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At least 109 records · Page 6

XPCS Microrheology and Rheology of Sterically Stabilized Nanoparticle Dispersions in Aprotic Solvents

In this study, X-ray photon correlation spectroscopy (XPCS) microrheology and conventional bulk rheology were performed on silica nanoparticle dispersions associated with battery electrolyte applications to probe the properties of these specific complex materials and to explore the utility of XPCS microrheology in characterizing nanoparticle dispersions. Sterically stabilized shear-thickening electrolytes were synthesized by grafting poly(methyl methacrylate) chains onto silica nanoparticles. Coated silica dispersions containing 5–30 wt % nanoparticles dispersed in propylene carbonate were studied. In general, both XPCS microrheology and conventional rheology showed that coated silica dispersions were more viscous at higher concentrations, as expected. The complex viscosity of coated silica dispersions showed shear-thinning behavior over the frequency range probed by XPCS measurements. However, measurements using conventional mechanical rheometry yielded a shear viscosity with weak shear-thickening behavior for dispersions with the highest concentration of 30% particles. Our results indicate that there is a critical concentration needed for shear-thickening behavior, as well as appropriate particle size and surface polymer chain length, for this class of nanoparticle-based electrolytes. The results of this study can provide insights for comparing XPCS microrheology and bulk rheology for related complex fluids and whether XPCS microrheology can capture expected macroscopic rheological properties by probing small-scale particle dynamics.

36 MATERIALS SCIENCE↗

Multidisciplinary studies with mutated HIV-1 capsid proteins reveal structural mechanisms of lattice stabilization

Abstract HIV-1 capsid (CA) stability is important for viral replication. E45A and P38A mutations enhance and reduce core stability, thus impairing infectivity. Second-site mutations R132T and T216I rescue infectivity. Capsid lattice stability was studied by solving seven crystal structures (in native background), including P38A, P38A/T216I, E45A, E45A/R132T CA, using molecular dynamics simulations of lattices, cryo-electron microscopy of assemblies, time-resolved imaging of uncoating, biophysical and biochemical characterization of assembly and stability. We report pronounced and subtle, short- and long-range rearrangements: (1) A38 destabilized hexamers by loosening interactions between flanking CA protomers in P38A but not P38A/T216I structures. (2) Two E45A structures showed unexpected stabilizing CA NTD -CA NTD inter-hexamer interactions, variable R18-ring pore sizes, and flipped N-terminal β-hairpin. (3) Altered conformations of E45A a α9-helices compared to WT, E45A/R132T, WT PF74 , WT Nup153 , and WT CPSF6 decreased PF74, CPSF6, and Nup153 binding, and was reversed in E45A/R132T. (4) An environmentally sensitive electrostatic repulsion between E45 and D51 affected lattice stability, flexibility, ion and water permeabilities, electrostatics, and recognition of host factors.

60 APPLIED LIFE SCIENCES↗

Understanding improved cycling and thermal stability of compositionally graded Ni-rich layered LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode materials

The concentration gradient is a strategic design, adjusting the distribution of Ni, typically with a higher Ni content in the core and a higher Mn content toward the surface. This design leverages the pivotal role of the Ni/Mn ratio, seeking to optimize cathode performance by balancing Ni's high capacity with Mn's stabilizing effects, particularly at the surface where degradation commonly occurs during cycling. Here, our study delves into the intricate structural and chemical transformations within concentration gradient cathode materials during electrochemical cycling. Utilizing advanced synchrotron X-ray techniques, including hard and soft X-ray absorption spectroscopy (hXAS, sXAS), and nanoscale X-ray imaging, we investigate buried changes in concentration gradient LiNi 0.6 Mn 0.2 Co 0.2 O 2 (CG NMC622). Contrary to conventional assumptions, our findings challenge the notion that cycling stability relies solely on Mn stability. Unraveling the roles of Ni and Mn, we uncover how their individual and collective contributions impact the cathode's overall performance. This investigation transcends established paradigms, shedding light on the crucial mechanisms governing the enhanced cycling stability of Nirich layered cathode materials.

