On the initiation of boudinage and folding instabilities in layered elasto-visco-plastic solids - Insights from natural microstructures and numerical simulations

The present understanding of the initiation of boudinage and folding structures is based on viscosity contrasts and stress exponents, considering an intrinsically unstable state of the layer. The criterion of localization is believed to be prescribed by geometry-material interactions, which are often encountered in natural structures. An alternative localization phenomenon has been established for ductile materials, in which instability emerges for critical material parameters and loading rates from homogeneous conditions. In this thesis, conditions are sought under which this type of instability prevails and whether localization in geological materials necessarily requires a trigger by geometric imperfections. The relevance of critical deformation conditions, material parameters and the spatial configuration of instabilities are discussed in a geological context. In order to analyze boudinage geometries, a numerical eigenmode analysis is introduced. This method allows determining natural frequencies and wavelengths of a structure and inducing perturbations on these frequencies. In the subsequent coupled thermo-mechanical simulations, using a grain size evolution and end-member flow laws, localization emerges when material softening through grain size sensitive viscous creep sets in. Pinch-and-swell structures evolve along slip lines through a positive feedback between the matrix response and material bifurcations inside the layer, independent from the mesh-discretization length scale. Since boudinage and folding are considered to express the same general instability, both structures should arise independently of the sign of the loading conditions and for identical material parameters. To this end, the link between material to energy instabilities is approached by means of bifurcation analyses of the field equations and finite element simulations of the coupled system of equations. Boudinage and folding structures develop at the same critical energy threshold, where dissipative work by temperature-sensitive creep overcomes the diffusive capacity of the layer. This finding provides basis for a unified theory for strain localization in layered ductile materials. The numerical simulations are compared to natural pinch-and-swell microstructures, tracing the adaption of grain sizes, textures and creep mechanisms in calcite veins. The switch from dislocation to diffusion creep relates to strain-rate weakening, which is induced by dissipated heat from grain size reduction, and marks the onset of continuous necking. The time-dependent sequence uncovers multiple steady states at different time intervals. Microstructurally and mechanically stable conditions are finally expressed in the pinch-and-swell end members. The major outcome of this study is that boudinage and folding can be described as the same coupled energy-mechanical bifurcation, or as one critical energy attractor. This finding allows the derivation of critical deformation conditions and fundamental material parameters directly from localized structures in the field.

(Table 1) Conditions of vertical near-bottom profiling and the main parameters of the benthic boundary layer in several regions of the Black Sea shelf

Measurements of 14 vertical profiles of currents and hydrological parameters in the near-bottom layer with depth resolution of 0.1 m were carried out in several regions of the Black Sea shelf, at five points over the continental slope, and in three deep water regions. The upper boundary of the benthic boundary layer (BBL) was reliably determined at a point at distance from 5-7 to 35-40 m from the bottom where the gradients of density and current velocity changed. Experimental data obtained were used to determine the coefficient of bottom friction, friction velocity, coefficients of vertical diffusion of momentum and density, and vertical fluxes of temperature and salinity in the BBL.

(Table S1) FMR and rock magnetic parameters for upper Paleocene to lower Eocene strata, Site Ancora

Previous workers identified a magnetically anomalous clay layer deposited on the northern United States Atlantic Coastal Plain during the Paleocene-Eocene thermal maximum (PETM). The finding inspired the highly controversial hypothesis that a cometary impact triggered the PETM. Here we present ferromagnetic resonance (FMR), isothermal and anhysteretic remanent magnetization, first-order reversal curve, and transmission electron microscopy analyses of late Paleocene and early Eocene sediments in drill core from Ancora, New Jersey. A novel paleogeographic analysis applying a recent paleomagnetic pole from the Faeroe Islands indicates that New Jersey during the initial Eocene had a ~6°-9° lower paleolatitude (~27.3° for Ancora) and a more zonal shoreline trace than in conventional reconstructions. Our investigations of the PETM clay from Ancora reveal abundant magnetite nanoparticles bearing signature traits of crystals produced by magnetotactic bacteria. This result, the first identification of ancient biogenic magnetite using FMR, argues that the anomalous magnetic properties of the PETM sediments are not produced by an impact. They instead reflect environmental changes along the eastern margin of North America during the PETM that led to enhanced production and/or preservation of magnetofossils.

