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At least 1,225 records · Page 68

Physical Processes Controlling the Distribution of Relative Humidity in the Tropical Tropopause Layer over the Pacific

The distribution of relative humidity with respect to ice (RHI) in the Boreal wintertime Tropical Tropopause Layer (TTL - about 14-19 km) over the Pacific is examined with the extensive dataset of measurements from the NASA Airborne Tropical TRopopause EXperiment (ATTREX). Multiple deployments of the Global Hawk during ATTREX provided hundreds of vertical profiles spanning the Pacific with accurate measurements of temperature, pressure, water vapor concentration, ozone concentration, and cloud properties. We also compare the measured RHI distributions with results from a transport and microphysical model driven by meteorological analysis fields. Notable features in the distribution of RHI versus temperature and longitude include (1) the common occurrence of RHI values near ice saturation over the western Pacific in the lower TTL (temperatures greater than 200 K) and in airmasses with low ozone concentrations indicating recent detrainment from deep convection; (2) low RHI values in the lower TTL over the eastern Pacific where deep convection is infrequent; (3) RHI values following a constant H2O mixing ratio in the upper TTL (temperatures below about 195 degrees Kelvin), particularly for samples with ozone mixing ratios greater than about 50-100 parts-per-billion-volume indicating mixtures of tropospheric and stratospheric air, and (4) RHI values typically near ice saturation in the coldest airmasses sampled (temperatures less than about 190 degrees Kelvin). We find that the typically saturated air in the lower TTL over the western Pacific is largely driven by the frequent occurrence of deep convection in this region. The nearly-constant water vapor mixing ratios in the upper TTL result from the combination of slow ascent (resulting in long residence times) and wave-driven temperature variability on a range of time scales (resulting in most air parcels having experienced low temperature and dehydration).

ozone↗

Correlating the Viscosity and Rate of Water Diffusion in Semisolid Gel-Forming Aerosol Particles

Aerosol particles are known to exist in highly viscous amorphous states at a low relative humidity and temperature. The slow diffusion of molecules in viscous particles impacts the uptake and loss of volatile and semivolatile species and the rate of heterogeneous chemistry. Recent work has demonstrated that in particles containing organic molecules and salts, the formation of two-phase gel states is possible, leading to observations of rigid particles that resist coalescence. The way that molecules diffuse and transport in gel systems is not well-characterized. In this work, we use an electrodynamic balance to levitate sample particles containing a range of organic compounds in mixtures with calcium chloride and measure the rate of water diffusion. Particles of the pure organics have been shown to form viscous amorphous states, while in mixtures with divalent salts, coalescence measurements have revealed the apparent solidification of particles, consistent with the formation of a gel state facilitated by ion–molecule interactions. We report in several cases that water transport can actually be increased in the rigid gel state relative to the pure compound that forms a viscous state under similar conditions. These measurements reveal the limitations of using viscosity as a metric for predicting molecular diffusion and that the gel structure that forms is a much stronger controlling factor in the rate of diffusion. In conclusion, this underscores the need for diffusion measurements as well as a deeper understanding of noncovalent molecular assembly that leads to supramolecular structures in aerosol particles.

organic-inorganic mixtures↗

The connection between Venus' free obliquity and its CMB oblateness

The most striking feature of Venus rotational state is its slow retrograde rotation which is apparently maintained by a balance between solid tidal friction and thermal tidal torques. Solid tides tend to drive the spin toward synchronous rotation while thermal tides drive it away. A balance is achieved at a specific rate because of the inverse frequency dependence of the thermal tide to the semi-diurnal heating. Atmospheric models have been constructed to estimate the thermal tidal torque based on ground heating. The solid friction dissipation factor Q approximately equal to 50 can be deduced assuming rotation has achieved steady state. The most perplexing feature of Venus orientation is its non-zero free obliquity epsilon approximately equal to 1.5 deg relative to its orbit. Although solid tides and perhaps atmospheric tides tend to increase the free obliquity on a time 1/K(sub t) approximately equal to 1 x 10(exp 8) yr, viscous friction (CMF) at a core-mantle boundary (CMB) resulting from the differential angular orientation Delta-epsilon of the core and mantle spin axes should have damped the free obliquity on a time scale as short as 10(exp 6) yr. One means of achieving a balance similar to that controlling rotation is to introduce a comparatively large CMB ellipticity e(sub c) to reduce Delta-epsilon such that there is a balance between solid-thermal tides and CMF. The balance depends not so much on the potential frequency dependence on the tides as on the quadratic dependence of CMF on Delta-epsilon if the layer is turbulent.

