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At least 739 records · Page 41

Measuring and Modeling Shared Visual Attention

Multi-person teams are sometimes responsible for critical tasks, such as flying an airliner. Here we present a method using gaze tracking data to assess shared visual attention, a term we use to describe the situation where team members are attending to a common set of elements in the environment. Gaze data are quantized with respect to a set of N areas of interest (AOIs); these are then used to construct a time series of N dimensional vectors, with each vector component representing one of the AOIs, all set to 0 except for the component corresponding to the currently fixated AOI, which is set to 1. The resulting sequence of vectors can be averaged in time, with the result that each vector component represents the proportion of time that the corresponding AOI was fixated within the given time interval.We present two methods for comparing sequences of this sort, one based on computing the time varying correlation of the averaged vectors, and another based on a chi-square test testing the hypothesis that the observed gaze proportions are drawn from identical probability distributions.We have evaluated the method using synthetic data sets, in which the behavior was modeled as a series of activities, each of which was modeled as a first-order Markov process. By tabulating distributions for pairs of identical and disparate activities, we are able to perform a receiver operating characteristic (ROC) analysis, allowing us to choose appropriate criteria and estimate error rates. Using these criteria, we have applied the methods to data from airline crews, collected in a high-fidelity flight simulator (Gontar Hoermann, 2014). We conclude by considering the problem of automatic (blind) discovery of activities, using methods developed for text analysis.

Mulligan, Jeffrey B.↗

Measuring and Modeling Shared Visual Attention

Multi-person teams are sometimes responsible for critical tasks, such as flying an airliner. Here we present a method using gaze tracking data to assess shared visual attention, a term we use to describe the situation where team members are attending to a common set of elements in the environment. Gaze data are quantized with respect to a set of N areas of interest (AOIs); these are then used to construct a time series of N dimensional vectors, with each vector component representing one of the AOIs, all set to 0 except for the component corresponding to the currently fixated AOI, which is set to 1. The resulting sequence of vectors can be averaged in time, with the result that each vector component represents the proportion of time that the corresponding AOI was fixated within the given time interval. We present two methods for comparing sequences of this sort, one based on computing the time-varying correlation of the averaged vectors, and another based on a chi-square test testing the hypothesis that the observed gaze proportions are drawn from identical probability distributions.We have evaluated the method using synthetic data sets, in which the behavior was modeled as a series of activities, each of which was modeled as a first-order Markov process. By tabulating distributions for pairs of identical and disparate activities, we are able to perform a receiver operating characteristic (ROC) analysis, allowing us to choose appropriate criteria and estimate error rates.We have applied the methods to data from airline crews, collected in a high-fidelity flight simulator (Haslbeck, Gontar Schubert, 2014). We conclude by considering the problem of automatic (blind) discovery of activities, using methods developed for text analysis.

attention↗

Measuring and Modeling Shared Visual Attention

Multi-person teams are sometimes responsible for critical tasks, such as flying an airliner. Here we present a method using gaze tracking data to assess shared visual attention, a term we use to describe the situation where team members are attending to a common set of elements in the environment. Gaze data are quantized with respect to a set of N areas of interest (AOIs); these are then used to construct a time series of N dimensional vectors, with each vector component representing one of the AOIs, all set to 0 except for the component corresponding to the currently fixated AOI, which is set to 1. The resulting sequence of vectors can be averaged in time, with the result that each vector component represents the proportion of time that the corresponding AOI was fixated within the given time interval. We present two methods for comparing sequences of this sort, one based on computing the time-varying correlation of the averaged vectors, and another based on a chi-square test testing the hypothesis that the observed gaze proportions are drawn from identical probability distributions. We have evaluated the method using synthetic data sets, in which the behavior was modeled as a series of "activities," each of which was modeled as a first-order Markov process. By tabulating distributions for pairs of identical and disparate activities, we are able to perform a receiver operating characteristic (ROC) analysis, allowing us to choose appropriate criteria and estimate error rates. We have applied the methods to data from airline crews, collected in a high-fidelity flight simulator (Haslbeck, Gontar & Schubert, 2014). We conclude by considering the problem of automatic (blind) discovery of activities, using methods developed for text analysis.