25 ENERGY STORAGE↗

Stability boundary and optimal operating parameter identification in milling using Bayesian learning

Here, this paper describes a novel Bayesian learning approach for stability boundary and optimal parameter identification in milling without the knowledge of the underlying tool dynamics or material cutting force coefficients. The paper is divided into two parts. First, a Bayesian learning method for stability lobe identification using test results is described. Each axial depth and spindle speed combination is characterized by a probability of stability which is updated using Bayes’ rule when a test result (stable or unstable) is made available. A novel likelihood function is defined which incorporates knowledge of the stability behavior. Numerical results show convergence to the analytical stability lobe diagram. Second, an adaptive experimental strategy to identify optimal operating parameters that maximize material removal rate is described. Numerical evaluation shows convergence to the optimal operating point with error less than 15 % within ten tests on average. The approach is validated using experimental results. Results show that the proposed method is an efficient and robust learning method to identify the stability lobe diagram and optimal operating parameters with a limited number of tests/data points.

Bayesian machine learning↗

Assessing Physical Relationships Between Atmospheric State, Fluxes, and Boundary Layer Stability at McMurdo Station, Antarctica

Observations at McMurdo Station, Antarctica from 24 November 2015 through 3 January 2017 were used to characterize the physical relationships between boundary layer stability and atmospheric state and fluxes. The basis of this analysis was self-organizing maps (SOMs), a neural network algorithm, used to identify the range of potential temperature profiles present in the twice-daily radiosonde data during the ARM (Atmospheric Radiation Measurement) West Antarctic Radiation Experiment (AWARE) campaign. The SOM identified profiles ranging from strongly stable to weakly stable regimes over the lowest 500 m of the atmosphere. It was found that in the winter (MJJA), moderate and strongly stable regimes occur most frequently (61%), while weakly stable regimes dominate in the summer (DJ, 83.4%). The mechanisms responsible for the dominance of different stability regimes in each season were analyzed to determine why these regimes occur with varying frequency throughout the year. This analysis found that wind speed variations and radiative cooling are responsible for the stability observed in the winter, radiative warming, as well as weaker wind speeds, are responsible for summer weak stability, and stability variations in the transition seasons (FMA, SON) are characterized by a change in sign of net radiation with increasing stability, as wind speed changes little across stability regimes. Low-level jets were observed to occur about 50% of the time below areas of enhanced stability aloft and were observed most frequently in the transition seasons. The boundary layer depth, as determined by the Bulk Richardson number, was found to decrease with increasing stability.

54 ENVIRONMENTAL SCIENCES↗

Toward Thermally Stimuli-Responsive Polymeric Vesicles Fabricated by Block Copolymer Blends for Nanocarriers

Polymeric vesicles, characterized by enhanced colloidal stability, excellent mechanical properties, controllable surface functionality, and adjustable membrane thickness, are extremely useful in nano- and bio-technology for potential applications as nanosized carriers for drugs and enzymes. However, a few preparative steps are necessary to achieve a unilamellar vesicle with a narrow size distribution. Herein, we report the spontaneous formation of unilamellar polymeric vesicles with nanometer sizes (<50 nm), fabricated by simply mixing diblock copolymers (P(EO-AGE)(2K-2K) and P(EO-AGE)(0.75K-2K)) with differing hydrophilic mass fractions in aqueous solutions. Depending on the mixing ratio of block copolymers and the temperature, the block copolymer mixtures self-assemble into various nanostructures, such as spherical and cylindrical micelles, or vesicles. The self-assembled structures of the block copolymer mixtures were characterized by small-angle neutron scattering, resulting in a phase diagram drawn as a function of temperature and the mixing condition. Notably, the critical temperature for the micelle-to-vesicle phase transition can be easily controlled by altering the mixing conditions; it decreases with an increase in the concentration of one of the block copolymers.

block copolymers↗

Flame stabilization in DME spray flames under engine-relevant conditions characterized by OH* chemiluminescence and formaldehyde laser-induced fluorescence