Yoder, C. F.↗

Carbon cycling in high-latitude ecosystems

The carbon-rich soils and peatlands of high-latitude ecosystems could substantially influence atmospheric concentrations of CO2 and CH4 in a changing climate. Currently, cold, often waterlogged conditions retard decomposition, and release of carbon back to the atmosphere may be further slowed by physical protection of organic matter in permafrost. As a result, many northern ecosystems accumulate carbon over time (Billings et al., 1982; Poole and Miller, 1982), and although such rates of accumulation are low, thousands of years of development have left Arctic ecosystems with an extremely high soil carbon content; Schlesinger's (1984) average value of 20.4 kg C/m(sup 2) leads to a global estimate of 163 x 10(exp 15) g C. All GCM simulations of a doubled CO2 climate predict the greatest warming to occur in the polar regions (Dickinson, 1986; Mitchell, 1989). Given the extensive northern carbon pools and the strong sensitivity of decomposition processes to temperature, even a slight warming of the soil could dramatically alter the carbon balance of Arctic ecosystems. If warming accelerates rates of decomposition more than rates of primary production, a sizeable additional accumulation of CO2 in the atmosphere could occur. Furthermore, CH4 produced in anaerobic soils and peatlands of the Arctic already composes a good percentage of the global efflux (Cicerone and Oremlund, 1988); if northern soils become warmer and wetter as a whole, CH4 emissions could dramatically rise. A robust understanding of the primary controls of carbon fluxes in Arctic ecosystems is critical. As a framework for a systematic examination of these controls, we discussed a conceptual model of regional-scale Arctic carbon turnover, including CH4 production, and based upon the Century soil organic matter model.

Townsend, Alan↗

Investigating the Effects of Exposure to Blue-Enriched Light or Peppermint Odor on Alertness, Mood, and Performance Upon Awakening from Deep Sleep at Night

Introduction: Sleep inertia refers the transient neurobehavioral impairments experienced immediately after waking from sleep. This period of reduced alertness and performance poses a significant safety risk to on-call workers who may be required to perform a safety-critical task immediately after waking (e.g., emergency services, health care, and military). In these operations, the need for a rapid return to full alertness is critical to mission safety and success. Several factors may exacerbate sleep inertia, resulting in greater impairment upon waking, including: waking from deep sleep, (i.e., slow wave sleep, SWS), waking at night, and waking following prior sleep loss. Awakenings under these conditions are common for on-call and extended shift workers who may need to perform safety-critical tasks soon after waking from unprotected sleep opportunities. Therefore, there is a need for evidence-based reactive countermeasures (i.e., used upon waking) to the cognitive consequences sleep inertia. Specifically, countermeasures that can rapidly restore alertness and performance immediately following sleep. A recent review of the literature on reactive countermeasures highlighted several research gaps and promising candidates for further investigation. The review also emphasized the need for countermeasures that are operationally viable and readily deployed in occupational settings. This study aims to address the identified gaps and limitations by assessing the efficacy of exposure to two known acute alerting stimuli - blue-enriched light and peppermint odor - to improve cognitive performance, alertness, and mood immediately after waking from SWS at night. Materials and Methods: Twelve participants completed a two-week within-subject, randomized, cross-over intervention study including two in-laboratory overnight visits. During each experimental week, the subjects experienced one intervention (light or peppermint) and a control condition upon awakening from SWS at night. The presentation order of the two conditions (intervention or control) at wake-up and the order of intervention (light or peppermint) by week was randomized by sex. Prior to each in-laboratory visit, participants maintained a sleep schedule of 8.5 h for 5 nights and 5 h for one night. Compliance with this sleep schedule was confirmed by actigraphy. In the laboratory, participants went to bed at their habitual bedtime and were monitored by standard polysomnography. After at least five minutes of continuous SWS, participants were awoken and exposed, in a randomized order, to either the control or intervention condition. During the hour after awakening from SWS (at 2, 17, 32, and 47 minutes after waking), participants completed a battery of tasks including a 5-minute psychomotor vigilance task (PVT), a subjective scale of alertness (Karolinska Sleepiness Scale, KSS), and visual analogue scales (VAS) of mood. Following this sleep inertia measurement period, all lights were turned off and participants were allowed to return to sleep. They were then awoken again from their subsequent SWS period and exposed to the alternative condition (control or intervention). Following this second awakening, participants were allowed to sleep until their habitual wake time and were then released from the laboratory. Participants then followed the at-home sleep schedule and returned to the laboratory for the second intervention (light or peppermint) following the procedures described above. The light intervention involved exposure to a blue-enriched light canvas illuminated for 1 hour at a distance of ~56 cm from the participant (~200 lux and ~60 melanopic lux at angle of gaze). For the peppermint intervention, peppermint oil was pipetted onto a mask, and participants inhaled the odor with the mask covering the nose and mouth for 1 minute. The control condition for both weeks involved a dim, red ambient light (<1 lux). An odorless mask, without any oil pipetted onto the mask, was also worn in the peppermint control condition. Results: Compared to the control condition, participants exposed to blue-enriched light had fewer PVT lapses (χ2 = 5.285, p = .022), reported feeling more alert (KSS: F1,77 = 4.955, p = .029; VASalert: F1,77 = 8.226, p = .005), and had improved mood (VAScheerful: F1,77 = 8.615, p = .004; VASdepressed: F1,77 = 4.649, p = .034; VASlethargic: F1,77 = 5.652, p = .020). Exposure to peppermint oil did not improve any outcome measures on any of the tasks compared to control condition (p > .05). Conclusions: We found that participants had fewer lapses of attention upon awakening when exposed to blue-enriched light compared to dim, red light. In addition, participants reported feeling more alert, more cheerful, less depressed, and less lethargic in the blue-enriched light condition. Brief exposure to a peppermint odor, however, did not appear to improve performance, alertness, or mood under the experimental conditions. Our null results in the peppermint condition may have been due to methodological limitations such as the duration and method of administration. Given the need to mitigate the potential impact of sleep inertia on safety-critical tasks in on-call operations, our findings suggest that blue-enriched light exposure upon awakening may help to improve performance and alertness during the sleep inertia period following awakening from deep, nocturnal sleep. We are currently exploring the potential mechanisms for the effect of light on cognitive performance upon awakening as well as investigating its application in real-world settings to explore the translational efficacy of this countermeasure to occupational environments. Continued exploration into light and other reactive countermeasures, and potentially their combination, is needed in order to provide evidence-based guidance on effective sleep inertia countermeasures to improve the alertness and performance of those required to perform safety-critical tasks soon after waking.

