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At least 1,387 records · Page 77

Development of an Uncertainty Model for the National Transonic Facility

This paper introduces an uncertainty model being developed for the National Transonic Facility (NTF). The model uses a Monte Carlo technique to propagate standard uncertainties of measured values through the NTF data reduction equations to calculate the combined uncertainties of the key aerodynamic force and moment coefficients and freestream properties. The uncertainty propagation approach to assessing data variability is compared with ongoing data quality assessment activities at the NTF, notably check standard testing using statistical process control (SPC) techniques. It is shown that the two approaches are complementary and both are necessary tools for data quality assessment and improvement activities. The SPC approach is the final arbiter of variability in a facility. Its result encompasses variation due to people, processes, test equipment, and test article. The uncertainty propagation approach is limited mainly to the data reduction process. However, it is useful because it helps to assess the causes of variability seen in the data and consequently provides a basis for improvement. For example, it is shown that Mach number random uncertainty is dominated by static pressure variation over most of the dynamic pressure range tested. However, the random uncertainty in the drag coefficient is generally dominated by axial and normal force uncertainty with much less contribution from freestream conditions.

Walter, Joel A.↗

Heterogeneous Mixtures of Dictionary Functions to Approximate Subspace Invariance in Koopman Operators: Why Deep Koopman Operators Work

Abstract Koopman operators model nonlinear dynamics as a linear dynamic system acting on a nonlinear function as the state. This nonstandard state is often called a Koopman observable and is usually approximated numerically by a superposition of functions drawn from a dictionary . In a widely used algorithm, extended dynamic mode decomposition (EDMD), the dictionary functions are drawn from a fixed class of functions. Deep learning combined with EDMD has been used to learn novel dictionary functions in an algorithm called deep dynamic mode decomposition (deepDMD). The learned representation both (1) accurately models and (2) scales well with the dimension of the original nonlinear system. In this paper, we analyze the learned dictionaries from deepDMD and explore the theoretical basis for their strong performance. We explore State-Inclusive Logistic Lifting (SILL) dictionary functions to approximate Koopman observables. Error analysis of these dictionary functions show they satisfy a property of subspace approximation, which we define as uniform finite approximate closure. Typically, a Koopman dictionary’s nonlinear functions are homogeneous. In this paper, we discover that structured mixing of heterogeneous dictionary functions drawn from different classes of nonlinear functions achieve the same accuracy and dimensional scaling as the deep-learning-based deepDMD algorithm Yeung et al. ( In: 2019 American Control Conference (ACC), 2019). We specifically show this by building a heterogeneous dictionary comprised of SILL functions and conjunctive radial basis functions (RBFs). This mixed dictionary achieves similar accuracy and dimensional scaling to deepDMD with an order of magnitude reduction in parameters, while maintaining geometric interpretability. These results strengthen the viability of dictionary-based Koopman models to solving high-dimensional nonlinear learning problems.

Johnson, Charles A.↗

Operando XPS for Plasma Process Monitoring: A Case Study on the Hydrogenation of Copper Oxide Confined under h-BN

Here, we demonstrate that ambient pressure x-ray photoelectron spectroscopy (APXPS) can be used for in situ studies of dynamic changes in surface chemistry in a plasma environment. This opens a new and vast application space for XPS and greatly complements modern spectroscopy techniques to probe plasma-solid/liquid interactions relevant to process monitoring in the semiconductor industry, bio-medical plasma applications and plasma remediation technologies. Hexagonal boron nitride (h-BN) grown on Cu was used in this study as a well-defined model system for plasma process monitoring and because of its unique chemical, optical and electrical properties that make it a prospective material for advanced electronics. To better understand the stability and surface chemistry of h-BN during plasma assisted processing, we track in real time the plasma-induced chemical state changes of B, N and the underlying Cu substrate using APXPS equipped with an AC discharge plasma source operating at 13 Pa. Residual gas analysis (RGA) mass-spectra were concurrently collected during plasma-XPS to track reaction products formed during plasma exposure. A clear reduction of Cu x O is seen, while an h-BN layer remains intact, suggesting hydrogen radical (H • ) species can attack the exposed and h-BN covered Cu oxide patches and partially reduce the underlying substrate without significantly damaging the overlaying h-BN, which is of practical importance for development of h-BN encapsulated devices and interfaces. In addition to demonstration of plasma-XPS capabilities we discuss the observed challenges (e.g., parasitic plasma-chamber walls reactions and charging effects) and propose potential solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

All Recent Mars Landers Have Landed Downrange - Are Mars Atmosphere Models Mis-Predicting Density?