The transient and quasi-steady flame structures of Dimethyl Ether (DME) fuel sprays, produced by a single-hole injector (Spray D), were investigated using Planar Laser-Induced Fluorescence (PLIF) and chemiluminescence imaging in a constant-volume chamber under Engine Combustion Network (ECN) Spray A conditions (900 K ambient temperature, 60 bar ambient pressure, 1500 bar injection pressure, and 22.8 kg/m 3 ambient density). Low-temperature chemical reaction zones were visualized using formaldehyde (CH 2 O) PLIF with 355 nm excitation, while high-temperature flame regions were captured via chemiluminescence imaging of excited-state hydroxyl radicals (OH*). Both transient and quasi-steady flame structures clearly show the transition from CH 2 O to OH*, highlighting the progression from low- to high-temperature combustion, while the position of the flame is displaced for DME compared to reference hydrocarbon n-dodecane. Homogeneous reactor calculations with detailed chemistry and using adiabatic mixing for initial temperature show that CH 2 O peaks are significantly higher for DME at the same equivalence ratio, with a higher heat-release during the cool-flame regime with respect to the fuel heating value. Thus, the cool-flame dynamic as a precursor to high-temperature combustion and flame stabilization exhibit distinct behavior for DME relative to conventional hydrocarbons, and these phenomena are effectively resolved through the soot-free nature of DME and the high-speed, time-resolved diagnostics.

CH2O laser-induced fluorescence↗

Effect of Hydrogen on Steady-State and Transient Combustion Instability Characteristics

This paper examines the effects of steady-state and transient hydrogen enrichment on thermoacoustic instability in a model gas turbine combustor. Combustion instability, a feedback loop between flame heat release rate oscillations and combustor acoustics, is characterized in a swirl-stabilized flame operated at a range of hydrogen–natural gas fuel blends and heat rates. Measurements of combustor chamber pressure fluctuations and CH* chemiluminescence imaging are used to characterize instability at a range of operating conditions. Steady-state tests show that both mixture heat rate and hydrogen content affect system stability. At a given heat rate, higher levels of hydrogen result in unstable combustion. As heat rate increases, instability occurs at lower concentrations of hydrogen in the fuel. Transient operation was tested in two directions—instability onset and decay—and two hydrogen-addition times—a short time of 1 ms and a longer time of 4 s. Results show that instability onset processes, through the transient addition of hydrogen, are highly repeatable regardless of the timescale of hydrogen addition. Certain instability decay processes are less repeatable, resulting in cases that do not fully transition from unstable to stable combustion despite similar changes in hydrogen fuel flow rate. Flame behavior before, during, and after the transient is characterized using high-speed CH* chemiluminescence imaging. Analysis of the high-speed images shows changes in flame stabilization and dynamics during the onset and decay processes. Finally, the results of this study can have implications for systems that experience variations in fuel composition, particularly in light of growing interest in hydrogen as a renewable fuel.

42 ENGINEERING↗

Connecting cation site location to alkane dehydrogenation activity in Ni/BEA catalysts

Ni-modified beta zeolite (Ni/BEA) catalysts activate carbon-hydrogen bonds in light alkanes, as demonstrated through isobutane reaction testing. Controlled synthesis of Ni/BEA allows for efficient introduction of ion-exchanged Ni sites at varying Ni loadings (0.43% - 1.8%). These catalysts exhibit site time yields (STY) for H2 production that increase with increasing Ni loading. A detailed analysis of secondary reactions and carbon deposition based on the relative molar flowrates of product C and H indicates that the observed increase in H2 STY with increasing Ni loading is likely attributed to both increasing alkane activation activity and increasing formation of hydrogen-deficient aromatic products retained within the catalyst pores. In situ diffuse-reflectance UV-visible-NIR absorbance and X-ray absorption spectroscopies indicate isolated, 4-coordinate Ni(2+) species for all loadings. Quantum mechanics/molecular mechanics modeling identifies two distinct Ni(2+) sites consistent with the structural characterization, but with differing relative stabilities due to their coordination environment. Computed reaction energetics for isobutane dehydrogenation demonstrate that the more stable Ni(2+) species at a six-membered 4Si-2Al ring, Ni-6MR, is less active for isobutane dehydrogenation than the less stable Ni(2+) at the five-membered 3Si-2Al ring, Ni-5MR. The differing local structure of the isolated cationic Ni sites in Ni/BEA offers a possible rationalization for the increased H2 STY observed at greater Ni loadings.