Back-calculation of layer parameters for LTPP test sections.

"October 2002."

Aquatic passive sampling of herbicides on naked particle loaded membranes: Accelerated measurement and empirical estimation of kinetic parameters

Water-sampler equilibrium partitioning coefficients and aqueous boundary layer mass transfer coefficients for atrazine, diuron, hexazionone and fluometuron onto C18 and SDB-RPS Empore disk-based aquatic passive samplers have been determined experimentally under a laminar flow regime (Re = 5400). The method involved accelerating the time to equilibrium of the samplers by exposing them to three water concentrations, decreasing stepwise to 50% and then 25% of the original concentration. Assuming first-order Fickian kinetics across a rate-limiting aqueous boundary layer, both parameters are determined computationally by unconstrained nonlinear optimization. In addition, a method of estimation of mass transfer coefficients-therefore sampling rates-using the dimensionless Sherwood correlation developed for laminar flow over a flat plate is applied. For each of the herbicides, this correlation is validated to within 40% of the experimental data. The study demonstrates that for trace concentrations (sub 0.1 mu g/L) and these flow conditions, a naked Empore disk performs well as an integrative sampler over short deployments (up to 7 days) for the range of polar herbicides investigated. The SDB-RPS disk allows a longer integrative period than the C18 disk due to its higher sorbent mass and/or its more polar sorbent chemistry. This work also suggests that for certain passive sampler designs, empirical estimation of sampling rates may be possible using correlations that have been available in the chemical engineering literature for some time.

The throughput order of multicast traffics with physical-layer network coding in random wireless ad hoc networks

This paper attempts to address the effectiveness of physical-layer network coding (PNC) on the throughput improvement for multi-hop multicast in random wireless ad hoc networks (WAHNs). We prove that the per session throughput order with PNC is tightly bounded as T((nvmR (n))-1) if m = O(R-2 (n)), where n is the total number of nodes, R(n) is the communication range, and m is the number of destinations for each multicast session. We also show that per-session throughput order with PNC is tight bounded as T(n-1), when m = O(R-2(n)). The results of this paper imply that PNC cannot improve the throughput order of multicast in random WAHNs, which is different from the intuition that PNC may improve the throughput order as it allows simultaneous signal access and combination.

Impulsive Partial Hyperbolic Functional Differential Equations of Fractional Order with State-Dependent Delay

MSC 2010: 26A33, 34A37, 34K37, 34K40, 35R11

Converging evidence that common timing processes underlie temporal-order and simultaneity judgments: a model-based analysis

Perception of simultaneity and temporal order is studied with simultaneity judgment (SJ) and temporal-order judgment (TOJ) tasks. In the former, observers report whether presentation of two stimuli was subjectively simultaneous; in the latter, they report which stimulus was subjectively presented first. SJ and TOJ tasks typically give discrepant results, which has prompted the view that performance is mediated by different processes in each task. We looked at these discrepancies from a model that yields psychometric functions whose parameters characterize the timing, decisional, and response processes involved in SJ and TOJ tasks. We analyzed 12 data sets from published studies in which both tasks had been used in within-subjects designs, all of which had reported differences in performance across tasks. Fitting the model jointly to data from both tasks, we tested the hypothesis that common timing processes sustain simultaneity and temporal order judgments, with differences in performance arising from task-dependent decisional and response processes. The results supported this hypothesis, also showing that model psychometric functions account for aspects of SJ and TOJ data that classical analyses overlook. Implications for research on perception of simultaneity and temporal order are discussed.

Binary Mixtures of 1-Butyl-1-Methylpyrrolidinium Bis{(trifluoromethyl)Sulfonyl}Imide and Aliphatic Nitrile Solvents As Electrolyte for Electrochemical Double Layer Capacitors (Invited).