sleep inertia↗

Effect of quasiperiodic and random noise on many-body dynamical decoupling protocols

Symmetries (and their spontaneous rupturing) can be used to protect and engender novel quantum phases and lead to interesting collective phenomena. In the work of K. Agarwal and I. Martin, the authors described a general dynamical decoupling (polyfractal) protocol that can be used to engineer multiple discrete symmetries in many-body systems. This work expands on the former by studying the effect of quasiperiodic and random noise on such a dynamical scheme. We find generally that relaxation of engineered symmetry generators proceeds by (i) an initial relaxation on microscopic timescales to a prethermal plateau whose height is independent of noise, (ii) a linear relaxation regime with a noise-dependent rate, followed by (iii) a slow logarithmic relaxation regime that is only present for quasiperiodic noise. We glean the essential features of these regimes via scaling collapses and show that they can be generally explained by the spectral properties of the various noise waveforms considered. In particular, the quasiperiodic noise is characterized by highly time-dependent spectrum with a noise floor that mimics white noise, and peaks that grow sharper with time. We argue that both the noise floor and peaks contribute to the initial linear-in-time relaxation while the logarithmic regime is initiated when the peaks become sufficiently well resolved and cease to contribute to further relaxation. Here, we provide numerical evidence to justify these findings.

74 ATOMIC AND MOLECULAR PHYSICS↗

Probing electrolyte–silica interactions through simulations of the infrared spectroscopy of nanoscale pores

The structural and dynamical properties of nanoconfined solutions can differ dramatically from those of the corresponding bulk systems. Understanding the changes induced by confinement is central to controlling the behavior of synthetic nanostructured materials and predicting the characteristics of biological and geochemical systems. A key outstanding issue is how the molecular-level behavior of nanoconfined electrolyte solutions is reflected in different experimental, particularly spectroscopic, measurements. This is addressed here through molecular dynamics simulations of the OH stretching infrared (IR) spectroscopy of NaCl, NaBr, and NaI solutions in isotopically dilute HOD/D 2 O confined in hydroxylated amorphous silica slit pores of width 1–6 nm and pH ~2. In addition, the water reorientation dynamics and spectral diffusion, accessible by pump–probe anisotropy and two-dimensional IR measurements, are investigated. In this work, the aim is to elucidate the effect of salt identity, confinement, and salt concentration on the vibrational spectra. It is found that the IR spectra of the electrolyte solutions are only modestly blue-shifted upon confinement in amorphous silica slit pores, with both the size of the shift and linewidth increasing with the halide size, but these effects are suppressed as the salt concentration is increased. This indicates the limitations of linear IR spectroscopy as a probe of confined water. However, the OH reorientational and spectral diffusion dynamics are significantly slowed by confinement even at the lowest concentrations. The retardation of the dynamics eases with increasing salt concentration and pore width, but it exhibits a more complex behavior as a function of halide.