catalysts↗

Disturbance Propagation Stability in Droop-Controlled Microgrids

The disturbance response of the angle dynamics for a droop-controlled islanded microgrid is characterized. Specifically, a notion of propagation stability is defined, which is concerned with spatial attenuation vs amplification of input- output responses in the network in a H8 or H2 sense. Criteria for propagation stability are developed, phrased in terms of the microgrid’s inverter control parameters. The input frequency range over which the network is susceptible to amplification is also characterized, in the case that the criteria are not met. Based on the formal analysis, a the design of resilient controls that trade off coherence and disturbance propagation goals is briefly conceptualized. Finally, the propagation stability analysis is illustrate using a 15-bus example microgrid network.

Roy, Sandip↗

Modeling the influence of the solid electrolyte interphase on the sand’s time and dendrite formation on lithium metal electrodes

Lithium metal is a sought after battery material for its high energy density due to the low electrochemical potential and density. However, lithium metal is also highly reactive, which results in a strong propensity for dendrite formation. The Sand’s time has previously been used to predict the time of dendrite initiation on metals that do not form a solid-electrolyte interphase (SEI), but it has been shown that the Sand’s time is not accurate for lithium electrodes when using transport parameters associated with the electrolyte. Thus, we built a numerical model to simulate lithium ion transport through a growing SEI to predict the Sand’s time. The numerical model is shown to be more accurate than previous analytical solutions, especially for low current densities. We then analyze the sensitivity of the Sand’s time to different SEI properties and the chemical potential gradients present in the SEI, driving lithium transport. The results showed that high lithium concentration has a greater impact at high current density, while fast diffusivity is more important at low current density. Lastly, we modeled the influence of surface roughness on the plating evolution and chemical potential gradients when an SEI is present in comparison to the electrolyte. As a result, we demonstrate that the SEI plays a critical role in lithium electrode stability, and that improved characterization techniques are needed to better understand transport through the SEI and increase lithium metal utilization in energy storage devices.

Chemistry↗

Quantifying Uncertainties in Modeling Wind Resource Data from Different PBL Schemes in the WRF Model: A Case Study Over the Puerto Rico Region

This study examines the modeling uncertainty of wind resource data stemming from the use of various planetary boundary layer (PBL) parameterizations available in the Weather Research and Forecasting (WRF) model. WRF-based wind simulations spanning 20 years at 3-km resolution using 11 different PBL schemes are used to objectively investigate the uncertainty in modeling wind speed for land-based wind (LBW) and offshore wind (OSW) locations in Puerto Rico. The uncertainty in the wind modeling for the 20-year dataset is quantified using the spread index (SI) and standard deviation (SD). For virtual LBW and OSW sites, the SI and SD values are analyzed as calculated across various spatial and temporal scales. Because the PBL's atmospheric stability conditions can be characterized into two dominant categories, the study focuses on analyzing the SI and SD for daytime (mainly unstable PBL conditions) and nighttime (mainly stable PBL conditions). For wind shear (10 m-200 m) at the OSW and LBW sites, WRF-based numerical experiments indicate the following SI (or SD) ranges: 39%-94% (0.74 m/s-1.44 m/s) during the daytime for OSW, 50%-75% (0.68 m/s-1.19 m/s) during the daytime for LBW, 37%-60% (0.73 m/s-1.12 m/s) during the nighttime for OSW, and 57%-143 % (0.65 m/s-1.43 m/s) during the nighttime for LBW. While a high SI is observed when modeling LBW during the nighttime, there are notable modeling uncertainties during the daytime on the leeward side of the orographic barriers for Puerto Rico.