Electrochemical double layer capacitors (EDLCs), also known as supercapacitors, are promising energy storage devices, especially when considering high power applications [1]. EDLCs can be charged and discharged within seconds [1], feature high power (10 kW·kg-1) and an excellent cycle life (>500,000 cycles). All these properties are a result of the energy storage process of EDLCs, which relies on storing energy by charge separation instead of chemical redox reactions, as utilized in battery systems. Upon charging, double layers are forming at the electrode/electrolyte interface consisting of the electrolyte’s ions and electric charges at the electrode surface.In state-of-the-art EDLC systems activated carbons (AC) are used as active materials and tetraethylammonium tetrafluoroborate ([Et4N][BF4]) dissolved in organic solvents like propylene carbonate (PC) or acetonitrile (ACN) are commonly used as the electrolyte [2]. These combinations of materials allow operative voltages up to 2.7 V - 2.8 V and an energy in the order of 5 Wh·kg-1[3]. The energy of EDLCs is dependent on the square of the operative voltage, thus increasing the usable operative voltage has a strong effect on the delivered energy of the device [1]. Due to their high electrochemical stability, ionic liquids (ILs) were thoroughly investigated as electrolytes for EDLCs, as well as, batteries, enabling high operating voltages as high as 3.2 V - 3.5 V for the former [2]. While their unique ionic structure allows the usage of neat ILs as electrolyte in EDLCs, ILs suffer from low conductivity and high viscosity increasing the intrinsic resistance and, as a result, a lower power output of the device. In order to overcome this issue, the usage of blends of ionic liquids and organic solvents has been considered a feasible strategy as they combine high usable voltages, while still retaining good transport properties at the same time.In our recent work the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide ([Pyrr14][TFSI]) was combined with two nitrile-based organic solvents, namely butyronitrile (BTN) and adiponitrile (ADN), and the resulting blends were investing regarding their usage in electrochemical double layer capacitors [4,5]. Firstly, the physicochemical properties were investigated, showing good transport properties for both blends, which are similar to the state-of-the-art combination of [Et4N][BF4] in PC. Secondly, the electrochemical properties for EDLC application were studied in depth revealing a high electrochemical stability with a maximum operative voltage as high as 3.7 V. In full cells these high voltage organic solvent based electrolytes have a good performance in terms of capacitance and an acceptable equivalent series resistance at cut-off voltages of 3.2 and 3.5 V. However, long term stability tests by float testing revealed stability issues when using a maximum voltage of 3.5 V for prolonged time, whereas at 3.2 V no such issues are observed (Fig. 1).Considering the obtained results, the usage of ADN and BTN blends with [Pyrr14][TFSI] in EDLCs appears to be an interesting alternative to state-of-the-art organic solvent based electrolytes, allowing the usage of higher maximum operative voltages while having similar transport properties to 1 mol∙dm-3 [Et4N][BF4] in PC at the same time.

Kinetics and coverage dependent reaction mechanisms of the copper atomic layer deposition from copper dimethylamino-2-propoxide and diethylzinc

Atomic layer deposition (ALD) has been recognized as a promising method to deposit conformal and uniform thin film of copper for future electronic devices. However, many aspects of the reaction mechanism and the surface chemistry of copper ALD remain unclear. In this paper, we employ plane wave density functional theory (DFT) to study the transmetalation ALD reaction of copper dimethylamino-2-propoxide [Cu(dmap)2] and diethylzinc [Et2Zn] that was realized experimentally by Lee et al. [ Angew. Chem., Int. Ed. 2009, 48, 4536−4539]. We find that the Cu(dmap)2 molecule adsorbs and dissociates through the scission of one or two Cu–O bonds into surface-bound dmap and Cu(dmap) fragments during the copper pulse. As Et2Zn adsorbs on the surface covered with Cu(dmap) and dmap fragments, butane formation and desorption was found to be facilitated by the surrounding ligands, which leads to one reaction mechanism, while the migration of ethyl groups to the surface leads to another reaction mechanism. During both reaction mechanisms, ligand diffusion and reordering are generally endothermic processes, which may result in residual ligands blocking the surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. We also find that the nearby ligands play a cooperative role in lowering the activation energy for formation and desorption of byproducts, which explains the advantage of using organometallic precursors and reducing agents in Cu ALD. The ALD growth rate estimated for the mechanism is consistent with the experimental value of 0.2 Å/cycle. The proposed reaction mechanisms provide insight into ALD processes for copper and other transition metals.