All recent Mars landers (Mars Pathfinder, the two Mars Exploration Rovers Spirit and Opportunity, and the Mars Phoenix Lander) have landed further downrange than their pre-entry predictions. Mars Pathfinder landed 27 km downrange of its prediction [1], Spirit and Opportunity landed 13.4 km and 14.9 km, respectively, downrange from their predictions [2], and Phoenix landed 21 km downrange from its prediction [3]. Reconstruction of their entries revealed a lower density profile than the best a priori atmospheric model predictions. Do these results suggest that there is a systemic issue in present Mars atmosphere models that predict a higher density than observed on landing day? Spirit Landing: The landing location for Spirit was 13.4 km downrange of the prediction as shown in Fig. 1. The navigation errors upon Mars arrival were very small [2]. As such, the entry interface conditions were not responsible for this downrange landing. Consequently, experiencing a lower density during the entry was the underlying cause. The reconstructed density profile that Spirit experienced is shown in Fig. 2, which is plotted as a fraction of the pre-entry baseline prediction that was used for all the entry, descent, and landing (EDL) design analyses. The reconstructed density is observed to be less dense throughout the descent reaching a maximum reduction of 15% at 21 km. This lower density corresponded to approximately a 1- low profile relative to the dispersions predicted. Nearly all the deceleration during the entry occurs within 10- 50 km. As such, prediction of density within this altitude band is most critical for entry flight dynamics analyses and design (e.g., aerodynamic and aerothermodynamic predictions, landing location, etc.).

Desai, Prasun N.↗

Asymmetric nanoparticle oxidation observed in-situ by the evolution of diffraction contrast

Abstract The use of transmission electron microscopy (TEM) to observe real-time structural and compositional changes has proven to be a valuable tool for understanding the dynamic behavior of nanomaterials. However, identifying the nanoparticles of interest typically require an obvious change in position, size, or structure, as compositional changes may not be noticeable during the experiment. Oxidation or reduction can often result in subtle volume changes only, so elucidating mechanisms in real-time requires atomic-scale resolution or in-situ electron energy loss spectroscopy, which may not be widely accessible. Here, by monitoring the evolution of diffraction contrast, we can observe both structural and compositional changes in iron oxide nanoparticles, specifically the oxidation from a wüstite-magnetite (FeO@Fe 3 O 4 ) core – shell nanoparticle to single crystalline magnetite, Fe 3 O 4 nanoparticle. The in-situ TEM images reveal a distinctive light and dark contrast known as the ‘Ashby-Brown contrast’, which is a result of coherent strain across the core – shell interface. As the nanoparticles fully oxidize to Fe 3 O 4 , the diffraction contrast evolves and then disappears completely, which is then confirmed by modeling and simulation of TEM images. This represents a new, simplified approach to tracking the oxidation or reduction mechanisms of nanoparticles using in-situ TEM experiments.

36 MATERIALS SCIENCE↗

Storage Enabled Flexibility of Conventional Generation Assets (StorFlex)