attention↗

Screening and Validation of Molecular Targeted Radiosensitizers

The development of molecular targeted drugs with radiation and chemotherapy is critically important for improving the outcomes of patients with hard-to-treat, potentially curable cancers. However, too many preclinical studies have not translated into successful radiation oncology trials. Major contributing factors to this insufficiency include poor reproducibility of preclinical data, inadequate preclinical modeling of intertumoral genomic heterogeneity that influences treatment sensitivity in the clinic, and a reliance on tumor growth delay instead of local control (TCD50) endpoints. There exists an urgent need to overcome these barriers to facilitate successful clinical translation of targeted radiosensitizers. To this end, we have used 3-dimensional (3D) cell culture assays to better model tumor behavior in vivo. Examples of successful prediction of in vivo effects with these 3D assays include radiosensitization of head and neck cancers by inhibiting epidermal growth factor receptor or focal adhesion kinase signaling, and radioresistance associated with oncogenic mutation of KRAS. To address the issue of tumor heterogeneity, we leveraged institutional resources that allow high-throughput 3D screening of radiation combinations with small-molecule inhibitors across genomically characterized cell lines from lung, head and neck, and pancreatic cancers. This high-throughput screen is expected to uncover genomic biomarkers that will inform the successful clinical translation of targeted agents from the National Cancer Institute Cancer Therapy Evaluation Program portfolio and other sources. Screening “hits” need to be subjected to refinement studies that include clonogenic assays, addition of disease-specific chemotherapeutics, target/biomarker validation, and integration of patient-derived tumor models. The chemoradiosensitizing activities of the most promising drugs should be confirmed in TCD50 assays in xenograft models with or without relevant biomarker and using clinically relevant radiation fractionation. We predict that appropriately validated and biomarker-directed targeted therapies will have a higher likelihood than past efforts of being successfully incorporated into the standard management of hard-to-treat tumors.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

A Mathematical Model of a Simple Amplifier Using a Ferroelectric Transistor

This paper presents a mathematical model characterizing the behavior of a simple amplifier using a FeFET. The model is based on empirical data and incorporates several variables that affect the output, including frequency, load resistance, and gate-to-source voltage. Since the amplifier is the basis of many circuit configurations, a mathematical model that describes the behavior of a FeFET-based amplifier will help in the integration of FeFETs into many other circuits.

Sayyah, Rana↗

Universal Behavior of a Cyclic Oxidation Model

A mathematical model has been generated to represent the iterative, discrete growth and spallation processes associated with cyclic oxidation. Parabolic growth kinetics (k(sub p)) over and a constant spall area (F(sub A)) were assumed, with spalling occurring interfacially at the thickest regions of the scale. Although most models require numerical techniques, the regularity and simplicity of this progression permitted an approximation by algebraic expressions. Normalization could now be performed to reflect all parametric effects, and a universal cyclic oxidation response was generated: W(sub u) = 1/2 {3J(sub u)(sup 1/2)+ J(sub u)(sup 3/2)} where W, is weight change normalized by the maximum and J(sub u) is the cycle number normalized by the number to reach maximum. Similarly, the total amount of metal consumed was represented by a single normalized curve. The factor [(S(sub c)-l)(raised dot)sqrt(F(sub A)k(sub p)DELTAt)] was identified as a general figure of merit, where S(sub c) is the mass ratio of oxide to oxygen and DELTAt is the cycle duration. A cyclic oxidation failure map was constructed, in normalized k(sub p)-F(sub A) space, as defined by the locus of points corresponding to a critical amount of metal consumption in a given time. All three constructions describe behavior for every value of growth rate, spall fraction, and cycle duration by means of single curves, but with two branches corresponding to the times before and after steady state is achieved.