High Precision Plasma Etch for Pattern Transfer: Towards Fluorocarbon Based Atomic Layer Etching

A basic requirement of a plasma etching process is fidelity of the patterned organic materials. In photolithography, a He plasma pretreatment (PPT) based on high ultraviolet and vacuum ultraviolet (UV/VUV) exposure was shown to be successful for roughness reduction of 193nm photoresist (PR). Typical multilayer masks consist of many other organic masking materials in addition to 193nm PR. These materials vary significantly in UV/VUV sensitivity and show, therefore, a different response to the He PPT. A delamination of the nanometer-thin, ion-induced dense amorphous carbon (DAC) layer was observed. Extensive He PPT exposure produces volatile species through UV/VUV induced scissioning. These species are trapped underneath the DAC layer in a subsequent plasma etch (PE), causing a loss of adhesion. Next to stabilizing organic materials, the major goals of this work included to establish and evaluate a cyclic fluorocarbon (FC) based approach for atomic layer etching (ALE) of SiO2 and Si; to characterize the mechanisms involved; and to evaluate the impact of processing parameters. Periodic, short precursor injections allow precise deposition of thin FC films. These films limit the amount of available chemical etchant during subsequent low energy, plasma-based Ar+ ion bombardment, resulting in strongly time-dependent etch rates. In situ ellipsometry showcased the self-limited etching. X-ray photoelectron spectroscopy (XPS) confirms FC film deposition and mixing with the substrate. The cyclic ALE approach is also able to precisely etch Si substrates. A reduced time-dependent etching is seen for Si, likely based on a lower physical sputtering energy threshold. A fluorinated, oxidized surface layer is present during ALE of Si and greatly influences the etch behavior. A reaction of the precursor with the fluorinated substrate upon precursor injection was observed and characterized. The cyclic ALE approach is transferred to a manufacturing scale reactor at IBM Research. Ensuring the transferability to industrial device patterning is crucial for the application of ALE. In addition to device patterning, the cyclic ALE process is employed for oxide removal from Si and SiGe surfaces with the goal of minimal substrate damage and surface residues. The ALE process developed for SiO2 and Si etching did not remove native oxide at the level required. Optimizing the process enabled strong O removal from the surface. Subsequent 90% H2/Ar plasma allow for removal of C and F residues.

TRANSFORMATIONS OF TASK-DEPENDENT PLASTICITY FROM A1 TO HIGHER-ORDER AUDITORY CORTEX

Everyday, humans and animals navigate complex acoustic environments, where multiple sound sources overlap. Somehow, they effortlessly perform an acoustic scene analysis and extract relevant signals from background noise. Constant updating of the behavioral relevance of ambient sounds requires the representation and integration of incoming acoustical information with internal representations such as behavioral goals, expectations and memories of previous sound-meaning associations. Rapid plasticity of auditory representations may contribute to our ability to attend and focus on relevant sounds. In order to better understand how auditory representations are transformed in the brain to incorporate behavioral contextual information, we explored task-dependent plasticity in neural responses recorded at four levels of the auditory cortical processing hierarchy of ferrets: the primary auditory cortex (A1), two higher-order auditory areas (dorsal PEG and ventral-anterior PEG) and dorso-lateral frontal cortex. In one study we explored the laminar profile of rapid-task related plasticity in A1 and found that plasticity occurred at all depths, but was greatest in supragranular layers. This result suggests that rapid task-related plasticity in A1 derives primarily from intracortical modulation of neural selectivity. In two other studies we explored task-dependent plasticity in two higher-order areas of the ferret auditory cortex that may correspond to belt (secondary) and parabelt (tertiary) auditory areas. We found that representations of behaviorally-relevant sounds are progressively enhanced during performance of auditory tasks. These selective enhancement effects became progressively larger as you ascend the auditory cortical hierarchy. We also observed neuronal responses to non-auditory, task-related information (reward timing, expectations) in the parabelt area that were very similar to responses previously described in frontal cortex. These results suggests that auditory representations in the brain are transformed from the more veridical spectrotemporal information encoded in earlier auditory stages to a more abstract representation encoding sound behavioral meaning in higher-order auditory areas and dorso-lateral frontal cortex.