Mesoporous material↗

Optical characterization of the oceanic unicellular cyanobacterium Synechococcus grown under a day-night cycle in natural irradiance

The optical properties of the ocenanic cyanobacterium Synechococcus (clone WH8103) were examined in a nutrient-replete laboratory culture grown under a day-night cycle in natural irradiance. Measurements of the spectral absorption and beam attenuation coefficients, the size distribution of cells in suspension, and microscopic analysis of samples were made at intervals of 2-4 hours for 2 days. These measurements were used to calculate the optical properties at the level of a single 'mean' cell representative of the acutal population, specifically, the optical cross sections for spectral absorption bar-(sigma(sub a)), scattering bar-sigma(sub b))(lambda), and attentuation bar-(sigma(sub c))(lambda). In addition, concurrent determinations of chlorophyll a and particulate organic carbon allowed calculation of the Chl a- and C-specific optical coefficients. The refractive index of cells was derived from the observed data using a theory of light absorption and scattering by homogeneous spheres. Low irradiance because of cloudy skies resulted in slow division rates of cells in the culture. The percentage of dividing cells was unusually high (greater than 30%) throughout the experiment. The optical cross sections varied greatly over a day-night cycle, with a minimum near dawn or midmorning and maximum near dusk. During daylight hours, bar-(sigma(sub b)) and bar-(sigma(sub c)) can increase more than twofold and bar-(sigma(sub a) by as much as 45%. The real part of the refractive index n increaed during the day; changes in n had equal or greater effect than the varying size distribution on changes in bar-(sigma(sub c)) and bar-(sigma(sub b)). The contribution of changes in n to the increase of bar-(sigma(sub c))(660) during daylight hours was 65.7% and 45.1% on day 1 and 2, respectively. During the dark period, when bar-(sigma(sub c))(660) decreased by a factor of 2.9, the effect of decreasing n was dominant (86.3%). With the exception of a few hours during the second light period, the imaginary part of the refractive index n' showed little variation over a day-night cycle, and bar-(sigma(sub a)) was largely controlled by variations in cell size. The real part of the refractive index at lambda = 660 nm was correlated with the intracellular C concentration and the imaginary part at lambda = 678 nm with the intracellular Chl a concentration. The C-specfic attenuation coefficient showed significant diel variability, which has implications for the estimation of oceanic primary production from measurements of diel variability in beam attenuation. This study provides strong evidence that diel variability is an important component of the optical characterization of marine phytoplankton.

Stramski, Dariusz↗

Encapsulation Enhances the Quantum Coherence of a Solid‐State Molecular Spin Qubit

Spins within molecules benefit from the atomistic control of synthetic chemistry for the realization of qubits. One advantage is that the quantum superpositions of the spin states encoding the qubit can be coherently manipulated using electromagnetic radiation. The main challenge is the fragility of these superpositions when qubits are to partake of solid-state devices. We address this issue with a supramolecular approach for protecting molecular spin qubits against decoherence. The molecular qubit [Cr(ox)3]3- has been encapsulated inside the diamagnetic triple-stranded helicate [Zn2L3]4+ (L is a bis-pyrazolylpyridine ligand). The quantum coherence of the protected qubit is then analyzed with pulsed EPR spectroscopy and compared with the unprotected qubit, both in solution and in the solid state. Crucially, the spin-spin relaxation in the solid state has been examined within diamagnetic crystal lattices of the isostructural ([Al(ox)3]@[Zn2L3])+ or [Al(ox)3]3- assemblies, respectively, doped with the Cr3+ qubit in two different (<10%) concentrations. The study unveils a surprising increase of the phase memory time of the qubit upon encapsulation only in the solid. Spin-lattice relaxation times also exhibit a significant enhancement, as established from inversion recovery pulse sequences and from slow relaxation of the magnetization of the protected qubit, not featured by the free qubit.

Swain, Abinash↗

Use of a controlled experiment and computational models to measure the impact of sequential peer exposures on decision making