Smialek, James L.↗

Turbulence Modeling for the Simulation of Transition in Wall Shear Flows

Our research involves study of the behavior of k-epsilon turbulence models for simulation of bypass-level transition over flat surfaces and turbine blades. One facet of the research has been to assess the performance of a multitude of k-epsilon models in what we call "natural transition", i.e. no modifications to the k-e models. The study has been to ascertain what features in the dynamics of the model affect the start and end of the transition. Some of the findings are in keeping with those reported by others (e.g. ERCOFTAC). A second facet of the research has been to develop and benchmark a new multi-time scale k-epsilon model (MTS) for use in simulating bypass-level transition. This model has certain features of the published MTS models by Hanjalic, Launder, and Schiestel, and by Kim and his coworkers. The major new feature of our MTS model is that it can be used to compute wall shear flows as a low-turbulence Reynolds number type of model, i.e. there is no required partition with patching a one-equation k model in the near-wall region to a two-equation k-epsilon model in the outer part of the flow. Our MTS model has been studied extensively to understand its dynamics in predicting the onset of transition and the end-stage of the transition. Results to date indicate that it far superior to the standard unmodified k-epsilon models. The effects of protracted pressure gradients on the model behavior are currently being investigated.

Crawford, Michael E.↗

Optimized bioregenerative space diet selection with crew choice

Previous studies on optimization of crew diets have not accounted for choice. A diet selection model with crew choice was developed. Scenario analyses were conducted to assess the feasibility and cost of certain crew preferences, such as preferences for numerous-desserts, high-salt, and high-acceptability foods. For comparison purposes, a no-choice and a random-choice scenario were considered. The model was found to be feasible in terms of food variety and overall costs. The numerous-desserts, high-acceptability, and random-choice scenarios all resulted in feasible solutions costing between 13.2 and 17.3 kg ESM/person-day. Only the high-sodium scenario yielded an infeasible solution. This occurred when the foods highest in salt content were selected for the crew-choice portion of the diet. This infeasibility can be avoided by limiting the total sodium content in the crew-choice portion of the diet. Cost savings were found by reducing food variety in scenarios where the preference bias strongly affected nutritional content.

Non-NASA Center↗

Simulating Human Cognition in the Domain of Air Traffic Control

Experiments intended to assess performance in human-machine interactions are often prohibitively expensive, unethical or otherwise impractical to run. Approximations of experimental results can be obtained, in principle, by simulating the behavior of subjects using computer models of human mental behavior. Computer simulation technology has been developed for this purpose. Our goal is to produce a cognitive model suitable to guide the simulation machinery and enable it to closely approximate a human subject's performance in experimental conditions. The described model is designed to simulate a variety of cognitive behaviors involved in routine air traffic control. As the model is elaborated, our ability to predict the effects of novel circumstances on controller error rates and other performance characteristics should increase. This will enable the system to project the impact of proposed changes to air traffic control procedures and equipment on controller performance.

Freed, Michael↗

Plasticity and Damage Modeling of Stress Asymmetry and Dynamic Behavior of AFS Additive Manufactured Aluminum Alloy 2219

