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At least 289 records · Page 16

The effective number of parameters in kernel density estimation

We devise a new formula for measuring the effective degrees of freedom (EDoF) in kernel density estimation (KDE). Starting from the orthogonal polynomial sequence (OPS) expansion for the ratio of the empirical to the oracle density, we show how convolution with the kernel leads to a new OPS with respect to which one may express the resulting KDE. The expansion coefficients of the two OPS systems can then be related via a kernel sensitivity matrix, which leads to a natural oracle definition of EDoF through the trace operator. Asymptotic properties of the (empirical) plug-in EDoF are worked out through influence functions, and connections with other empirical EDoFs are established. Minimization of Kullback-Leibler divergence is investigated as an alternative to integrated squared error based bandwidth selection rules, yielding a new normal scale rule. The methodology, which arises from a proper oracle formulation and is not restricted to convolution kernels, suggests the possibility of a new bandwidth selection rule based on an information criterion such as AIC.

bandwidth selection↗

Burn parameters affect PAH emissions at conditions relevant for prescribed fires

Wildfire smoke is a health hazard as it contains carcinogenic volatile compounds and fine particulate matter. In particular, exposure to polycyclic aromatic hydrocarbons (PAHs) is a major concern, since these compounds have been recognized as important contributors to the overall carcinogenic risk. In this work, gas and particle-phase PAH emissions from combustion of Eastern White Pine (Pinus strobus) were quantified using time-of-flight mass spectrometry over a range of burn conditions representative of wildfires and prescribed fires, including fuel moisture, heat flux, and oxygen concentration. We found that changing the burn environment lead to a variability of up to 77% in phenanthrene/anthracene emissions. This could explain a large part of the variability in PAH emission factors from biomass combustion reported in the literature. Here, we found that optimal conditions for fuel moisture content of 20–30%, sample heat load of 60 - 70 kW m -2 , and oxygen concentrations of 5–15% can significantly reduce the emissions of heavy molar weight PAHs. Our analysis showed that the relative carcinogenic risk from PAH exposure can be reduced by more than 50% under optimal conditions. In light of the increasing use of prescribed fire for forest management, the relationship between emissions and burn conditions that we have established provides a guidance for assessing the expected health impact from prescription burns, and can inform strategies to reduce PAH emissions from prescribed fire activities.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Hydrogen from low-density polyethylene via nonthermal plasma: Effects of energy density and process parameters

Nonthermal plasma processes are promising for the modular valorization of plastic waste, especially into hydrogen and carbon materials, due to their high intensity, lack of reliance on catalysts or consumables, and suitability to be directly powered by electricity. We investigate the production of hydrogen from low-density polyethylene (LDPE) as a plastic waste model using streamer Dielectric Barrier Discharge (sDBD) plasma in nitrogen at atmospheric pressure. Here, we examine the effects of process energy density (energy input per unit of feedstock mass), feedstock mass, and plasma intensity (electric voltage) on plasma properties, hydrogen yield and energy efficiency via gas chromatography, optical emission spectroscopy, and electrical diagnostics, together with reactor-scale and nonlinear electric circuit modeling. The characteristic temperature of free electrons in the sDBD plasma is approximately 15000 K (1.3 eV), and that of gas species 10 times lower, demonstrating strong thermal non-equilibrium that can lead to molecular bond scission via charged species impact rather than direct heating. Experimental results show that higher energy density leads to greater hydrogen production and diminishing energy efficiency, and that higher plasma intensity and larger feedstock mass lead to greater hydrogen yield due to higher plasma temperatures and enhanced energy fluxes to the feedstock.

08 HYDROGEN↗

Hydrogen influences thermal activation parameters for dislocation glide during low cycle fatigue of 316L stainless steel

Measurements of activation areas are used to investigate the effect of hydrogen on the kinetics of dislocation glide during cyclic deformation in cold-worked 316L stainless steel. Non-charged and hydrogen-precharged (H-precharged) specimens were tested in low cycle fatigue (LCF) under plastic strain control. A series of plastic strain rate changes was performed periodically at the peak true plastic strain from the first cycle to half-life, and at various plastic strain values around stable hysteresis loops near half-life to determine the operational activation area, Δ a ∗. Both material conditions demonstrate a rapid increase in Δ a ∗ during the initial rapid softening followed by a region of approximately constant values coinciding with a reduced rate of softening. Near half-life, hydrogen reduces Δ a ∗ at a given true stress due to its effect on the activation distance and obstacle spacing. The magnitudes of Δ a ∗ reveal that bypassing solutes, cutting forest dislocations, and initiating cross slip are important mechanisms of thermally activated dislocation glide at all amplitudes, except hydrogen suppresses cross slip at the lowest plastic strain amplitudes. These results are supported by electron microscopy characterization of deformed microstructures. A Haasen plot analysis indicates that forest dislocations control the kinetics of deformation in both material conditions. It also reveals the presence of athermal obstacles in both non-charged and H-precharged conditions, likely dense dislocation tangles and cell walls. Additionally, the effect of hydrogen on microstructure evolution (by reducing the propensity for cross slip) leads to a dependence of athermal stress on plastic strain amplitude.

Activation area↗

Microwave-Assisted Plastic Upcycling: Dynamic Data Reconciliation, Parameter Estimation, and Kinetic Modeling

Microwave (MW)-assisted catalytic pyrolysis offers a promising pathway for efficient plastic upcycling. This work develops an integrated modeling framework combining dynamic data reconciliation, a temperature-dependent rate model, and a yield model to represent the time-varying production rate of components in MW-assisted LDPE pyrolysis conducted in a batch reactor. An Arrhenius-type rate model with a temperature-dependent reaction order is developed. A biexponential correlation is proposed for the yield of gaseous products that enables to capture the evolving product formation behavior during conversion. In the yield correlation, one term is used to represent the initial increase in yield, reflecting the rapid formation of intermediate or primary products at the early stages of the reaction when a larger fraction of the reactant remains available. As conversion progresses, the influence of this term gradually diminishes. The other term accounts for the subsequent decrease in the predicted yield, representing secondary reactions such as further cracking or coke formation that reduce the concentration of certain products at higher conversion. The model is found to accurately represent reconciled experimental flow rate profiles from an in-house MW-assisted catalytic batch reactor for major products, including ethylene, ethane, 1-butene, and benzene, across 250−350 °C. Ethylene remains the dominant product but decreases from about 41.95% at 250 °C to 30.14% at 350 °C, while heavier products increase significantly, with 1-butene rising to nearly 8.37% and benzene reaching 2.17% at intermediate temperatures. The model shows that the ethylene production rate can be maximized at around 270 °C. The models developed in this work can be utilized for process optimization, reactor design and scale-up of microwave-assisted plastic conversion technologies, and economic analysis.

Damahe, Harish [West Virginia Univ., Morgantown, W↗