It is widely believed that one’s peers influence product adoption behaviors. This relationship has been linked to the number of signals a decision-maker receives in a social network. But it is unclear if these same principles hold when the “pattern” by which it receives these signals vary and when peer influence is directed towards choices which are not optimal. To investigate that, we manipulate social signal exposure in an online controlled experiment using a game with human participants. Each participant in the game decides among choices with differing utilities. We observe the following: (1) even in the presence of monetary risks and previously acquired knowledge of the choices, decision-makers tend to deviate from the obvious optimal decision when their peers make a similar decision which we call the influence decision, (2) when the quantity of social signals vary over time, the forwarding probability of the influence decision and therefore being responsive to social influence does not necessarily correlate proportionally to the absolute quantity of signals. To better understand how these rules of peer influence could be used in modeling applications of real world diffusion and in networked environments, we use our behavioral findings to simulate spreading dynamics in real world case studies. We specifically try to see how cumulative influence plays out in the presence of user uncertainty and measure its outcome on rumor diffusion, which we model as an example of sub-optimal choice diffusion. Together, our simulation results indicate that sequential peer effects from the influence decision overcomes individual uncertainty to guide faster rumor diffusion over time. However, when the rate of diffusion is slow in the beginning, user uncertainty can have a substantial role compared to peer influence in deciding the adoption trajectory of a piece of questionable information.

97 MATHEMATICS AND COMPUTING↗

The Transactive Energy Network Template Metamodel

While transactive energy, which is defined as an allocation of electricity based on dynamically discovered values or prices, has been extensively studied, its uptake and use has been slow. This report describes a tool, the transactive network template, which should hasten the creation and uptake of transactive energy networks. Some basic principles of transactive energy are familiar from existing wholesale electricity markets. Locational prices are calculated today for zones within bulk electric transmission systems. Locational prices differ while accounting for the locational costs of electricity generation and the losses and constraints incurred when electricity is transmitted from generators and distributed to consumers. A transactive energy network might include these transmission zones. However, current research strives to apply transactive energy also in electricity distribution circuits, buildings, and even for individual generating and consuming devices. At the same time, researchers explore how to apply transactive energy in real time during increasingly shorter time intervals. Automated computational agents become necessary as transactive energy becomes applied to smaller circuit zones and at faster dynamic timescales. A transactive energy network is an example of a multi-agent system. Each zone in the network is represented by its transactive agent, which makes decisions for and acts on behalf of a business entity that is responsible for and manages one of the circuit regions. A transactive energy network is also an example of a decentralized, distributed control system. Control decisions and responsibilities are distributed among the network’s transactive agents. The transactive agents are independent; that is, there typically is no centralized authority or oversight function. Instead, transactive agents exchange transactive signals and thereby negotiate the prices and quantities of electricity that they will exchange. Initially, the circuit regions and responsibilities of transactive agents appear to be very dissimilar. Each circuit region may comprise transmission, distribution, or building-level circuits. Each has a unique position and electrical connectivity within the transactive energy network. Each possesses unique assets that either generate or consume electricity, and these (e.g., renewable energy generator, diesel generator, aggregate utility load, building load, space conditioning, refrigerator, etc.) may further differ in their price flexibility and in their strategies for responding to dynamic electricity prices. Given such diversity, an implementer’s first inclination might be to start from scratch to define all these devices and to engineer their seemingly unique interactions. Given that each implementer’s perspective may be narrow within a transactive energy network, it is unlikely that uniquely engineered systems would interact well. This is where the transactive network template is applicable. The transactive network template is a metamodel that has been developed to guide implementers as they configure their own transactive agent within a network of such agents. The object-oriented design of the transactive network template provides basic code object types that may be used and extended by implementers to represent each of the assets in their circuit region. These objects further facilitate the transactive agent’s necessary computations, which are divided among responsibilities to schedule power usage, balance electric supply and demand, and coordinate the exchange of electricity with the other transactive agents. This report addresses the conceptual transactive network template design. Implementers are directed to more formal design documents and reference implementations. A Python™-based1 reference implementation of the transactive network template has been coded, and three implementations have been configured to represent a national laboratory and two university campuses. Version 2 of the transactive node template generalizes the market class and its methods to facilitate multiple, and more diverse market coordination mechanisms than were facilitated by and demonstrated using Version 1. Version 3 includes new Appendix B, which addresses the designs of methods that would make dynamic prices track approved electricity rates. In the future, the author wishes to make the transactive network template more generally applicable to networks that require more accurate power flow. Development of the transactive network template is jointly funded by the U.S. Department of Energy (DOE) Energy Efficiency and Renewable Energy and the DOE Office of Electricity. In late 2015, one of the first projects to be funded by the DOE Grid Laboratory Modernization Laboratory Consortium was the Clean Energy and Transactive Campus project, led by Pacific Northwest National Laboratory. DOE funds were matched by an investment by the Washington Department of Commerce through its Clean Energy Fund. The transactive network template was developed to guide the implementation of transactive energy networks within this project’s scope.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Slow Auger Recombination of Trapped Excitons Enables Efficient Multiple Electron Transfer in CdS–Pt Nanorod Heterostructures