The Solid State Additive Manufacturing (AM) process referred as MELD that fabricated the samples in this study, provides a new path for repairing, coating, joining and additive manufacturing metals and metal matrix composites. This research will be the first application of a physics-based microstructure dependent internal state variable (ISV) plasticity and damage material model to capture the mechanical response of an AM Aluminum Alloy (AA) 2219 via the MELD process. In this research, a microstructure-based internal state variable (ISV) plasticity-damage model was used to capture the mechanical behavior of AFS 2219 aluminum alloy. Aeroprobe Corporation, creator and patent holder for the MELD process, fabricated the material by pushing a solid filler rod of AA2219-T861 material through a hollow rotating tool onto an AA2219 T851 plate substrate. As feedstock, solid or powder precursor metals are pushed through a nonconsumable rotating cylindrical tool. Herein, added layers are deposited and metallurgically bonded to substrate material or previously deposited layers by the heat generated from the rotating tool through plastic deformation of the filler material. Once a layer has been added, the tool height increases, and starts the deposition of the next layer. This process results in beneficial properties such as grain refinement, homogenization and reduced porosity (fully dense). This process will experience temperatures similar to those in the weld nugget zone (WNZ) in friction stir welding (FSW), ranging from 0.6-0.9 Tm, with Tm being the melting point of the material. MELD is highly scalable with AA deposition rates reaching over 1000 cm3/hr, which allows for MELD being used for repairs, coatings, and building components. A motivating factor driving the research for physics-based history dependent material modeling of MELD components is the ability to accurately capture the stress-state and strain rate dependence in the material caused by variations in material microstructure from the MELD processing of new or repaired components. The ISV model incorporates microstructural content and is consistent with continuum level kinematics, kinetics, and thermodynamics. These features allow the ISV model to capture large deformations at the structural scale using the kinematic and isotropic hardening, while microscale damage is obtained from the microstructural features. The benefits of the ISV model arise from the inclusion of structure-property relationships identified from microstructural characterization and experimentation. The Bauschinger effect (BE) is an important concept, vital in the accurate prediction of cyclic stress-strain response of ductile materials such as metals. The ISV model has been successfully used to capture the behavior and damage, and the BE of different aluminum alloys and steels. The ISV model uses kinematic and isotropic hardening to help capture deformations of the material at the macro scale. To understand this hardening relationship, calculating the kinematic and isotropic hardening relationship in the material is warranted for a high-fidelity model. Electron Backscattered Diffraction (EBSD) was used to characterize the as-fabricated microstructure, where a fully-dense equiaxed grain morphology with average grain size of 2.5 μm was observed. Microhardness mapping of the as-built structures, monotonic tension and compression experiments at both quasi-static (0.001/s) strain rates, tension-followed-by-compression and compression-followed-by-tension experiments were performed to obtain the set of plasticity and damage constants necessary to capture strain rate and stress state behavior of this additive material. To calibrate the plasticity-damage model, a single set of constants were determined to capture the different stress states the MELD AA2219. One set of the constants was determined from experimental true stress-strain curves for the tension and compression data. Additionally, microstructural information and data from the open literature were used as the other model constants. This research is a first of its kind for AFS AA2219, includes correlating the ISV model to the monotonic experimental results that capture the isotropic and kinematic plasticity mechanical response.

Rivera, O. G.↗

Phase transitions in Schloegl's second model for autocatalysis on a Bethe lattice

Schloegl's second model (also known as the quadratic contact process) on a lattice involves spontaneous particle annihilation at rate p and autocatalytic particle creation at empty sites with n ≥ 2 occupied neighbors. The particle creation rate for exactly n occupied neighbors is selected here as n(n - 1)/[z(z - 1)] for lattice coordination number z. We analyze this model on a Bethe lattice. Precise behavior for stochastic models on regular periodic infinite lattices is usually surmised from kinetic Monte Carlo simulation on a finite lattice with periodic boundary conditions. However, the persistence of boundary effects for a Bethe lattice complicates this process, e.g., by inducing spatially heterogenous states. This motivates the exploration of various boundary conditions and unconventional simulation ensembles on the Bethe lattice to predict behavior for infinite size. Here, we focus on z = 3, and predict a discontinuous transition to the vacuum state on the infinite lattice when p exceeds a threshold value of around 0.053.

