Estimation of Landfill Gas Generation Rate and Gas Permeability Field of Refuse Using Inverse Modeling

Landfill methane must be captured to reduce emissions of greenhouse gases; moreover it can be used as an alternative energy source. However, despite the widespread use of landfill gas (LFG) collection systems for over three decades, little information about their capture efficiency is available, because LFG generation rates usually remain unknown. Therefore, to assess the efficiency of greenhouse gas capture and to estimate the amount of fugitive emissions, LFG generation rates should be properly determined. In addition, to improve the capture efficiency of methane while minimizing air intrusion from the atmosphere, it is important to quantify gas flow patterns within landfills. In this study, a methodology to quantify methane generation rates and to estimate the gas permeability field was examined using inverse modeling. To account for the heterogeneous, but spatially correlated structure of refuse, the pilot point method involving geostatistical techniques and optimization algorithms was used. Synthetic observation data were generated from forward simulations for a pumping test and a baro-pneumatic test, and these data were used to test the inversion procedure. The inverse model was able to reproduce the spatial permeability distribution using the transient pressure changes in response to the withdrawal of LFG during the pumping test. The LFG generation rate was also successfully estimated using the data from the baro-pneumatic test with errors less than 2%. While this methodology was developed and successfully tested using synthetic data, it will be investigated in the future using field data from the bioreactor test cells at the Yolo County Central Landfill, CA.     

A Direct Approach to Organic/Inorganic Semiconductor Hybrid Particles via Functionalized Polyfluorene Ligands

Controlled Suzuki–Miyaura coupling polymerization of 7′‐bromo‐9′,9′‐dioctyl‐fluoren‐2′‐yl‐4,4,5,5‐tetramethyl‐[1,3,2]dioxaborolane initiated by bromo(4‐tert‐butoxycarbonylamino‐phenyl)(tri‐tert‐butylphosphine)palladium ( 1 ) or bromo(4‐diethoxyphosphoryl‐phenyl)(tri‐tert‐butylphosphine)palladium ( 2 ) yields functionalized polyfluorenes (M_n = 4 × 10³ g mol^?1, M_w/M_n < 1.2) with a single amine or phosphonic acid, respectively, end‐group. High temperature synthesis of cadmium selenide quantum dots with these functionalized polyfluorenes as stabilizing ligands yields hybrid particles consisting of good quality (e.g. emission full width at half maximum of 30 nm; size distribution σ < 10%) inorganic nanocrystals with polyfluorene attached to the surface, as corroborated by transmission electron microscopy analysis and analytical ultracentrifugation. Sedimentation studies on particle dispersions show that a substantial portion (ca. half) of the phosphonic acid terminated polyfluorene ligands is bound to the inorganic nanocrystals, versus ca. 5% for the amino‐functionalized polyfluorene ligands. Single particle micro‐photoluminescence spectroscopy shows an efficient and complete energy transfer from the polyfluorene layer to the inorganic quantum dot.     

High Precision,Electrochemical Detection of Reversible Binding of Recombinant Proteins on Wide Bandgap GaN Electrodes Functionalized with Biomembrane Models

We report a novel hybrid charge sensor realized by the deposition of phospholipid monolayers on highly doped n‐GaN electrodes. To detect the binding of recombinant proteins with histidine‐tags, lipid vesicles containing chelator lipids were deposited on GaN electrodes pre‐coated with octadecyltrimethoxysilane monolayers. Owing to its optical transparency, GaN allows the confirmation of the fluidity of supported membranes by fluorescence recovery after photo‐bleaching (FRAP). The electrolyte‐(organic) insulator‐semiconductor (EIS) setup enables one to transduce variations in the surface charge density ΔQ into a change in the interface capacitance ΔC _p and, thus, the flat‐band potential ΔU _FB. The obtained results demonstrate that the membrane‐based charge sensor can reach a high sensitivity to detect reversible changes in the surface charge density on the membranes by the formation of chelator complexes, docking of eGFP with histidine tags, and cancellation by EDTA. The achievable resolution of ΔQ ≥ 0.1 μC/cm² is better than that obtained for membrane‐functionalized p‐GaAs, 0.9 μC/cm², and for ITO coated with a polymer supported lipid monolayer, 2.2 μC/cm². Moreover, we examined the potential application of optically active InGaN/GaN quantum dot structures, for the detection of changes in the surface potential from the photoluminescence signals measured at room temperature.     