The power systems have faced progressively more demanding operational requirements over the last two decades. Several factors contribute to these challenging operating conditions, including load growth, aging infrastructure, increasing penetrations of distributed energy resources (DERs), electrification of the economy, and policy initiatives such as decarbonization. The power system and its components must provide high operational flexibility to mitigate these challenges. For example, the proliferation of intermittent DERs such as wind and solar has increased the need for conventional generation assets like hydropower plants to respond to sudden load-generation imbalances. The higher flexibility requirements for hydropower plants cause more wear and tear, potentially shortening the useful lifespan of hydropower turbines. To reduce the need for hydropower plants to follow sudden changes in the dispatch signal, we investigate their combined operation with the energy storage systems (ESSs; “ESS-based hybridization”). Our analyses focuses on improving the lifespan of hydropower plants through ESS-based hybridization. Wear and tear on hydropower turbines (particularly Francis turbines) is modeled using a loss-of-life concept that is based on damage experienced by the turbine due to various cycles of operation. Then, we show that using ESSs to offset some of the high variation increases the remaining life of the hydropower plants. To demonstrate this, a few modeling tools were developed for this work: (1) a dynamic model for various components of the turbine and its governor; (2) a control strategy that assigns a slow-varying dispatch signal to a hydropower unit versus a fastmoving signal to ESS, such that the overall power request remains the same; and (3) models for the financial analysis to quantify the economic merits of such a framework. We used the models we developed to analyze the dispatch pattern of an actual hydropower plant with a power output of 50 MW and a head height of 152 m. This work showed that ESS-based hybridization could extend the life of the hydropower plant by 5% on average. This extension in life was then used to estimate the economic benefit in terms of cost deferrals associated with hydropower plant maintenance and replacement: on average, $3.6 million. Sensitivity analysis with respect to the size of ESS and cost of turbines was performed to show the variation in benefits over the range of turbine costs and ESS sizes. Crucially, stacking damage reduction and lifetime extension with other ESS value streams such as providing ancillary services could substantially increase the financial benefits of ESS-based hybridization. The higher costs associated with ESS of appropriate size would make more financial sense when multiple value streams are stacked and co-optimized to extract the maximum benefit. This dimension will be explored in future work.

13 HYDRO ENERGY↗

Sulfite Is Not Required for N 2 Reduction Catalyzed by Mo-Nitrogenase

Mo-nitrogenase catalyzes the reduction of dinitrogen (N 2 ) to two ammonia (NH 3 ) at the active-site FeMo-cofactor. Substrate activation requires the accumulation of three or four electrons and protons as two Fe-bound hydrides and is coupled to obligatory H 2 release through reductive hydride elimination. Subsequent delivery of four or five additional electrons and protons to the bound N 2 yields two NH 3 molecules. Increasing evidence suggests that at least one belt sulfide within FeMo-cofactor is dynamically involved in the catalytic cycle. A recent report further proposed that sulfite (SO 3 2− ) is required for N 2 reduction, with sulfite binding required for NH 3 release and a subsequent six-electron reduction of the bound sulfite to regenerate the resting cofactor. To test this proposal, we conducted turnover studies of Mo-nitrogenase under sulfite-free conditions using a reduced viologen as reductant and protein preparations devoid of dithionite or sulfite. Under these conditions, nitrogenase effectively catalyzed both N 2 reduction and proton reduction, exhibiting steady-state turnover under N 2 for 6 min, with a turnover number exceeding 150, approaching that observed with dithionite as reductant. The same H 2 -formed/N 2 -reduced ratio was observed whether dithionite or the viologen species was used as reductant. Further, EPR spectroscopic analyses showed that the FeMo-cofactor returned to its resting state after multiple catalytic cycles in the absence of sulfite. Finally, physiological bypass of sulfite formation does not affect the capacity for diazotrophic growth of the model nitrogen-fixing organism Azotobacter vinelandii . Finally, these results demonstrate that sulfite is not required for Mo-nitrogenase-catalyzed N 2 reduction either in vitro or in vivo .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Management of Risk and Uncertainty Through Optimized Co-Operation of Transmission Systems and Microgrids with Responsive Loads (Final Report)

