask pattern can be optimized to provide better image quality than that of a URA.
Typically, when three or more antenna beams along a single axis are required, the answer has been multiple antenna phase-centers, essentially a phase-monopulse system. Such systems and their design parameters are well-reported in the literature. Less appreciated is that three or more antenna beams can also be generated in an amplitude-monopulse fashion. Consequently, design guidelines and performance analysis of such antennas is somewhat under-reported in the literature. We provide discussion herein of three beams arrayed in a single axis with an amplitude-monopulse configuration.
An improved system was developed to recover the initial parameters and operating conditions from spent nuclear fuel. This work is an expansion of a previous proof-of-concept system developed by the author. The improved system increases the fidelity of the forward model within the spent fuel forensic inverse analysis using two unique methodologies. The first improvement consists of developing a system to accurately create one-group neutron crosssection libraries for any user-specified reactor system. As such, a detailed model using the depletion code MONTEBURNS is developed. During MONTEBURNS execution, cross-section libraries are generated at every user specified burnup step in time. These libraries could be developed for many reactor systems, then housed in a database and used for analyzing spent fuel.
Ormond, Eugene C.; Bozman, Dan R.; Garcia, Michael R.; Henderson, David J.; Hogge, Keith W.; Huber, Steven R.; Larsen, Monty L.; Misch, Michael K.; Mitton, Charles V.; Molina, Isidro; Nelson, Daniel S.; Stucki, Kyle M.
Storage systems are a foundational component of computational, experimental, and observational science today. The success of Department of Energy (DOE) activities in these areas is inextricably tied to the usability, performance, and reliability of storage and input/output (I/O) technologies.
Sandia journal manuscript; Not yet accepted for publication
Ferson, Scott; Kreinovich, Vladik; Grinzburg, Lev; Myers, Davis; Sentz, Kari
This report summarizes a variety of the most useful and commonly applied methods for obtaining Dempster-Shafer structures, and their mathematical kin probability boxes, from empirical information or theoretical knowledge. The report includes a review of the aggregation methods for handling agreement and conflict when multiple such objects are obtained from different sources.
Sandia journal manuscript; Not yet accepted for publication
Ferson, Scott; Nelsen, Roger B.; Hajagos, Janos; Berleant, Daniel J.; Zhang, Jianzhong; Tucker, W.T.; Ginzburg, Lev R.; Oberkampf, William L.
This report summarizes methods to incorporate information (or lack of information) about inter-variable dependence into risk assessments that use Dempster-Shafer theory or probability bounds analysis to address epistemic and aleatory uncertainty. The report reviews techniques for simulating correlated variates for a given correlation measure and dependence model, computation of bounds on distribution functions under a specified dependence model, formulation of parametric and empirical dependence models, and bounding approaches that can be used when information about the intervariable dependence is incomplete. The report also reviews several of the most pervasive and dangerous myths among risk analysts about dependence in probabilistic models.
Ormond, Eugene C.; Bozman, Dan R.; Garcia, Michael R.; Henderson, David J.; Hogge, Keith W.; Huber, Steven R.; Larsen, Monty L.; Misch, Michael K.; Mitton, Charles V.; Molina, Isidro; Nelson, Daniel S.; Stucki, Kyle M.
Weak link (WL)/strong link (SL) systems are important parts of the overall operational design of high - consequence systems. In such designs, the SL system is very robust and is intended to permit operation of the entire system under, and only under, intended conditions. In contrast, the WL system is intended to fail in a predictable and irreversible manner under accident conditions and render the entire system inoperable before an accidental operation of the SL system. The likelihood that the WL system will fail to d eactivate the entire system before the SL system fails (i.e., degrades into a configuration that could allow an accidental operation of the entire system) is referred to as probability of loss of assured safety (PLOAS). This report describes the Fortran 90 program CPLOAS_2 that implements the following representations for PLOAS for situations in which both link physical properties and link failure properties are time - dependent: (i) failure of all SLs before failure of any WL, (ii) failure of any SL before f ailure of any WL, (iii) failure of all SLs before failure of all WLs, and (iv) failure of any SL before failure of all WLs. The effects of aleatory uncertainty and epistemic uncertainty in the definition and numerical evaluation of PLOAS can be included in the calculations performed by CPLOAS_2. Keywords: Aleatory uncertainty, CPLOAS_2, Epistemic uncertainty, Probability of loss of assured safety, Strong link, Uncertainty analysis, Weak link
To address a variety of difficulties surrounding the use of finite element analysis (FEA) in product development at Sandia, this research explored a 'designerly' insertion of FEA into the design-build-test product development cycle. Designerly FEA is characterized by the use of simplified FEA models, designer-friendly FEA software, an FEA analyst embedded in the product design team, relative comparisons of design options, and a deliberate leveraging of routine prototype testing to collect model validation data. Two case study projects were used to explore the impact of this approach on the product development teams' thinking and perceptions of FEA. The case study data was collected using mixed methods and analyzed using a theory-building approach. The results were synthesized into a framework describing how the use of FEA to build confidence in a product design is related to the process by which product development teams gain or lose confidence in FEA itself. The implications may extend to other organizations that desire to increase the impact of simulation technologies in their product development process.