17 WIND ENERGY↗

The role of Ca-bridged organic matter in an alkaline soil, as revealed by multimodal chemical imaging

Mineral–organic matter (OM) studies have predominantly focused on acidic soils that are abundant in iron (Fe) oxides and aluminum (Al) oxides. We have probed mineral–OM interactions in an alkaline or calcareous soil of the Aridisols class. Unlike the role of Fe and Al, the role of Ca-minerals (particularly calcite), which are ubiquitous in alkaline soils, in OM sequestration is not well understood. Multiple recent model studies with aqueous Ca2+ or synthetic calcite and a suite of OM compounds have shown Ca-OM assemblages to be spatially correlated with calcite at the microscale. To study the chemical state of both Ca and Fe and their competing role in soil organic matter (SOM) stabilization, we performed laboratory characterization using x-ray diffraction, Mössbauer spectroscopy, x-ray photoelectron spectroscopy, scanning electron microscopy, and scanning transmission electron microscopy, alongside synchrotron-based microscale chemical imaging using scanning transmission x-ray microscopy combined with near-edge x-ray absorption fine structure. Ca mineral–organic associations were found to be ubiquitous in this system and are likely critical for understanding SOM stabilization/degradation in alkaline soils. From our findings on mineralogy, speciation, and the nature of Ca-OM bridging, we identified differences in C and Ca chemistry based on the relative location of OM to Ca minerals. The OM near the calcite crystal was enriched in lipid and protein moieties, Ca-OM next to Fe minerals displayed a strong contribution from aromatic compounds, while on the surface of microbes, the carbonate was believed to be of microbial in origin, as also suggested by preliminary works reporting on the formation of amorphous calcite or nano-calcite. In Ca-OM admixed with carbonate, it was difficult to distinguish Ca-associated OM from amorphous calcite or nano-calcite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of high thermal conductivity fuel surrogates before and after ion irradiation

High thermal conductivity nuclear fuels offer important potential advantages over traditional oxide-based fuels such as higher burnup, reduction in fission gas release, and better overall safety of the system. One proposed approach to high thermal conductivity fuels utilizes high thermal conductivity nonfissile additives with UO 2 fuel to lower the fuel operating temperature and thereby take advantage of the highly favorable radiation resistance of UO 2 at lower operating temperatures. However, differential swelling in the matrix and high conductivity additive phases during high dose irradiation could lead to internal cracking and poor performance. In the current study, ceria (CeO 2 ) and zirconia (ZrO 2 ) surrogate matrices were used to model UO2 behavior. Additives of 10 vol. % Al 2 O 3 or SiC in the form of short fibers or platelets were used for the high conductivity second phase. The nuclear fuel surrogates were sintered to achieve densities greater than 93% of the ideal values. Scanning electron microscopy (SEM) imaging and X-ray diffraction confirmed the uniform distribution of the second phase and that no intermetallic second phase was formed during sintering. The thermal conductivity of the sintered samples was measured from 50 °C to 900 °C and confirmed the desirable increase compared to pure CeO 2 /ZrO 2 pellets. Samples were irradiated with 20 MeV Ni 6+ ions at midrange doses ranging from 1 to 15 displacements per atom (dpa) and temperatures from 300 °C to 700 °C. Post irradiation characterization revealed a good stability of the samples at low to medium doses with matrix lattice parameter swelling of < 0.14 % but showed a significant microstructural deterioration and decrease of the mechanical properties at 15 dpa.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High Density Two-Component Glasses of Organic Semiconductors Prepared by Physical Vapor Deposition

Physical Vapor Deposition (PVD) is widely utilized for the production of organic semiconductor devices due to its ability to form thin layers with exceptional properties. Although the layers in the device usually consist of two or more components, there is limited understanding about the fundamental characteristics of such multi-component vapor-deposited glasses. Here, spectroscopic ellipsometry was employed to characterize the densities, thermal stabilities and optical properties of co-vapor deposited NPD and TPD glasses across the entire range of composition. We find that co-deposited NPD and TPD form high density glasses with enhanced thermal stability. The dependences of density and stability upon substrate temperature are correlated, and the birefringence of the co-deposited glasses is determined by the reduced substrate temperature of mixtures. Additionally, we observe that the transformation of a highly stable and dense two-component glass into its supercooled liquid initiates from the free surface and propagates into the bulk at constant velocity, like single component PVD glasses. As a result, all these features are consistent with the surface equilibration mechanism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Non-catalytic oxidative depolymerization of lignin in perfluorodecalin to produce phenolic monomers