We report solar-to-fuel conversion reaction often requires multiple proton-coupled electron transfer (PCET) processes powered by the energetic electrons and/or holes generated by the absorption of multiple photons. The effective coupling of multiple electron transfer from the light absorber with the multiple PCET reactions at the catalytic center is one of the key challenges in efficient and selective conversion of solar energy to chemical fuels. In this paper, we examine the dynamics of multiple electron transfer in quantum confined CdS nanorods with a Pt tip, in which the CdS rod functions as the light absorber and the Pt tip the catalytic center. By excitation-fluence-dependent transient absorption spectroscopic measurements, we show that the multiexciton Auger recombination rate in CdS rods follows a carrier-collision model, k n A = n 2 (n – 1)/4k 2 A , with a biexciton lifetime (1/k 2 A ) of 2.0 ± 0.2 ns. In CdS–Pt nanorods, electron transfer kinetics from the CdS conduction band edge to the Pt show negligible dependence on the excitation fluence, occurring with a half-life time of 5.6 ± 0.6 ps. The efficiency of multiple exciton dissociation by multiple electron transfer to Pt decreases from 100% in biexciton states to ~41% at 22 exciton state due to the competition with Auger recombination. The half-lifetime of the n-charge separated state recombination (with n electrons in the Pt and n holes in the CdS) decreases from 10 μs in the single charge separated state to 42 ns in nine charge separated states. Our findings suggest the possibility of driving multielectron photocatalytic reactions under intense illumination and controlling product selectivity through multielectron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental comparison of time synchronization techniques by means of light signals and clock transport on the rotating earth

An experiment was conducted to investigate the equivalence of two methods of time transfer in a noninertial reference frame: by means of an electromagnetic signal using laser light pulses and by means of the slow ground transport of a hydrogen maser atomic clock. The experiment may also be interpreted as an investigation of whether the one-way speeds of light in the east-west and west-east directions on the rotating earth are the same. The light pulses were sent from a laser coupled to a telescope at the NASA Goddard Optical Research Facility (GORF) in Greenbelt, Maryland to the U.S. Naval Observatory (USNO) in Washington, DC. The optical path was made possible by a 30-cm flat mirror on a water tower near GORF and a 25-cm flat mirror on top of the Washington National Cathedral near USNO. The path length was 26.0 km with an east-west component of 20.7 km. The pulses were reflected back over the same path by a portable array of corner cube reflectors. The transmission and return times were measured with a stationary Sigma Tau hydrogen maser and a University of Maryland event timer at GORF, while the times of reflection were measured with a similar maser and event timer combination carefully transported to USNO. Both timekeeping systems were housed in highly insulated enclosures and were maintained at constant temperatures to within +/- 0.1 C by microprocessor controllers. The portable system was also protected from shock and vibration by pneumatic supports. The difference delta(T) between the directly measured time of reflection according to the portable clock and the time of reflection calculated from the light pulse signal times measured by the stationary clock was determined. For a typical trip delta(T) is less than 100 ps and the corresponding limit on an anisotropy of the one-way speed of light is delta(c/c) is less than 1.5 x 10(exp -6). This the only experiment to date in which two atomic clocks were calibrated at one location, one was slowly transported to the other end of a path, and the times of transmission, reflection, and return of short light pulses sent in different directions along the path were registered.

Nelson, R. A.↗

Numerical Simulations in Support of a Long-Term Test of Gas Production from Hydrate Accumulations on the Alaska North Slope: Reservoir Response to Interruptions of Production (Shut-Ins)

In this work, we investigate by means of numerical simulation a planned year-long field test of depressurization-induced production from a permafrost-associated hydrate reservoir on the Alaska North Slope at the site of the recently drilled Hydrate-01 Stratigraphic Test Well. The main objective of this study is to assess quantitatively the impact of temporary interruptions (well shut-ins) on the expected fluid production performance from the B1 Sand of the stratigraphic Unit B during controlled depressurization over different time scales, as well as on other relevant aspects of the system response that have the potential to significantly affect the design of the field test. We consider eight different cases of depressurization, including (a) rapid depressurization over a 60-day period to a terminal bottomhole pressure P W of 2.8 MPa and (b) a slower depressurization rate to a final P W of 0.6 MPa at the end of the year-long production test, in addition to (c) a multi-step depressurization regime and (d) a quasi-linear continuous depressurization strategy. The results of the study indicate that shut-ins obviously reduce gas release and production during and immediately after their occurrence, but their longer-term effects are strongly dependent on the depressurization regime and on the time of observation, covering the entire range of potential outcomes. Shut-ins (a) have a universally strong negative effect when quasi-linear depressurization is involved regardless of the length of the production period, and (b) have a strong positive effect in multi-step depressurization schemes that becomes apparent earlier for large initial pressure drops, but (c) can also appear to have practically no effect for slow stepwise depressurization at the end of the year-long production test. Shut-ins lead to a rapid reformation of hydrates, even to the point of disappearance of a free gas phase in the reservoir. Rapid depressurization regimes lead to early maximum rates of hydrate dissociation and gas production, while the maximum rates occur at the end of the production test for the cases of slower depressurization. Shut-ins do not appear to have a significant impact on water production, as the cessation of production is followed by higher rates production when depressurization resumes. Similarly, (a) the fraction of produced CH 4 originating from exsolution from the water, (b) the water-to-gas ratio, and (c) the rate of replenishment of produced water by boundary inflows do not appear significantly affected by shut-ins, the effects of which seem to be temporary in the majority of the cases. The study confirmed the superiority of multi-step depressurization methods as the most effective strategies for hydrate dissociation and gas production and showed that two observation wells (located at distances of 30 and 50 m from the production well) are appropriately positioned and both able to capture the P, T, and S G behavior during the fluid production and shut-ins in any of the eight cases we investigated.