An assessment of the effects of cation concentration on the thermophysical properties of salts in the temperature range of 300 to 500°C was investigated. The latent heat and density exhibit a statistically relevant dependence upon mixtures, while heat capacity, viscosity, and thermal conductivity did not exhibit statistical differences among mixtures in the range of temperature studied. Heat capacity tended to be nearly flat while in the liquid state for mixtures at each temperature. Density of the mixtures decreases linearly with temperature. Mixture composition influenced density, with a relative variation up to 2% over the temperature range investigated. Viscosity decreased as a function of temperature in a non-linear fashion and methods used here tended to exhibit a higher value than literature values. Thermal conductivity used laser flash and transient wire methods. Transient wire found no differences between mixtures within repeatability of the measurement, while laser flash was found to not work well for molten nitrate salts due to the large error.
Tensor factorizations with nonnegativity constraints have found application in analysing data from cyber traffic, social networks, and other areas. We consider application data best described as being generated by a Poisson process (e.g. count data), which leads to sparse tensors that can be modelled by sparse factor matrices. In this paper, we investigate efficient techniques for computing an appropriate canonical polyadic tensor factorization based on the Kullback–Leibler divergence function. We propose novel subproblem solvers within the standard alternating block variable approach. Our new methods exploit structure and reformulate the optimization problem as small independent subproblems. We employ bound-constrained Newton and quasi-Newton methods. Finally, we compare our algorithms against other codes, demonstrating superior speed for high accuracy results and the ability to quickly find sparse solutions.
In this study, the properties of mechanically stable single-nanoparticle (NP)-thick membranes have largely been studied at room temperature. How these membranes soften as nanoparticle ligands disorder with increasing temperature is unknown. Molecular dynamics simulations are used to probe the temperature dependence of the mechanical and nanostructural properties of nanoparticle membranes made of 6 nm diameter Au nanoparticles coated with dodecanethiol ligands and terminated with either methyl (CH3) or carboxyl (COOH) terminal groups. For methyl-terminated ligands, interactions along the alkane chain provide mechanical stiffness, with a Young's modulus of 1.7 GPa at 300 K. For carboxyl-terminated chains, end-group interactions are significant, producing stiffer membranes at all temperatures, with a Young's modulus of 3.8 GPa at 300 K. For both end-group types, membrane stiffness is reduced to zero at about 400 K. Ligand structure and mechanical properties of membranes at 300 K that have been annealed at 400 K are comparable to samples that do not undergo thermal annealing.
TlBr is promising for g- and x- radiation detection, but suffers from rapid performance degradation under the operating external electric fields. To enable molecular dynamics (MD) studies of this degradation, we have developed a Stillinger-Weber type of TlBr interatomic potential. During this process, we have also addressed two problems of wider interests. First, the conventional Stillinger-Weber potential format is only applicable for tetrahedral structures (e.g., diamond-cubic, zinc-blende, or wurtzite). Here we have modified the analytical functions of the Stillinger-Weber potential so that it can now be used for other crystal structures. Second, past modifications of interatomic potentials cannot always be applied by a broad community because any new analytical functions of the potential would require corresponding changes in the molecular dynamics codes. Here we have developed a polymorphic potential model that simultaneously incorporates Stillinger-Weber, Tersoff, embedded-atom method, and any variations (i.e., modified functions) of these potentials. As a result, we have implemented this polymorphic model in MD code LAMMPS, and demonstrated that our TlBr potential enables stable MD simulations under external electric fields.
