On the equivalence of the mechanisms governing switching and hysteresis phenomena

The nucleation and growth model, which is usually applied to switching phenomena, is adapted for explaining surface potential measurements on the P(VDF-TrFE) (polyvinylidene fluoride-trifluoroethylene) copolymer obtained in a constant current corona triode. It is shown that the growth is one-dimensional and that the nucleation rate is unimportant, probably because surface potential measurements take much longer than the switching ones. The surface potential data can therefore be accounted for by a growth model in which the velocity of growth varies exponentially with the electric field. Since hysteresis loops can be obtained from surface potential measurements, it is suggested that similar mechanisms can be used when treating switching and hysteresis phenomena, provided that account is taken of the difference in the time scale of the measurements.

Modulational instability analysis of surface-waves in the Bénard-Marangoni phenomenon

By using the long-wave approximation, a system of coupled evolutions equations for the bulk velocity and the surface perturbations of a Bénard-Marangoni system is obtained. It includes nonlinearity, dispersion and dissipation, and it is interpreted as a dissipative generalization of the usual Boussinesq system of equations. Then, by considering that the Marangoni number is near the critical value M = -12, we show that the modulation of the Boussinesq waves is described by a perturbed Nonlinear Schrödinger Equation, and we study the conditions under which a Benjamin-Feir instability could eventually set in. The results give sufficient conditions for stability, but are inconclusive about the existence or not of a Benjamin-Feir instability in the long-wave limit. © 1995.

Study of the phenomena of fatigue using the finite element method

About 99% of mechanical failures are consequence of the phenomena of fatigue, which consists on the progressive weakening of the resistant section of a mechanical component due to the growing of cracks caused by fluctuating loadings. A broad diversity of factors influences the fatigue life of a mechanical component, like the surface finishing, scale factors, among others, but none is as significantly as the presence of geometric severities. Stress concentrators are places where fatigue cracks have a greater probability to occur, and so on, the intuit of this work is to develop a consistent and trustfully methodology to determine the theoretical stress concentration factor of mechanical components. Copyright © 2007 SAE International.

Local and regional features of surface radiation fluxes over the tropical Atlantic ocean near Sao Pedro and Sao Paulo archipelago: Evidence of small scale upwelling

To properly describe the interactions between the ocean and atmosphere, it is necessary to assess a variety of time and spatial scales phenomena. Here, high resolution oceanographic and meteorological data collected during an observational campaign carried out aboard a ship in the tropical Atlantic Ocean, on May 15-24, 2002, is used to describe the radiation balance at the ocean interface. Data collected by two PIRATA buoys, along the equator at 23°W and 35°W and satellite and climate data are compared with the data obtained during the observational campaign. Comparison indicates remarkable similarity for daily and hourly values of radiation fluxes components as consequence of the temporal and spatial consistence presented by the air and water temperatures measured in situ and estimated from large scale information. The discrepancy, mainly in the Sao Pedro and Sao Paulo Archipelago area, seems to be associated to the local upwelling of cold water, which is not detected in all other estimates investigated here. More in situ data are necessary to clarify whether this upwelling flow has a larger scale effect and what are the meteorological and oceanographic implications of the local upwelling area on the tropical waters at the Brazilian coast.

Organic acids and protein compounds causing the photoluminescence properties of natural rubber membranes and the quenching phenomena from Au nanoparticle incorporation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Experimental investigations of heat transfer coefficients of cutting fluids in metal cutting processes: analysis of workpiece phenomena in a given case study

This paper reports an experimental method to estimate the convective heat transfer of cutting fluids in a laminar flow regime applied on a thin steel plate. The heat source provided by the metal cutting was simulated by electrical heating of the plate. Three different cooling conditions were evaluated: a dry cooling system, a flooded cooling system and a minimum quantity of lubrication cooling system, as well as two different cutting fluids for the last two systems. The results showed considerable enhancement of convective heat transfer using the flooded system. For the dry and minimum quantity of lubrication systems, the heat conduction inside the body was much faster than the heat convection away from its surface. In addition, using the Biot number, the possible models were analyzed for conduction heat problems for each experimental condition tested.

Application of the log-conformation tensor to three-dimensional time-dependent free surface flows

The numerical simulation of flows of highly elastic fluids has been the subject of intense research over the past decades with important industrial applications. Therefore, many efforts have been made to improve the convergence capabilities of the numerical methods employed to simulate viscoelastic fluid flows. An important contribution for the solution of the High-Weissenberg Number Problem has been presented by Fattal and Kupferman [J. Non-Newton. Fluid. Mech. 123 (2004) 281-285] who developed the matrix-logarithm of the conformation tensor technique, henceforth called log-conformation tensor. Its advantage is a better approximation of the large growth of the stress tensor that occur in some regions of the flow and it is doubly beneficial in that it ensures physically correct stress fields, allowing converged computations at high Weissenberg number flows. In this work we investigate the application of the log-conformation tensor to three-dimensional unsteady free surface flows. The log-conformation tensor formulation was applied to solve the Upper-Convected Maxwell (UCM) constitutive equation while the momentum equation was solved using a finite difference Marker-and-Cell type method. The resulting developed code is validated by comparing the log-conformation results with the analytic solution for fully developed pipe flows. To illustrate the stability of the log-conformation tensor approach in solving three-dimensional free surface flows, results from the simulation of the extrudate swell and jet buckling phenomena of UCM fluids at high Weissenberg numbers are presented. (C) 2012 Elsevier B.V. All rights reserved.