03 NATURAL GAS↗

Investigations of the stability of etched or platinized p-InP(100) photocathodes for solar-driven hydrogen evolution in acidic or alkaline aqueous electrolytes

Here, the stability of p-InP photocathodes performing the hydrogen-evolution reaction (HER) has been evaluated in contact with either 1.0 M H 2 SO 4 (aq) or 1.0 M KOH(aq), with a focus on identifying corrosion mechanisms. Stability for the solar-driven HER was evaluated using p-InP electrodes that were either etched or coated with an electrodeposited Pt catalyst (p-InP/Pt). Variables such as trace O 2 were systematically controlled during the measurements. Changes in surface characteristics after exposure to electrochemical conditions as well as electrode dissolution processes were monitored using X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). In either H 2 SO 4 or KOH, etched p-InP photoelectrodes corroded cathodically under illumination, forming metallic In 0 at the electrode surface. In contrast, electrodeposition of Pt kinetically stabilized illuminated p-InP photocathodes in both H 2 SO 4 and KOH by inhibiting the cathodic corrosion pathway. Notably, when held at 0 V vs. the reversible hydrogen electrode (RHE) in 1.0 M H 2 SO 4 (aq), p-InP/Pt exhibited a stable current density (J) of ~–18 mA cm –2 for >285 h under simulated 1 Sun illumination. The long-term current density vs. potential (J–E) behavior at pH 0 and pH 14 of p-InP/Pt photocathodes correlated with changes in the surface chemistry as well as the dissolution of p-InP. In acidic media, the J–E behavior of p-InP/Pt photocathodes remained nearly constant with time, but the surface of a p-InP/Pt electrodes gradually turned P-rich via a slow and continuous leaching of In ions. In alkaline electrolyte, the surface of p-InP/Pt electrodes was passivated by formation of an InO x layer that exhibited negligible dissolution but led to a substantial degradation in the J–E characteristics. Consequently, changes in the catalytic kinetics and surface stoichiometry are both important considerations for determining the corrosion chemistry and the long-term operational stability of InP photoelectrodes.

14 SOLAR ENERGY↗

Uses of Computed Tomography in the NASA Materials Science Program

Computed Tomography (CT) has proved to be of inestimable use in providing a rapid evaluation of a variety of samples from Mechanics of Granular Materials (MGM) to electronic materials (Ge-Si alloys) to space grown materials such as meteorites. The system at Kennedy Space Center (KSC), because of its convenient geographical location, is ideal for examining samples immediately after returning to Earth. It also has the advantage of the choice of fluxes, and in particular the use of a radioactive cobalt source, which is basically monochromatic. This permits a reasonable measurement of density to be made from which chemical composition can be determined. Due to the current dearth of long duration space grown materials, the CT instrument has been used to characterize materials in preparation for flight, to determine thermal expansion values, and to examine long duration space grown materials, i.e. meteorites. The work will first describe the establishment of the protocol for obtaining the optimum density readings for any material. This will include both the effects of the hardware or instrumental parameters that can be controlled, and the techniques used to process the CT data. Examples will be given of the compositional variation along single crystals of germanium-silicon alloys. Density variation with temperature has been measured in preparation for future materials science experiments; this involved the fabrication and installation of a single zone furnace incorporating a heat pipe to ensure of high temperature uniformity. At the time of writing the thermal expansion of lead has been measured from room temperature to 900 C. Three methods are available. Digital radiography enable length changes to be determined. Prior to melting the sample is small than the container and the diameter change can be measured. Most critical, however, is the density change in solid, through the melting region, and in the liquid state. These data are needed for engineering purposes to aid in the design of containment cartridges, and for enabling fluid flow calculations. A second sample, with the lead alloyed with antimony is ready for scanning. This corresponds to the planned composition of Dr. Poirier's flight experiment. Finally, three-dimensional results will be shown of the structure of a two-phase metallic meteorite of metal and sulfide, in which the iron-nickel phase has coarsened during slow cooling over hundreds of millions of years.