Carbon‐Based Anodes for Lithium Sulfur Full Cells with High Cycle Stability

The lithium sulfur battery system has been studied since the late 1970s and has seen renewed interest in recent years. However, even after three decades of intensive research, prolonged cycling can only be achieved when a large excess of electrolyte and lithium is used. Here, for the first time, a balanced and stable lithium sulfur full cell is demonstrated with silicon–carbon as well as all‐carbon anodes. More than 1000 cycles, a specific capacity up to 1470 mAh g^?1 _sulfur (720 mAh g^?1 _cathode), and a high coulombic efficiency of over 99% even with a low amount of electrolyte are achieved. The alternative anodes do not suffer from electrolyte depletion, which is found to be the main cause of cell failure when using metallic lithium anodes.     

Mechanism of Crystallization and Implications for Charge Transport in Poly(3‐ethylhexylthiophene) Thin Films

In this work, crystallization kinetics and aggregate growth of poly(3‐ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X‐ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time‐dependent, field‐effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter‐aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.     

Cellulose‐Based Ionogels for Paper Electronics

A new class of biofriendly ionogels produced by gelation of microcellulose thin films with tailored 1‐ethyl‐3‐methylimidazolium methylphosphonate ionic liquids are demonstrated. The cellulose ionogels show promising properties for application in flexible electronics, such as transparency, flexibility, transferability, and high specific capacitances of 5 to 15 μF cm^?2. They can be laminated onto any substrate such as multilayer‐coated paper and act as high capacitance dielectrics for inorganic (spray‐coated ZnO and colloidal ZnO nanorods) and organic (poly[3‐hexylthiophene], P3HT) electrolyte‐gated field‐effect transistors (FETs), that operate at very low voltages (<2 V). Field‐effect mobilities in ionogel‐gated spray‐coated ZnO FETs reach 75 cm² V^?1 s^?1 and a typical increase of mobility with decreasing specific capacitance of the ionogel is observed. Solution‐processed, colloidal ZnO nanorods and laminated cellulose ionogels enable the fabrication of the first electrolyte‐gated, flexible circuits on paper, which operate at bending radii down to 1.1 mm.     

Derivation of mean-field equations for stochastic particle systems

We study stochastic particle systems on a complete graph and derive effective mean-field rate equations in the limit of diverging system size, which are also known from cluster aggregation models. We establish the propagation of chaos under generic growth conditions on particle jump rates, and the limit provides a master equation for the single site dynamics of the particle system, which is a non-linear birth death chain. Conservation of mass in the particle system leads to conservation of the first moment for the limit dynamics, and to non-uniqueness of stationary distributions. Our findings are consistent with recent results on exchange driven growth, and provide a connection between the well studied phenomena of gelation and condensation.     

A Geometric Framework for Stochastic Shape Analysis

We introduce a stochastic model of diffeomorphisms, whose action on a variety of data types descends to stochastic evolution of shapes, images and landmarks. The stochasticity is introduced in the vector field which transports the data in the large deformation diffeomorphic metric mapping framework for shape analysis and image registration. The stochasticity thereby models errors or uncertainties of the flow in following the prescribed deformation velocity. The approach is illustrated in the example of finite-dimensional landmark manifolds, whose stochastic evolution is studied both via the Fokker–Planck equation and by numerical simulations. We derive two approaches for inferring parameters of the stochastic model from landmark configurations observed at discrete time points. The first of the two approaches matches moments of the Fokker–Planck equation to sample moments of the data, while the second approach employs an expectation-maximization based algorithm using a Monte Carlo bridge sampling scheme to optimise the data likelihood. We derive and numerically test the ability of the two approaches to infer the spatial correlation length of the underlying noise.