Atmospheric inversions are frequently used to estimate fluxes of atmospheric greenhouse gases (e.g., biospheric CO2 flux fields) at Earth's surface. These inversions typically assume that flux departures from a prior model are spatially smoothly varying, which are then modeled using a multi-variate Gaussian. When the field being estimated is spatially rough, multi-variate Gaussian models are difficult to construct and a wavelet-based field model may be more suitable. Unfortunately, such models are very high dimensional and are most conveniently used when the estimation method can simultaneously perform data-driven model simplification (removal of model parameters that cannot be reliably estimated) and fitting. Such sparse reconstruction methods are typically not used in atmospheric inversions. In this work, we devise a sparse reconstruction method, and illustrate it in an idealized atmospheric inversion problem for the estimation of fossil fuel CO2 (ffCO2) emissions in the lower 48 states of the USA. Our new method is based on stagewise orthogonal matching pursuit (StOMP), a method used to reconstruct compressively sensed images. Our adaptations bestow three properties to the sparse reconstruction procedure which are useful in atmospheric inversions. We have modified StOMP to incorporate prior information on the emission field being estimated and to enforce non-negativity on the estimated field. Finally, though based on wavelets, our method allows for the estimation of fields in non-rectangular geometries, e.g., emission fields inside geographical and political boundaries. Our idealized inversions use a recently developed multi-resolution (i.e., wavelet-based) random field model developed for ffCO2 emissions and synthetic observations of ffCO2 concentrations from a limited set of measurement sites. We find that our method for limiting the estimated field within an irregularly shaped region is about a factor of 10 faster than conventional approaches. It also reduces the overall computational cost by a factor of 2. Further, the sparse reconstruction scheme imposes non-negativity without introducing strong nonlinearities, such as those introduced by employing log-transformed fields, and thus reaps the benefits of simplicity and computational speed that are characteristic of linear inverse problems.
In this study, the magnetized liner inertial fusion concept [S. A. Slutz et al., Phys. Plasmas17, 056303 (2010)] utilizes a magnetic field and laser heating to relax the pressure requirements of inertial confinement fusion. The first experiments to test the concept [M. R. Gomez et al., Phys. Rev. Lett. 113, 155003 (2014)] were conducted utilizing the 19 MA, 100 ns Z machine, the 2.5 kJ, 1 TW Z Beamlet laser, and the 10 T Applied B-field on Z system. Despite an estimated implosion velocity of only 70 km/s in these experiments, electron and ion temperatures at stagnation were as high as 3 keV, and thermonuclear deuterium-deuterium neutron yields up to 2 × 1012 have been produced. X-ray emission from the fuel at stagnation had widths ranging from 50 to 110 μm over a roughly 80% of the axial extent of the target (6–8 mm) and lasted approximately 2 ns. X-ray yields from these experiments are consistent with a stagnation density of the hot fuel equal to 0.2–0.4 g/cm3. In these experiments, up to 5 ×1010 secondary deuterium-tritium neutrons were produced. Given that the areal density of the plasma was approximately 1–2 mg/cm2, this indicates the stagnation plasma was significantly magnetized, which is consistent with the anisotropy observed in the deuterium-tritium neutron spectra. Control experiments where the laser and/or magnetic field were not utilized failed to produce stagnation temperatures greater than 1 keV and primary deuterium-deuterium yields greater than 1010. An additional control experiment where the fuel contained a sufficient dopant fraction to substantially increase radiative losses also failed to produce a relevant stagnation temperature. The results of these experiments are consistent with a thermonuclear neutron source.
Direct visualization and tracking of small particles at high spatial and temporal resolution provides a powerful approach to probing complex dynamics and interactions in chemical and biological processes. Analysis of the rotational dynamics of particles adds a new dimension of information that is otherwise impossible to obtain with conventional 3-D particle tracking. In this review, we survey recent advances in single-particle rotational tracking, with highlights on the rotational tracking of optically anisotropic Janus particles. Furthermore, strengths and weaknesses of the various particle tracking methods, and their applications are discussed.
This paper focuses on the combustion chemistry of 2-methylfuran (2-MF), a potential biofuel, and it is built on the previous work of Tran et al. [Combust. Flame 161 (2014) 766]. In their work, they had combined detailed flame chemistry modeling with flame speciation data based on flame-sampling molecular beam mass spectrometry (MBMS) with electron ionization and gas chromatography with MS detection. In this work, we significantly extend those previous studies by in-situ isomer-resolving species identification and quantification. Specifically, we have determined the detailed chemical structure of a premixed laminar 2-MF flame using flame-sampling high-resolution MBMS with synchrotron-generated vacuum-ultraviolet radiation. Mole fraction profiles of 60 intermediate, reactant, and product species were measured in order to assess the pollutant potential of this possible next-generation biofuel. Special emphasis is paid towards the fuel's ability to form aromatic and oxygenated intermediates during incomplete combustion processes, with the latter species representing a variety of different classes including alcohols, ethers, enols, ketones, aldehydes, acids, and ketenes. Whenever possible the experimental data are compared to the results of model calculations using the 2-MF combustion chemistry model of Tran et al., but it should be noted that many newly detected species are not included in the calculations. The experimental data presented in this work provides guidance towards to development of a next-generation 2-MF combustion chemistry model.