97 MATHEMATICS AND COMPUTING↗

Power Operations of the Mars Exploration Rovers

The rovers of the National Aeronautics and Space Administration’s (NASA) Mars Exploration Rovers (MER) project, Spirit (MER-A) and Opportunity (MER-B), safely landed on the surface of Mars three weeks apart during January 2004. Spirit and Opportunity were built and operated by the Jet Propulsion Laboratory (JPL), which is managed by the California Institute of Technology (Caltech) for NASA. Spirit landed at Gusev Crater, 14.8 degrees south of the equator, and operated continuously on the surface of Mars from January 4, 2004 until last contact from Spirit on March 22, 2010. Opportunity landed at Meridiani Planum, a location 2.5 degrees south of the Martian equator. Opportunity operated continuously on the Martian surface from January 25, 2004 until the last received transmission from Opportunity on June 10, 2018. The goal of the MER project was to determine if Mars ever had a habitable environment, in particular, if it ever had water. During their missions, both Spirit and Opportunity found evidence that liquid water once flowed on the surface of Mars. Both Spirit and Opportunity used a 1.33 m2 triple-junction solar array as their power sources. Based on observations of the original Mars rover, the Sojourner rover of the Mars Pathfinder mission that landed on Mars on July 4, 1997, the expectation was that the Martian dust would rapidly accumulate on the solar arrays of Spirit and Opportunity, and that the rovers would not have enough energy to continue operations after 90 Martian days (sols). Instead, due in part to lower dust accumulation rates than expected and numerous dust cleaning events, the Spirit and Opportunity rovers continued to operate on the Martian surface for over 2000 sols (MER-A) and 5000 sols (MER-B), respectively. During this time, the rovers experienced multiple Martian winters and several dust storms. Because the sources of solar array energy loss were known, the solar array energy output offered a method to scientifically estimate the loading and aeolian removal of dust from the solar arrays each sol. The MER Power operations team called this value that they calculated the solar array Dust Factor (DF). Dust Factor was defined as the fraction of sunlight that penetrates the accumulated dust on the surface of the solar array. A Dust Factor of 1.0 would indicate that the solar array was perfectly clean. A Dust Factor of 0.6 would indicate that only 60% of the available sunlight was able to penetrate the accumulated dust on the solar arrays. The MER Power subsystem operations team used the Multi-Mission Power Analysis Tool (MMPAT) to perform these Dust Factor calculations. The MMPAT software tool modeled the behavior of the solar arrays and the batteries as they interacted with the spacecraft power loads over the mission timeline. MMPAT also had knowledge (through telemetry and user inputs) of telemetered Power subsystem voltages and currents, atmospheric opacity (Tau), rover surface location, rover attitude, the planetary tilt and distance of Mars from the sun based on day of year, the instantaneous elevation of the sun based on time of day, temperatures (internal and external), terrain masking, and shadowing (due to the camera mast and antennas). Once all of the known sources of array energy loss are accounted, the remaining difference between the expected array energy and the actual array energy determines the solar array Dust Factor. The assumptions made while determining the Dust Factor are 1) that the single measured atmospheric opacity value (Tau) is constant over the course of the entire sol, 2) there is no measurable solar cell degradation, 3) there are no shorted strings and therefore, 4) all unexpected solar array energy losses are due to accumulated dust on the solar array. Although it cannot provide an absolute measure of dust loading, the determination of solar array Dust Factor provides a useful way of tracking dust accumulation and aeolian dust removal trends on Martian spacecraft. Any spacecraft on the Martian surface is vulnerable to dust, especially solar-powered spacecraft. The Spirit and Opportunity rovers were operational on the Martian surface for much longer than expected due in part to aeolian removal of dust from their solar arrays. The first few dust removal events were a pleasant surprise to the MER operations teams; however, over time a pattern began to arise. In over three Mars Years on the surface, the Power operations team tracked the solar array Dust Factor at Gusev Crater (location of MER-A) and observed that there were several significant dust removal and deposition events in Mars Year (MY) 27, even in the absence of a large dust storm. In MY 28 at Gusev Crater, the large atmospheric opacity (Tau) increase lagged significant dust removal events. Overall at Gusev Crater, there was a pattern of steady dust accumulation on the solar arrays, with a small number of significant dust cleaning events. At Meridiani Planum, where Opportunity rover operated for over seven Mars Years (late MY 26 to mid MY 34), a clear and consistent pattern of dust movement emerged. Meridiani Planum had a predictable, seasonally dependent pattern of gradual and continuous dust accumulation and removal. In summary, this paper explains the reasons for the development of the solar array Dust Factor and how it was used in mission operations. In particular, this paper describes the MMPAT software package, how it models array energy, including the important assumptions, model inputs and sources of error. And finally, this paper will show how the calculated solar array Dust Factor was used at Gusev Crater and Meridiani Planum to predict dust accumulation rates and weather patterns, and the importance of this generated data set for current and future solar- powered missions to Mars, such as the InSight lander and the planned Mars Sample Return rover.