Engel, H. Peter↗

In situ Detection of Plasma Induced Surface Interaction based on Deep Learning based Visual Diagnostics (Technical Report)

It is characteristic for many plasma devices to undergo plasma-material interaction leading to surface erosion. These processes, often not easily detectable, lead to changes in device performance and lifespan. State-of-the-art lifetime tests and wear experiments require over 1000s hours. A self-consistent model for accurately predicting the erosion's effects is not available. In situ detection of these processes is not a trivial task since the surface variations at the early stages have a micron scale. Such limitations not only restrict testing and prediction capabilities but also slow the development of new thrusters and limit mission duration. To address these challenges, an in-situ diagnostic for real-time erosion assessment has been developed, aiming to expedite lifetime testing and broaden experimental campaigns. Several works were dedicated to real-time and in situ monitoring of material erosion during plasma exposure using laser holography, microscopy, and with telemicroscopes. However, the applicability of these approaches is limited due to complexity, cost and less flexibility as they often require placing diagnostic equipment inside the vacuum chamber. In collaboration with Princeton Collaborative Research Facility (PCRF), Princeton Plasma Physics Laboratory (PPPL), a new diagnostic approach is developed, where geometry modifications to the ceramic channel walls were introduced that would result in accelerated channel erosion. We employed Long-distance microscope (LDM) imagery, combined with Deep-Learning based Shape from focus or depth from focus (DFF or SFF) approach, that provides an accessible and cost-effective solution. LDM employs focus variation techniques to continuously capture multiple images of the target object at distinct focal planes. DFF, an optical focus variation method, generates a 3D topographical surface depth map from a sequence of variably focused images. Combined with the developed diagnostic, this approach offers a controllable means to study erosion under accelerated conditions. In this work, we develop Neural Network-based DFF algorithm applicable for LDM data to quantitatively evaluate plasma induced surface modification from LDM data. Next, we develop Deep Learning-based super-resolution depth map image reconstruction technique to increase the resolution of depth maps obtained from DFF algorithm to improve the accuracy of erosion measurements. Thirdly, we develop several image processing techniques to remove noise and improve the quality of depth map image. Here we report the results of initial tests for this approach. An experimental setup designed and built in PPPL was employed that consists of a 3-cm gridded ion source that produces a neutralized argon beam with energies up to 600 eV. A hexagonal boron nitride (h-BN) ceramic target, designed based on computational predictions, was used. Tests were conducted to reconstruct the complex geometry of the target under the lighting conditions of the operated ion source.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

UO 2 + 5 vol% ZrB 2 nano composite nuclear fuels with full boron retention and enhanced oxidation resistance

The boron isotope ( 10 B) can be used as a neutron absorber in UO 2 to control the reactivity of nuclear fuel pellets, however, the boron source can react with oxygen source in UO 2 to form B 2 O 3 that vaporize readily at temperatures above 1200 °C. Unfortunately, the sintering of UO 2 fuel requires hours holding at high temperature (>1700 °C), resulting in an inevitable B loss during sintering and unpredictable B concentration in final product. It is challenging to incorporate boron through a conventional sintering method. In this work, we demonstrated that spark plasma sintering (SPS), a field assisted sintering technology, can effectively densify UO 2 + 5 vol% ZrB 2 composite fuel pellets by rapid consolidation at 1600 °C for a short duration of 5 min under an applied pressure of 40 MPa. Further, thermogravimetric analysis (TGA) measurements confirm that ZrB 2 is fully retained inside the composite fuel pellets. Inside the composite fuel pellets, nano sized ZrB 2 particles are uniformly distributed along the grain boundaries of the UO 2 matrix. The ZrB 2 particle transforms to a glassy B 2 O 3 phase covering the sample surface and grain boundaries of UO 2 matrix after a simple post-sintering annealing at 1000 °C in flowing Argon gas for 4 h. The formed glassy B 2 O 3 slows down the diffusion of oxygen ions and postpones the onset temperature for oxidation of UO 2 from 400 °C to 550 °C. This study demonstrates the capability of SPS, an advanced fuel manufacturing technique, to achieve a full retention of ZrB 2 in UO 2 oxide fuel and increase oxidation resistance through a simple post-sintering annealing. The reported work holds great engineering potential for development of advanced oxide fuel for nuclear application.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