The transport properties of ceramic materials strongly depend on oxygen activity, which is tuned by changing the partial oxygen pressure (pO2) prior to and during measurement. Within, we describe an instrument for highly stable measurements of Seebeck coefficient and electrical resistivity at temperatures up to 1300 K with controlled oxygen partial pressure. An all platinum construction is used to avoid potential materials instabilities that can cause measurement drift. Two independent heaters are employed to establish a small temperature gradient for Seebeck measurements, while keeping the average temperature constant and avoiding errors associated with pO2-induced drifts in thermocouple readings. Oxygen equilibrium is monitored using both an O2 sensor and the transient behavior of the resistance as a proxy. A pO2 range of 10-25–100 atm can be established with appropriate gas mixtures. Seebeck measurements were calibrated against a high purity platinum wire, Pt/Pt–Rh thermocouple wire, and a Bi2Te3 Seebeck coefficient Standard Reference Material. To demonstrate the utility of this instrument for oxide materials we present measurements as a function of pO2 on a 1 % Nb-doped SrTiO3 single crystal, and show systematic changes in properties consistent with oxygen vacancy defect chemistry. Thus, an approximately 11% increase in power factor over a pO2 range of 10-19–10-8 atm at 973 K for the donor-doped single crystals is observed.
Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm2 leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. The effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. We discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.
Garcia, Gustavo A.; Tang, Xiaofeng; Gil, Jean F.; Nahon, Laurent; Ward, Michael; Batut, Sebastien; Fittschen, Christa; Taatjes, Craig A.; Osborn, David L.
We present a microwave discharge flow tube coupled with a double imaging electron/ion coincidence device and vacuum ultraviolet (VUV) synchrotron radiation. The system has been applied to the study of the photoelectron spectroscopy of the well-known radicals OH and OD. The coincidence imaging scheme provides a high selectivity and yields the spectra of the pure radicals, removing the ever-present contributions from excess reactants, background, or secondary products, and therefore obviating the need for a prior knowledge of all possible byproducts. The photoelectron spectra encompassing the X3Σ- ground state of the OH+ and OD+ cations have been extracted and the vibrational constants compared satisfactorily to existing literature values. Future advantages of this approach include measurement of high resolution VUV spectroscopy of radicals, their absolute photoionization cross section, and species/isomer identification in chemical reactions as a function of time.
Yilmaz, Nadir; Vigil, Francisco M.; Vigil, Miquela S.; Branam, Robert; Tolendino, Greg; Gill, Walter; Donaldson, Burl
Aluminum is commonly used for structural applications in the aerospace industry because of its high strength in relation to its weight. It is necessary to understand the mechanical response of aluminum structures at elevated temperatures such as those experienced in a fire. Aluminum alloys exhibit many complicated behaviors that require further research and understanding, such as aluminum combustion, oxide skin formation and creep behavior. This paper discusses the effect of grain orientation on aluminum deformation subjected to heating at incipient melt conditions. Experiments were conducted by applying a vertical compressive force to aluminum alloy 7075 block test specimens. Compression testing was done on test specimens with the applied load on the long transverse and short transverse orientations. Results showed that the grain orientation significantly influences aluminum's strength and mode of failure.
In this study, we describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4–5 h for corresponding lipid networks). The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.