We demonstrate for the first time non-catalytic, oxidative cracking with molecular oxygen (O 2 ) to depolymerize native lignin into oxygenated phenolic monomers. Maximum monomer yield of 10.5 wt% was achieved at 250 °C after only 10 min of reaction and included vanillin, syringaldehyde, vanillic acid, and syringic acid. High rates of oxidation are attributed to the use of perfluorodecalin as solvent. Perfluorodecalin is a perfluorocarbon (PFC), characterized by their chemical stability and exceptionally high solubility for O 2 . Monomer yields were typically five-fold higher in perfluorodecalin compared to solvents more commonly employed in lignin conversion, such as methanol, butanol, acetonitrile, and ethyl acetate. Phenolic monomer production in perfluorodecalin favors high temperatures and short reaction times to prevent further oxidation of the produced monomers. Lignin oil obtained under oxidative conditions in perfluorodecalin showed lower molecular weight and smaller polydispersity compared to other solvents. Increasing the reaction time further decreased the molecular weight, while increasing reaction time in an inert atmosphere increased the molecular weight of the lignin oil. High concentrations of O 2 in perfluorodecalin not only increased lignin depolymerization but suppressed undesirable condensation reactions. Depolymerization is likely initiated by thermally induced homolytic cleavage of ether linkages in lignin to form phenoxy and carbon-based radicals. These radicals bind with O 2 as a radical scavenger and further react to form phenolic monomeric products rather than repolymerizing to large oligomers. The PFC process was scaled from 5 mL to 250 mL without any loss of yield. Because most organic compounds are not soluble in perfluorodecalin, recycling is easily achieved via liquid–liquid separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Network stability of FKM rubber compounds under hydrogen pressure

Fluorocarbon-based rubber (FKM) compounds are typically utilized in the aeronautical industry due to its exceptional chemical and thermal resistance and recently has drawn significant interest from the hydrogen community for various hydrogen applications, but there exists little data evaluating its hydrogen compatibility. In this paper, a formulated FKM compound was exposed to ultrahigh hydrogen pressure (90 MPa) and analyzed by attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy and crosslinking densities by solvent swelling measurement. ATR-FTIR spectroscopic data demonstrated that high-pressure hydrogen not only caused cleavages in polymer backbone and cross linkages, but also induced additional degradation of FKM compounds by breaking intermolecular hydrogen bonding between carboxylic acids, which were produced during rubber molding and post curing processes. This hydrogen pressure-driven degradation was significantly higher towards the core of the material than at the surface due to its weaker bonding between polymers and fillers.

Polymers, hydrogen, stability, degradation, Charac↗

Isotope effects under the influence of global radial electric fields in a helical configuration

Isotope effects under the influence of a radial electric field are examined in a helical magnetic field configuration. We perform global gyrokinetic simulations with additional poloidal rotations to estimate quasi-linear heat flux due to ion temperature gradient mode under the mixing length model. In single-ion-species plasmas, the mass number dependency of heat flux agrees with gyro-Bohm scaling in the absence of a radial electric field. Favorable mass number dependencies violating gyro-Bohm scaling are observed in the presence of a global radial electric field or a heavy hydrogen component in multi-ion-species plasmas. The radial electric field and the heavy hydrogen component affect the heat flux through an increase of wavelength as well as mode stabilization. Poloidal Mach number characterizes the transition from unfavorable to favorable mass number dependency under radial electric fields. While the heat flux is independent of mass number for a given poloidal Mach number, the heat flux decreases for higher mass numbers in a given radial electric field. The heat flux is also independent of average mass number in multi-ion-species plasmas because the heavy hydrogen component effectively enhances the light hydrogen heat flux. The present results are potentially relevant to the violation of gyro-Bohm scaling observed in the recent deuterium experiments in the Large Helical Device.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