The evolution of the power system to the reliable, efficient and sustainable system of the future will involve development of both demand- and supply-side technology and operations. Ambitious national and state-level goals around the decarbonization of electricity relies on the integration of very high levels of renewable resources, most of which are variable and intermittent. The use of demand response is an ideal approach to counterbalance the intermittency of renewable generation and brings the consumer into the spotlight. Until recently, very little research had been conducted on the co-optimization of these two systems due to computational limitations. However, advances in computational capabilities, and the judicious use of decomposition methods and innovative approximation methods for high-dimension dynamic programming made this goal a viable objective for this project, leading to a fundamental shift in the ability to integrate and fully utilize demand-side resources. To this end, the modeling framework developed introduces a novel co-optimization framework, to include the operations of both the transmission and distribution systems (or microgrids) in operational decision making. This framework was used to analyze renewable and distributed generation along with responsive demand and to compare the capability of co-optimized systems to perform with higher levels of variable renewables. Results show that the use of a bi-level optimization approach is an appropriate structure, capable of co-optimizing a transmission system with multiple distribution systems and microgrids. While increasing the number of connected systems provides increasing flexibility for renewables integration this can also the economic benefits to the low-voltage subsystems with each additional system connected. Comparison of a traditional single-level decision structure with the co-optimization approach illustrates a reduction in overall system cost under co-optimization, while specific cost allocations to transmission and distribution systems are changed.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Techno-Economic Analysis and Optimization of a Compressed-Air Energy Storage System Integrated with a Natural Gas Combined-Cycle Plant

To address the rising electricity demand and greenhouse gas concentration in the environment, considerable effort is being carried out across the globe on installing and operating renewable energy sources. However, the renewable energy production is affected by diurnal and seasonal variability. To ensure that the electric grid remains reliable and resilient even for the high penetration of renewables into the grid, various types of energy storage systems are being investigated. In this paper, a compressed-air energy storage (CAES) system integrated with a natural gas combined-cycle (NGCC) power plant is investigated where air is extracted from the gas turbine compressor or injected back into the gas turbine combustor when it is optimal to do so. First-principles dynamic models of the NGCC plant and CAES are developed along with the development of an economic model. The dynamic optimization of the integrated system is undertaken in the Python/Pyomo platform for maximizing the net present value (NPV). NPV optimization is undertaken for 14 regions/cases considering year-long locational marginal price (LMP) data with a 1 h interval. Design variables such as the storage capacity and storage pressure, as well as the operating variables such as the power plant load, air injection rate, and air extraction rate, are optimized. Results show that the integrated CAES system has a higher NPV than the NGCC-only system for all 14 regions, thus indicating the potential deployment of the integrated system under the assumption of the availability of caverns in close proximity to the NGCC plant. The levelized cost of storage is found to be in the range of 136–145 $/MWh. Roundtrip efficiency is found to be between 74.6–82.5%. A sensitivity study with respect to LMP shows that the LMP profile has a significant impact on the extent of air injection/extraction while capital expenditure reduction has a negligible effect.

25 ENERGY STORAGE↗

Experimental Investigation of Low Cost, Low Thermal Conductivity Thermal Barrier Coating on HCCI Combustion, Efficiency, and Emissions

In-cylinder surface temperature is of heightened importance for Homogeneous Charge Compression Ignition (HCCI) combustion since the combustion mechanism is thermo-kinetically driven. Thermal Barrier Coatings (TBCs) selectively manipulate the in-cylinder surface temperature, providing an avenue for improving thermal and combustion efficiency. A surface temperature swing during combustion/expansion reduces heat transfer losses, leading to more complete combustion and reduced emissions. At the same time, achieving a highly dynamic response sidesteps preheating of charge during intake and eliminates the volumetric efficiency penalty. The magnitude and temporal profile of the dynamic surface temperature swing is affected by the TBC material properties, thickness, morphology, engine speed, and heat flux from the combustion process. This study follows prior work of authors with Yttria Stabilized Zirconia, which systematically engineered coatings for HCCI combustion. Herein, a modeling study was used to assess the impacts of various TBC material properties, e.g. density, thickness, and thermal conductivity on the temperature swing effect. Reducing conductivity emerged as a most promising avenue, rather than reducing both the density and effective conductivity by increasing porosity, the current work emphasizes a material with natively low conductivity. A novel TBC formulation was developed, leverages a class of materials that, to the author’s best knowledge, have not been used as a thermal barrier coating previously. Here, a systematic experimental investigation was carried out using single-cylinder research engine. Experimental engine studies utilizing the novel ‘glassy’ low-K coating exhibit advanced ignition phasing and reduced combustion duration relative to the baseline engine. Heat transfer measurements indicate a net reduction in heat flux over the entire cycle, although main effect is felt during expansion, and the reduced heat transfer losses manifest in higher gross indicated thermal efficiency by approximately 5-6% on a relative basis.