We investigated the combustion process in a dual-fuel, reactivity-controlled compression-ignition (RCCI) engine using a combination of optical diagnostics and chemical kinetics modeling to explain the role of equivalence ratio, temperature, and fuel reactivity stratification for heat-release rate control. An optically accessible engine is operated in the RCCI combustion mode using gasoline primary reference fuels (PRF). A well-mixed charge of iso-octane (PRF = 100) is created by injecting fuel into the engine cylinder during the intake stroke using a gasoline-type direct injector. Later in the cycle, n-heptane (PRF = 0) is delivered through a centrally mounted diesel-type common-rail injector. This injection strategy generates stratification in equivalence ratio, fuel blend, and temperature. The first part of this study uses a high-speed camera to image the injection events and record high-temperature combustion chemiluminescence. Moreover, the chemiluminescence imaging showed that, at the operating condition studied in the present work, mixtures in the squish region ignite first, and the reaction zone proceeds inward toward the center of the combustion chamber. The second part of this study investigates the charge preparation of the RCCI strategy using planar laser-induced fluorescence (PLIF) of a fuel tracer under non-reacting conditions to quantify fuel concentration distributions prior to ignition. The fuel-tracer PLIF data show that the combustion event proceeds down gradients in the n-heptane distribution. The third part of the study uses chemical kinetics modeling over a range of mixtures spanning the distributions observed from the fuel-tracer fluorescence imaging to isolate the roles of temperature, equivalence ratio, and PRF number stratification. The simulations predict that PRF number stratification is the dominant factor controlling the ignition location and growth rate of the reaction zone. Equivalence ratio has a smaller, but still significant, influence. Lastly, temperature stratification had a negligible influence due to the NTC behavior of the PRF mixtures.
We investigated error and uncertainty in Raman thermal conductivity measurements via finite element based numerical simulation of two geometries often employed -- Joule-heating of a wire and laser-heating of a suspended wafer. Using this methodology, the accuracy and precision of the Raman-derived thermal conductivity are shown to depend on (1) assumptions within the analytical model used in the deduction of thermal conductivity, (2) uncertainty in the quantification of heat flux and temperature, and (3) the evolution of thermomechanical stress during testing. Apart from the influence of stress, errors of 5% coupled with uncertainties of ±15% are achievable for most materials under conditions typical of Raman thermometry experiments. Error can increase to >20%, however, for materials having highly temperature dependent thermal conductivities or, in some materials, when thermomechanical stress develops concurrent with the heating. A dimensionless parameter -- termed the Raman stress factor -- is derived to identify when stress effects will induce large levels of error. Together, the results compare the utility of Raman based conductivity measurements relative to more established techniques while at the same time identifying situations where its use is most efficacious.
Mixtures of light elements with heavy elements are important in inertial confinement fusion. We explore the physics of molecular scale mixing through a validation study of equation of state (EOS) properties. Density functional theory molecular dynamics (DFT-MD) at elevated temperature and pressure is used to obtain the thermodynamic state properties of pure xenon, ethane, and various compressed mixture compositions along their principal Hugoniots. To validate these simulations, we have performed shock compression experiments using the Sandia Z-Machine. A bond tracking analysis correlates the sharp rise in the Hugoniot curve with the completion of dissociation in ethane. The DFT-based simulation results compare well with the experimental data along the principal Hugoniots and are used to provide insight into the dissociation and temperature along the Hugoniots as a function of mixture composition. Interestingly, we find that the compression ratio for complete dissociation is similar for several compositions suggesting a limiting compression for C-C bonded systems.
We report here the characteristics of photoelectrochemical (PEC) etching of epitaxial InGaN semiconductor thin films using a narrowband laser with a linewidth less than ∼1 nm. In the initial stages of PEC etching, when the thin film is flat, characteristic voltammogram shapes are observed. At low photo-excitation rates, voltammograms are S-shaped, indicating the onset of a voltage-independent rate-limiting process associated with electron-hole-pair creation and/or annihilation. At high photo-excitation rates, voltammograms are superlinear in shape, indicating, for the voltage ranges studied here, a voltage-dependent rate-limiting process associated with surface electrochemical oxidation. As PEC etching proceeds, the thin film becomes rough at the nanoscale, and ultimately the self-limiting etch kinetics lead to an ensemble of nanoparticles. This change in InGaN film volume and morphology leads to a characteristic dependence of PEC etch rate on time: an incubation time, followed by a rise, then a peak, then a slow decay.