Regimes of spray vaporization and combustion in counterflow configurations

This article addresses the problem of spray vaporization and combustion in axisymmetric opposed-jet configurations involving a stream of hot air counterflowing against a stream of nitrogen carrying a spray of fuel droplets. The Reynolds numbers of the jets are assumed to be large, so that mixing of the two streams is restricted to a thin mixing layer that separates the counterflowing streams. The evolution of the droplets in their feed stream from the injection location is seen to depend fundamentally on the value of the droplet Stokes number, St, defined as the ratio of the droplet acceleration time to the mixing layer strain time close to the stagnation point. Two different regimes of spray vaporization and combustion can be identified depending on the value of St. For values of St below a critical value, equal to 1/4 for dilute sprays with small values of the spray liquid mass loading ratio, the droplets decelerate to approach the gas stagnation plane with a vanishing axial velocity. In this case, the droplets located initially near the axis reach the mixing layer, where they can vaporize due to the heat received from the hot air, producing fuel vapor that can burn with the oxygen in a diffusion flame located on the air side of the mixing layer. The character of the spray combustion is different for values of St of order unity, because the droplets cross the stagnation plane and move into the opposing air stream, reaching distances that are much larger than the mixing layer thickness before they turn around. The vaporization of these crossing droplets, and also the combustion of the fuel vapor generated by them, occur in the hot air stream, without significant effects of molecular diffusion, generating a vaporization-assisted nonpremixed flame that stands on the air side outside the mixing layer. Separate formulations will be given below for these two regimes of combustion, with attention restricted to the near-stagnation-point region, where the solution is self-similar and all variables are only dependent on the distance to the stagnation plane. The resulting formulations display a reduced number of controlling parameters that effectively embody dependences of the structure of the spray flame on spray dilution, droplet inertia, and fuel preferential diffusion. Sample solutions are given for the limiting cases of pure vaporization and of infinitely fast chemistry, with the latter limit formulated in terms of chemistry-free coupling functions that allow for general nonunity Lewis numbers of the fuel vapor.

Unpolarized transverse momentum dependent parton distribution and fragmentation functions at next-to-next-to-leading order

The transverse momentum dependent parton distribution/fragmentation functions (TMDs) are essential in the factorization of a number of processes like Drell-Yan scattering, vector boson production, semi-inclusive deep inelastic scattering, etc. We provide a comprehensive study of unpolarized TMDs at next-to-next-to-leading order, which includes an explicit calculation of these TMDs and an extraction of their matching coefficients onto their integrated analogues, for all flavor combinations. The obtained matching coefficients are important for any kind of phenomenology involving TMDs. In the present study each individual TMD is calculated without any reference to a specific process. We recover the known results for parton distribution functions and provide new results for the fragmentation functions. The results for the gluon transverse momentum dependent fragmentation functions are presented for the first time at one and two loops. We also discuss the structure of singularities of TMD operators and TMD matrix elements, crossing relations between TMD parton distribution functions and TMD fragmentation functions, and renormalization group equations. In addition, we consider the behavior of the matching coefficients at threshold and make a conjecture on their structure to all orders in perturbation theory.