42 ENGINEERING↗

Mechanisms by which heat release affects the flow field in a chemically reacting, turbulent mixing layer

The mechanisms by which heat release affects the fluid dynamics in a turbulent reacting mixing layer are studied by direct numerical simulation. In agreement with previous laboratory experiments, the heat release is observed to lower the rate at which the mixing layer grows and to reduce the rate at which chemical products are formed. The baroclinic torque and thermal expansion in the mixing layer are shown to produce changes in the flame vortex structure that act to produce more diffuse vortices than in the constant density case, resulting in lower rotation rates of fluid elements. Previously unexplained anomalies observed in the mean velocity profiles of reacting jets and mixing layers are shown to result from vorticity generation by baroclinic torques. The density reductions also lower the generation rates of turbulent kinetic energy and the turbulent shear stresses, resulting in less turbulent mixing of fluid elements. Calculations of the energy in the various wave numbers show that the heat release has a stabilizing effect on the growth rates of individual modes. A linear stability analysis of a simlified model problem confirms this, showing that low density fluid in the mixing region will result in a shift of the frequency of the unstable modes to lower wave numbers (longer wavelengths). The growth rates of the unstable modes decrease, contributing to the slower growth of the mixing layer.

Riley, J. J.↗

Relationship between ozone and temperature trends in the lower stratosphere: Latitude and seasonal dependences

A one-dimensional radiative transfer model with fixed dynamical heating is used to calculate the approximate latitude and seasonal dependences of lower stratospheric temperature changes associated with observed ozone trends. The spatial and temporal distribution of ozone profile trends in the lower stratosphere is estimated from a combination of Nimbus 7 Solar Backscattered Ultraviolet (SBUV) global measurements of the ozone column below 32 mbar for the period 1979-1990 and balloon ozonesonde profile trends at northern middle latitudes. The calculated temperature trends near 100 mbar compare favorably with those recently derived by Randel and Cobb (1994) using data from Channel 4 of the Microwave Sounding Unit (MSU) on the NOAA operational satellites, although a number of quantitative differences are found. An independent analysis reported here of 100 mbar temperatures derived from northern hemisphere radiosonde data at the Free University of Berlin (FUB) supports the validity of the satellite-derived lower stratospheric temperature trends. These results are therefore generally consistent with the hypothesis that observed lower stratospheric cooling trends are predominantly determined by reductions in radiative heating associated with stratospheric ozone depletion.

Mccormack, John P.↗

Impact of collisionality on turbulence in the edge of tokamak plasma using 3D global simulations

Collisionality is one of the key parameters in determining turbulent transport in the plasma edge, regulating phenomena such as 'shoulder formation', separation of scale lengths in the scrape-off layer (SOL), turbulence damping and zonal flow dynamics. Understanding its role is therefore of primary importance for future reactors like ITER. Getting reliable predictions and a better characterization of plasma flow properties when varying collisionality remains, however, a critical challenge for the simulations. This paper focuses on the impact of varying collisionality in a non-isothermal three-dimensional fluid model of the plasma edge. A high field side limited configuration encompassing open and closed magnetic field lines with parameters typical of a medium-sized tokamak is considered. The present model can consistently account for the variations of collisionality and its impact on both the parallel resistivity η ∥ and the ion and electron parallel thermal conductivities χ ∥e,i . Details on mean flow and turbulence properties are given. Changing collisionality leads to significant changes in the flow properties both on the mean and fluctuating quantities. In particular, lowering collisionality decreases the size of coherent structures, the fluctuation levels of turbulence, and steepens the density and temperature equilibrium profiles around the separatrix leading to a global reduction of the turbulent transport. The SOL width is observed to increase with collisionality, eventually resulting in the disappearance of the scale lengths separation between near and far SOL, consistently with previous experimental observations. At low collisionality, where the presence of narrow feature is well-established, a contribution of heat conduction increases up to compete with heat convection.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A fast particle-based approach for calibrating a 3-D model of the Antarctic ice sheet