Yersinia enterocolitica is typically considered an extracellular pathogen; however, during the course of an infection, a significant number of bacteria are stably maintained within host cell vacuoles. Little is known about this population and the role it plays during an infection. To address this question and to elucidate the spatially and temporally dynamic gene expression patterns of Y. enterocoliticabiovar 1B through the course of an in vitro infection, transcriptome sequencing and differential gene expression analysis of bacteria infecting murine macrophage cells were performed under four distinct conditions. Bacteria were first grown in a nutrient-rich medium at 26°C to establish a baseline of gene expression that is unrelated to infection. The transcriptomes of these bacteria were then compared to bacteria grown in a conditioned cell culture medium at 37°C to identify genes that were differentially expressed in response to the increased temperature and medium but not in response to host cells. Infections were then performed, and the transcriptomes of bacteria found on the extracellular surface and intracellular compartments were analyzed individually. The upregulated genes revealed potential roles for a variety of systems in promoting intracellular virulence, including the Ysa type III secretion system, the Yts2 type II secretion system, and the Tad pilus. It was further determined that mutants of each of these systems had decreased virulence while infecting macrophages. Overall, these results reveal the complete set of genes expressed by Y. enterocolitica in response to infection and provide the groundwork for future virulence studies.
Until recently, modern theory has lacked a fundamentally based model to predict the operating pressures where classical sprays transition to dense-fluid mixing with diminished surface tension. In this paper, such a model is presented to quantify this transition for liquid-oxygen–hydrogen and n-decane–gaseous-oxygen injection processes. The analysis reveals that respective molecular interfaces break down not necessarily because of vanishing surface tension forces but instead because of the combination of broadened interfaces and a reduction in mean free molecular path. When this occurs, the interfacial structure itself enters the continuum regime, where transport processes rather than intermolecular forces dominate. Using this model, regime diagrams for the respective systems are constructed that show the range of operating pressures and temperatures where this transition occurs. The analysis also reveals the conditions where classical spray dynamics persists even at high supercritical pressures. As a result, it demonstrates that, depending on the composition and temperature of the injected fluids, the injection process can exhibit either classical spray atomization, dense-fluid diffusion-dominated mixing, or supercritical mixing phenomena at chamber pressures encountered in state-of-the-art liquid rocket engines.
Graphene films grown by vapour deposition tend to be polycrystalline due to the nucleation and growth of islands with different in-plane orientations. Here, using low-energy electron microscopy, we find that micron-sized graphene islands on Ir(111) rotate to a preferred orientation during thermal annealing. We observe three alignment mechanisms: the simultaneous growth of aligned domains and dissolution of rotated domains, that is, â €- ripeningâ €™; domain boundary motion within islands; and continuous lattice rotation of entire domains. By measuring the relative growth velocity of domains during ripening, we estimate that the driving force for alignment is on the order of 0.1â €‰meV per C atom and increases with rotation angle. A simple model of the orientation-dependent energy associated with the moiré corrugation of the graphene sheet due to local variations in the graphene-substrate interaction reproduces the results. This work suggests new strategies for improving the van der Waals epitaxy of 2D materials.
A design of experiments approach was used to describe process parameter—spray pattern relationships in the Twin Wire Arc process using zinc feed stock in a TAFA 8835 (Praxair, Concord, NH, USA) spray torch. Specifically, the effects of arc current, primary atomizing gas pressure, and secondary atomizing gas pressure on spray pattern size, spray pattern flatness, spray pattern eccentricity, and coating deposition rate were investigated. Process relationships were investigated with the intent of maximizing or minimizing each coating property. It was determined that spray pattern area was most affected by primary gas pressure and secondary gas pressure. Pattern eccentricity was most affected by secondary gas pressure. Pattern flatness was most affected by primary gas pressure. Lastly, coating deposition rate was most affected by arc current.
High-energy short-pulse lasers are pushing the limits of plasma-based particle acceleration, x-ray generation, and high-harmonic generation by creating strong electromagnetic fields at the laser focus where electrons are being accelerated to relativistic velocities. Understanding the relativistic electron dynamics is key for an accurate interpretation of measurements. We present a unified and self-consistent modeling approach in quantitative agreement with measurements and differing trends across multiple target types acquired from two separate laser systems, which differ only in their nanosecond to picosecond-scale rising edge. Insights from high-fidelity modeling of laser-plasma interaction demonstrate that the ps-scale, orders of magnitude weaker rising edge of the main pulse measurably alters target evolution and relativistic electron generation compared to idealized pulse shapes. This can lead for instance to the experimentally observed difference between 45 MeV and 75 MeV maximum energy protons for two nominally identical laser shots, due to ps-scale prepulse variations. Our results indicate that the realistic inclusion of temporal laser pulse profiles in modeling efforts is required if predictive capability and extrapolation are sought for future target and laser designs or for other relativistic laser ion acceleration schemes.