Chin, Keith B.↗

What Makes You Hold on to That Old Car? Joint Insights From Machine Learning and Multinomial Logit on Vehicle-Level Transaction Decisions

What makes you hold on to that old car? While the vast majority of household vehicles are still powered by conventional internal combustion engines, the progress of adopting emerging vehicle technologies will critically depend on how soon the existing vehicles are transacted out of the household fleet. Leveraging a nationally representative longitudinal data set, the Panel Study of Income Dynamics, this study examines how household decisions to dispose of or replace a given vehicle are: 1) influenced by the vehicle’s attributes, 2) mediated by households’ concurrent socio-demographic and economic attributes, and 3) triggered by key life cycle events. Coupled with a newly developed machine learning interpretation tool, TreeExplainer, we demonstrate an innovative use of machine learning models to augment traditional logit modeling to both generate behavioral insights and improve model performance. We find the two gradient-boosting-based methods, CatBoost and LightGBM, are the best performing machine learning models for this problem. The multinomial logistic model can achieve similar performance levels after its model specification is informed by TreeExplainer. Both machine learning and multinomial logit models suggest that while older vehicles are more likely to be disposed of or replaced than newer ones, such probability decreases as the vehicles serve the family longer. Pickup trucks and sport utility vehicles are less likely to be disposed of or replaced than cars, and leased vehicles are more likely to be transacted than owned vehicles. We find that married families, families with higher education levels, homeowners, and older families tend to keep their vehicles longer. Life events such as childbirth, residential relocation, and change of household composition and income are found to increase vehicle disposal and/or replacement. We provide additional insights on the timing of vehicle replacement or disposal, in particular, the presence of children and childbirth events are more strongly associated with vehicle replacement among younger parents.

33 ADVANCED PROPULSION SYSTEMS↗

Wildfire towers drive firebrand lofting: insights from coupled fire-atmosphere model simulations

Wildfire behavior is shaped by complex fire dynamics, with firebrands playing a critical role in spot fire ignition and fire spread. While previous studies have explored firebrand generation and transport, the specific role of towers and troughs from wildland fires in the lofting of firebrands remains unquantified. This study addresses that gap by using physics-based coupled fire-atmosphere model simulations to examine how wildfire towers (updrafts) and troughs (downdrafts) influence firebrand lofting. Our results show that the majority of firebrands (78.85%) are lofted from towers, where strong updrafts drive long-range transport. In contrast, only 21.15% of firebrands are lofted within troughs, where downdrafts cause most firebrands to fall near the fireline. We also find that firebrand size significantly influences lofting behavior, with smaller particles (1 mm radius) exhibiting the strongest correlation with updraft intensity. These findings highlight the dominant role of wildfire towers in promoting long-distance firebrand dispersal—an essential factor in rapid wildfire growth and wildland-urban interface (WUI) fire risks. By quantifying the relationship between firebrand lofting and fire-induced atmospheric features, this study provides critical insights to improve spot fire modeling, support mitigation planning, and enhance firefighter and WUI community safety in spot fire-prone regions.

54 ENVIRONMENTAL SCIENCES↗

Tip‐Enhanced Imaging and Control of Infrared Strong Light‐Matter Interaction

Optical antenna resonators enable control of light‐matter interactions on the nano‐scale via electron–photon hybrid states in strong coupling. Specifically, mid‐infrared (MIR) nano‐antennas coupled to saturable intersubband transitions in multi‐quantum‐well (MQW) semiconductor heterostructures allow for the coupling strength to be tuned through antenna resonance and field intensity. Here, in this study, tip‐enhanced nano‐scale variation of antenna‐MQW coupling across the antenna is demonstrated, with a spatially‐dependent coupling strength $g_{\textrm{aq}}$ varying from 73 (strong coupling) to 24 cm -1 (weak coupling). This behavior is modeled based on the spatially dependent local constructive and destructive interference between tip and antenna fields. Using a quantum‐mechanical density‐matrix model of the MQW system with its designed values of transition dipole moment, doping density, and population decay time, the picosecond IR pulse coupling to intersubband transitions and the associated tip induced strong‐field saturation effects are described. These results present a new regime of nonlinear IR light‐matter control based on the dynamic manipulation of quantum hybrid states on the nanoscale and in the infrared, with a perspective regarding extension to molecular vibrations.