We consider the scientifically challenging and policy-relevant task of understanding the past and projecting the future dynamics of the Antarctic ice sheet. The Antarctic ice sheet has shown a highly nonlinear threshold response to past climate forcings. Triggering such a threshold response through anthropogenic greenhouse gas emissions would drive drastic and potentially fast sea level rise with important implications for coastal flood risks. Previous studies have combined information from ice sheet models and observations to calibrate model parameters. These studies have broken important new ground but have either adopted simple ice sheet models or have limited the number of parameters to allow for the use of more complex models. These limitations are largely due to the computational challenges posed by calibration as models become more computationally intensive or when the number of parameters increases. Here, we propose a method to alleviate this problem: a fast sequential Monte Carlo method that takes advantage of the massive parallelization afforded by modern high-performance computing systems. We use simulated examples to demonstrate how our sample-based approach provides accurate approximations to the posterior distributions of the calibrated parameters. The drastic reduction in computational times enables us to provide new insights into important scientific questions, for example, the impact of Pliocene era data and prior parameter information on sea level projections. These studies would be computationally prohibitive with other computational approaches for calibration such as Markov chain Monte Carlo or emulation-based methods. We also find considerable differences in the distributions of sea level projections when we account for a larger number of uncertain parameters. For example, based on the same ice sheet model and data set, the 99th percentile of the Antarctic ice sheet contribution to sea level rise in 2300 increases from 6.5 m to 13.1 m when we increase the number of calibrated parameters from three to 11. With previous calibration methods, it would be challenging to go beyond five parameters. Here, this work provides an important next step toward improving the uncertainty quantification of complex, computationally intensive and decision-relevant models.

54 ENVIRONMENTAL SCIENCES↗

Understanding LIB Battery Electrodes Through Classical Electrochemical Interface Theory

Classical models of the electrochemical interface can be applied to complex and dynamic electrodes to understand important mechanisms that are relevant to device-level phenomena like calendar aging or cycle life. Here, we show that negative alloy electrodes with wide electrochemical windows cannot be assumed to have static interfaces throughout all states of charge. Under high states of charge, the interface -including the solid electrolyte interphase - has characteristics that resemble a highly polarized electrode far from the point of zero charge. Under these conditions, the interface can be understood through the Helmholtz model. At lower states of charge, the interface capacitance decreases and the space charge layer length increases. This transformation resembles a metal electrode approaching the point of zero charge which is understood through the Gouy-Chapman-Stern-Grahame model of the electrochemical interface. This transformation happens at both silicon and carbon-coated silicon interfaces. From voltage-limited cycling experiments, in the limit of the diffuse double layer, the silicon electrode impedance rises significantly in the first few cycles. This rise is related to the continuous electrochemical reduction of electrolyte components from an interface that is not electronically screened from the electrolyte. In other words, an electrode interface for batteries should resemble a 'Helmholtz-like' structure.

anode↗

Machine learning modeling and model predictive control of a closed-circuit reverse osmosis system

Closed-circuit reverse osmosis (CCRO) offers a flexible and energy-efficient alternative to conventional reverse osmosis by operating in a semi-batch mode that recycles brine, enabling higher recovery rates and reduced specific energy consumption (SEC). However, developing accurate, system-level dynamic models for CCRO remains challenging due to its nonlinear, multi-phase operation and sensitivity to variable feed water conditions. Traditional modeling approaches, such as NARMAX (nonlinear autoregressive moving average with exogenous inputs), often struggle to generalize across varying inlet feed concentrations, necessitating frequent parameter re-estimation and limiting their utility for real-time control applications. To address these limitations, we developed a long short-term memory (LSTM) neural network model trained on an extensive experimental data set from a CCRO pilot plant. The model accepts three inputs, feed flow rate, recirculation flow rate, and initial feed conductivity, and predicts three key outputs: reject conductivity, feed pump power draw, and recirculation pump power draw. We validated the LSTM model against experimental data, demonstrating its ability to distinguish between different feed conductivities and adapt to variable flow rates. Subsequently, we incorporated the LSTM model within a nonlinear model predictive control (MPC) scheme and conducted closed-loop simulations to optimize the integrated SEC (iSEC). In conclusion, the results project up to a 6% reduction in iSEC by using MPC to optimize performance over the entire experiment duration, without requiring any random excitation for data collection or parameter re-estimation.