Time-resolved measurements of carrier recombination are reported for a midwave infrared InAs/InAs0.66Sb0.34 type-II superlattice (T2SL) as a function of pump intensity and sample temperature. By including the T2SL doping level in the analysis, the Shockley-Read-Hall (SRH), radiative, and Auger recombination components of the carrier lifetime are uniquely distinguished at each temperature. SRH is the limiting recombination mechanism for excess carrier densities less than the doping level (the low-injection regime) and temperatures less than 175 K. A SRH defect energy of 95 meV, either below the T2SL conduction-band edge or above the T2SL valence-band edge, is identified. Auger recombination limits the carrier lifetimes for excess carrier densities greater than the doping level (the high-injection regime) for all temperatures tested. Additionally, at temperatures greater than 225 K, Auger recombination also limits the low-injection carrier lifetime due to the onset of the intrinsic temperature range and large intrinsic carrier densities. Radiative recombination is found to not have a significant contribution to the total lifetime for all temperatures and injection regimes, with the data implying a photon recycling factor of 15. Using the measured lifetime data, diffusion currents are calculated and compared to calculated Hg1-xCdxTe dark current, indicating that the T2SL can have a lower dark current with mitigation of the SRH defect states. These results illustrate the potential for InAs/InAs1-xSbx T2SLs as absorbers in infrared photodetectors.
Vascomax® maraging C250 and C300 alloys were dynamically characterized in tension with Kolsky tension bar techniques. Compared with conventional Kolsky tension bar experiments, a pair of lock nuts was used to minimize the pseudo stress peak and a laser system was applied to directly measure the specimen displacement. Dynamic engineering stress–strain curves of the C250 and C300 alloys were obtained in tension at 1000 and 3000 s–1. The dynamic yield strengths for both alloys were similar, but significantly higher than those obtained from quasi-static indentation tests. Both alloys exhibited insignificant strain-rate effect on dynamic yield strength. The C300 alloy showed approximately 10 % higher in yield strength than the C250 alloy at the same strain rates. Necking was observed in both alloys right after yield. The Bridgman correction was applied to calculate the true stress and strain at failure for both alloys. The true failure stress showed a modest strain rate effect for both alloys but no significant difference between the two alloys at the same strain rate. As a result, the C250 alloy was more ductile than the C300 alloy under dynamic loading.
The appropriateness of treating crossing seams of electronic states of different spins as nonadiabatic transition states in statistical calculations of spin-forbidden reaction rates is considered. We show that the spin-forbidden reaction coordinate, the nuclear coordinate perpendicular to the crossing seam, is coupled to the remaining nuclear degrees of freedom. We found that this coupling gives rise to multidimensional effects that are not typically included in statistical treatments of spin-forbidden kinetics. Three qualitative categories of multidimensional effects may be identified: static multidimensional effects due to the geometry-dependence of the local shape of the crossing seam and of the spin–orbit coupling, dynamical multidimensional effects due to energy exchange with the reaction coordinate during the seam crossing, and nonlocal(history-dependent) multidimensional effects due to interference of the electronic variables at second, third, and later seam crossings. Nonlocal multidimensional effects are intimately related to electronic decoherence, where electronic dephasing acts to erase the history of the system. A semiclassical model based on short-time full-dimensional trajectories that includes all three multidimensional effects as well as a model for electronic decoherence is presented. The results of this multidimensional nonadiabatic statistical theory (MNST) for the 3O + CO → CO2 reaction are compared with the results of statistical theories employing one-dimensional (Landau–Zener and weak coupling) models for the transition probability and with those calculated previously using multistate trajectories. The MNST method is shown to accurately reproduce the multistate decay-of-mixing trajectory results, so long as consistent thresholds are used. Furthermore, the MNST approach has several advantages over multistate trajectory approaches and is more suitable in chemical kinetics calculations at low temperatures and for complex systems. The error in statistical calculations that neglect multidimensional effects is shown to be as large as a factor of 2 for this system, with static multidimensional effects identified as the largest source of error.