Wang, Yueying↗

Elastic thermobarometry on metapelites across the crustal section of the Famatinian Arc, Argentina

We applied elastic thermobarometry on garnet-bearing migmatites along two transects through the crustal section at Sierra Valle Fértil-La Huerta, Argentina. We performed quartz-in-garnet barometry and zircon-in-garnet thermometry on metapelites from different paleo-depths across the crustal section. Our work recovers entrapment pressures ranging from 240 to 1330 MPa and entrapment temperatures between 691 and 1574 °C. The entrapment conditions are broadly consistent with anticipated pressures and temperatures along the crustal section derived previously using conventional, thermodynamic thermobarometers. The quartz-in-garnet barometer reproduces those conventionally established entrapment conditions when samples only experienced conditions within the alpha-quartz stability field. Raman-derived pressures for samples that experienced beta-quartz reference conditions are commonly much higher than those established by conventional barometry. Samples that preserve compressive (positive) residual pressures best reproduce reference entrapment pressures. Entrapment temperatures show high variability and overestimation of temperature conditions compared to conventional results. These results indicate elastic thermobarometry over- or under-estimates crystallization conditions in rocks crystallized at high temperatures, as is common in the Famatinian Arc deep-crust. We suggest that modeling quartz behavior across the alpha–beta transition may present challenges, as does shape maturation, viscous deformation, and radiation damage in zircon.

58 GEOSCIENCES↗

Oxidation Behavior of Candidate NiCr Alloys for Engine Exhaust Valves: Part I—Effect of Minor Alloying Elements

Oxidation-induced degradation of structural materials employed as exhaust valves within internal combustion engines (ICEs) will be a relevant life-limiting mechanism, in addition to creep and mechanical fatigue, due to ever-increasing severity of operating temperatures and pressures. Ni–Cr-based alloys, which form external chromia-based scales at the relevant operating temperatures are being considered as suitable candidate materials. Thermal cycling of these alloys in water vapor-containing atmospheres, such as those present during hydrocarbon fuel combustion within ICEs, can considerably influence their oxidation behavior. Here, the role of typical alloying additions such as Mn, Si, Al and Ti on the cyclic oxidation behavior of model NiCr–X (X = Mn,Si,Al,Ti) alloys exposed in dry air and air + 10% H 2 O at 800°C and 950°C was investigated. Combined additions of Mn and Si reduced scaling rates compared to binary Ni–22Cr alloys. The presence of water vapor possibly suppressed formation of NiMnCr spinel and thereby the Cr depletion in the alloy. Combined Al and Ti additions mainly resulted in accelerated oxidation kinetics due to the Ti doping of chromia scales. More porous external scales were observed in water vapor leading to a much deeper depth of nitridation in the Ni–22Cr–Al–Ti alloys.

36 MATERIALS SCIENCE↗

Understanding Self-Assembly and the Stabilization of Liquid/Liquid Interfaces: The Importance of Ligand Tail Branching and Oil-Phase Solvation

Organophosphorus-based ligands represent a versatile set of solvent extraction reagents whose chemical makeup plays an important role in extraction mechanism. We hypothesize that the branching of the extractant hydrophobic tail and its oil-phase solvation affect the liquid/liquid interfacial structure. Understanding the structure mediated adsorption and interfacial ordering becomes key in designing ligands with enhanced selectivity and efficiency for targeted extractions. We employed vibrational sum frequency generation spectroscopy and interfacial tension measurements to extract thermodynamic adsorption energies, map interfacial ordering, and rationalize disparate behaviors of model di-(2-ethylhexyl) phosphoric acid and dioctyl phosphoric acid ligands at the hexadecane water interface. With increased surface loading, ligands with branched hydrophobic tails formed stable interfaces at much lower concentrations than those observed for ligands with linear alkyl tails. The lack of an oil phase and associated solvation results in markedly different interfacial properties, and thus measurements made at air/liquid surfaces cannot be assumed to correlate with the processes occurring at buried liquid/liquid interfaces. Here, we attribute these differences in the surface mediated self-assembly to key variations in hydrophobic interactions and tail solvation taking place in the oil phase demonstrating that interactions in both the polar and nonpolar phases are essential to understand self-assembly and function.

36 MATERIALS SCIENCE↗