Desalination↗

Segmental Dynamics and Vitrification in Associating Copolymer Melts: Role of Cluster Formation, Microdomains, and Cross-Linking

A microscopic statistical mechanical theory of the structure, self-assembly, and activated segmental relaxation is employed to study associating copolymer melts with high attractive sticker fractions, local clustering, and disordered microphase ordering. The stickers are dynamically pinned in a manner that does not affect equilibrium structure which mimics the much slower physical bond breaking process or postassembly cross-linking of sticky monomers. Local sticker clustering and microdomain spatial correlations significantly modify the activated relaxation of nonstickers and glass transition temperature, T g . A re-entrant glass-melting feature is predicted as sticker attraction strength is initially increased corresponding to a speed up of segmental relaxation, and hence reduction of T g relative to the cross-linked homopolymer network. A mechanistic analysis reveals three competing effects: a purely kinetic slowing down of nonstickers down due to cross-linking, disordering of the nonsticker local cage and weakening of effective forces they experience due to sticker physical clustering, and a longer range impact of microdomain scale correlations that results in nonmonotonic dynamical effects. At high enough attraction strength, a qualitative change emerges corresponding to a sticker fraction dependent elevation of T g , which eventually surpasses that of the cross-linked homopolymer network. Dynamically, the new physics arises from a complex evolution of the amplitude of the collective elastic field that dresses the large amplitude mobile segment hopping within a coupled local-nonlocal description of the alpha relaxation. Furthermore, the results are qualitatively consistent with recent experiments on associating PDMS and PPG telechelics of fixed sticker fraction but with chemically different end groups of variable attraction strengths. Finally, possible tests using simulation and the influence of material or model specific interaction potentials and other real world complications are discussed.

Copolymers↗

Performance Tests of Snow-Related Variables Over the Tibetan Plateau and Himalayas Using a New Version of NASA GEOS-5 Land Surface Model that Includes the Snow Darkening Effect

The snow darkening effect, i.e. the reduction of snow albedo, is caused by absorption of solar radiation by absorbing aerosols (dust, black carbon, and organic carbon) deposited on the snow surface. This process is probably important over Himalayan and Tibetan glaciers due to the transport of highly polluted Atmospheric Brown Cloud (ABC) from the Indo-Gangetic Plain (IGP). This effect has been incorporated into the NASA Goddard Earth Observing System model, version 5 (GEOS-5) atmospheric transport model. The Catchment land surface model (LSM) used in GEOS-5 considers 3 snow layers. Code was developed to track the mass concentration of aerosols in the three layers, taking into account such processes as the flushing of the compounds as liquid water percolates through the snowpack. In GEOS-5, aerosol emissions, transports, and depositions are well simulated in the Goddard Chemistry Aerosol Radiation and Transport (GO CART) module; we recently made the connection between GOCART and the GEOS-5 system fitted with the revised LSM. Preliminary simulations were performed with this new system in "replay" mode (i.e., with atmospheric dynamics guided by reanalysis) at 2x2.5 degree horizontal resolution, covering the period 1 November 2005 - 31 December 2009; we consider the final three years of simulation here. The three simulations used the following variants of the LSM: (1) the original Catchment LSM with a fixed fresh snowfall density of 150 kg m-3 ; (2) the LSM fitted with the new snow albedo code, used here without aerosol deposition but with changes in density formulation and melting water effect on snow specific surface area, (3) the LSM fitted with the new snow albedo code as same as (2) but with fixed aerosol deposition rates (computed from GOCART values averaged over the Tibetan Plateau domain [Ion.: 60-120E; lat.: 20-50N] during March-May 2008) applied to all grid points at every time step. For (2) and (3), the same setting on the fresh snowfall density as in (1) was used.

Yasunari, Tppei J.↗