Based on the ensemble-averaged velocity results, flow asymmetry characterized by the swirl center offset and the associated tilting of the vortex axis is quantified. The observed vertical tilting of swirl center axis is similar for tested swirl ratios (2.2 and 3.5), indicating that the details of the intake flows are not of primary importance to the late-compression mean flow asymmetry. Instead, the geometry of the piston pip likely impacts the flow asymmetry. The PIV results also confirm the numerically simulated flow asymmetry in the early and late compression stroke: at BDC, the swirl center is located closer to the exhaust valves for swirl-planes farther away from the fire deck; near TDC, the swirl center is located closer to the intake valves for swirl-planes farther away from the fire deck. It is evident from experimentally determined velocity fields that the transition between these two asymmetries has a different path for various swirl ratios, suggesting the influence of intake port flows. Flow field asymmetry can lead to an asymmetric mixture preparation in Diesel engines. To understand the evolution of this asymmetry, it is necessary to characterize the in-cylinder flow over the full compression stroke. Moreover, since bowl-in-piston cylinder geometries can substantially impact the in-cylinder flow, characterization of these flows requires the use of geometrically correct pistons. In this work, the flow has been visualized via a transparent piston top with a realistic bowl geometry, which causes severe experimental difficulties due to the spatial and temporal variation of the optical distortion. An advanced optical distortion correction method is described to allow reliable particle image velocimetry (PIV) measurements through the full compression stroke.
A detailed understanding of the various factors affecting the trends in gross-indicated thermal efficiency with changes in key operating parameters has been carried out, applied to a one-liter displacement single-cylinder boosted Low-Temperature Gasoline Combustion (LTGC) engine. This work systematically investigates how the supplied fuel energy splits into the following four energy pathways: gross-indicated thermal efficiency, combustion inefficiency, heat transfer and exhaust losses, and how this split changes with operating conditions. Additional analysis is performed to determine the influence of variations in the ratio of specific heat capacities (γ) and the effective expansion ratio, related to the combustion-phasing retard (CA50), on the energy split. Heat transfer and exhaust losses are computed using multiple standard cycle analysis techniques. The various methods are evaluated in order to validate the trends. This work focuses on explaining the trends in thermal efficiency and the various energy-loss terms for independent sweeps of fueling rate, intake temperature and engine speed. Trends in thermal efficiency can be well-explained by considering variations in combustion efficiency, CA50 retard, γ and heat transfer. By identifying the energy losses, these results provide a new understanding that can help to optimize the thermal efficiency across the load/speed range in LTGC engines. Of particular importance, a picture is provided of how the heat transfer varies with changes in engine operating conditions. For example, results indicate that CA50 and the magnitude of the acoustic oscillations (i.e. knock) are fundamental parameters affecting the heat transfer.
Low-temperature gasoline combustion (LTGC), based on the compression ignition of a premixed or partially premixed dilute charge, can provide thermal efficiencies (TE) and maximum loads comparable to those of turbo-charged diesel engines, and ultra-low NOx and particulate emissions. Intake boosting is key to achieving high loads with dilute combustion, and it also enhances the fuel's autoignition reactivity, reducing the required intake heating or hot residuals. These effects have the advantages of increasing TE and charge density, allowing greater timing retard with good stability, and making the fuel Φ- sensitive so that partial fuel stratification (PFS) can be applied for higher loads and further TE improvements. However, at high boost the autoignition reactivity enhancement can become excessive, and substantial amounts of EGR are required to prevent overly advanced combustion. Accordingly, an experimental investigation has been conducted to determine how the tradeoff between the effects of intake boost varies with fuel-type and its impact on load range and TE. Five fuels are investigated: a conventional AKI=87 petroleum-based gasoline (E0), and blends of 10 and 20% ethanol with this gasoline to reduce its reactivity enhancement with boost (E10 and E20). Furthermore, a second zero-ethanol gasoline with AKI=93 (matching that of E20) was also investigated (CF-E0), and some neat ethanol data are also reported.
In this work computational and experimental approaches are combined to characterize in-cylinder flow structures and local flow field properties during operation of the Sandia 1.9L light-duty optical Diesel engine. A full computational model of the single-cylinder research engine was used that considers the complete intake and exhaust runners and plenums, as well as the adjustable throttling devices used in the experiments to obtain different swirl ratios. The in-cylinder flow predictions were validated against an extensive set of planar PIV measurements at different vertical locations in the combustion chamber for different swirl ratio configurations. Principal Component Analysis was used to characterize precession, tilting and eccentricity, and regional averages of the in-cylinder turbulence properties in the squish region and the piston bowl. Complete sweeps of the port throttle configurations were run to study their effects on the flow structure, together with their correlation with the swirl ratio. Significant deviations between the flows in the piston bowl and squish regions were observed. Piston bowl design, more than the swirl ratio, was identified to foster flow homogeneity between these two regions. Also, analysis of the port-induced flow showed that port geometry, more than different intake port mass flow ratios, can improve turbulence levels in-cylinder.