Sulfur Radicals as Tethers for the Adsorption of Aromatic Molecules on Silicon Surface

In this work we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of benzenethiol and diphenyl disulfide with the silicon (001) surface. A direct comparison of different adsorption structures with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) allow us to identify that benzenethiol and diphenyl disulfide dissociatively adsorb on the silicon surface. In addition, theoretically obtained data suggests that the C6H5SH:Si(001) presents a higher Schottky barrier height contact when compared to other similar aromatic molecules.

Study of surface free energy on a lattice-gas model applied to Liquid bridge

The pulmonary crackling and the formation of liquid bridges are problems that for centuries have been attracting the attention of scientists. In order to study these phenomena, it was developed a canonical cubic lattice-gas­ like model to explain the rupture of liquid bridges in lung airways [A. Alencar et al., 2006, PRE]. Here, we further develop this model and add entropy analysis to study thermodynamic properties, such as free energy and force. The simulations were performed using the Monte Carlo method with Metropolis algorithm. The exchange between gas and liquid particles were performed randomly according to the Kawasaki dynamics and weighted by the Boltzmann factor. Each particle, which can be solid (s), liquid (l) or gas (g), has 26 neighbors: 6 + 12 + 8, with distances 1, √2 and √3, respectively. The energy of a lattice's site m is calculated by the following expression: Em = ∑k=126 Ji(m)j(k) in witch (i, j) = g, l or s. Specifically, it was studied the surface free energy of the liquid bridge, trapped between two planes, when its height is changed. For that, was considered two methods. First, just the internal energy was calculated. Then was considered the entropy. It was fond no difference in the surface free energy between this two methods. We calculate the liquid bridge force between the two planes using the numerical surface free energy. This force is strong for small height, and decreases as the distance between the two planes, height, is increased. The liquid-gas system was also characterized studying the variation of internal energy and heat capacity with the temperature. For that, was performed simulation with the same proportion of liquid and gas particle, but different lattice size. The scale of the liquid-gas system was also studied, for low temperature, using different values to the interaction Jij.

Modeling of complex chemical reactions and macromolecular orientation phenomena in confined geometries

The cooperative motion algorithm was applied on the molecular simulation of complex chemical reactions and macromolecular orientation phenomena in confined geometries. First, we investigated the case of equilibrium step-growth polymerization in lamellae, pores and droplets. In such systems, confinement was quantified as the area/volume ratio. Results showed that, as confinement increases, polymerization becomes slower and the average molecular weight (MW) at equilibrium decreases. This is caused by the sterical hindrance imposed by the walls since chain growth reactions in their close vicinity have less realization possibilities. For reactions inside droplets at surfaces, contact angles usually increased after polymerization to compensate conformation restrictions imposed by confinement upon growing chains. In a second investigation, we considered monodisperse and chemically inert chains and focused on the effect of confinement on chain orientation. Simulations of thin polymer films showed that chains are preferably oriented parallel to the surface. Orientation increases as MW increases or as film thickness d decreases, in qualitative agreement with experiments with low MW polystyrene. It is demonstrated that the orientation of simulated chains results from a size effect, being a function of the ratio between chain end-to-end distance and d. This study was complemented by experiments with thin films of pi-conjugated polymers like MEH-PPV. Anisotropic refractive index measurements were used to analyze chain orientation. With increasing MW, orientation is enhanced. However, for MEH-PPV, orientation does not depend on d even at thicknesses much larger than the chain contour length. This contradiction with simulations was discussed by considering additional causes for orientation, for instance the appearance of nematic-like ordering in polymer films. In another investigation, we simulated droplet evaporation at soluble surfaces and reproduced the formation of wells surrounded by ringlike deposits at the surface, as observed experimentally. In our simulations, swollen substrate particles migrate to the border of the droplet to minimize the contact between solvent and vacuum, which costs the most energy. Deposit formation in the beginning of evaporation results in pinning of the droplet. When polymer chains at the substrate surface have strong uniaxial orientation, the resulting pattern is no longer similar to a ring but to a pair of half-moons. In a final stage, as an extension for the model developed for polymerization in nanoreactors, we studied the effect of geometrical confinement on a hypothetical oscillating reaction following the mechanism of the so called periodically forced Brusselator. It was shown that a reaction which is chaotic in the bulk may be driven to periodicity by confinement and vice-versa, opening new perspectives for chaos control.

Polymer-nanoparticle composites: from orientation phenomena to optoelectronic applications

Polymer-nanoparticle hybrids show synergistic effects, demonstrating both, the unique properties of nanosized structures and the good processability and functionalities of polymeric materials. This work shows the synthesis and application of block copolymers containing a soluble, functional block and a short anchor block, which efficiently binds to the surface of nanocrystals. We functionalized anisotropic, semiconducting nanoparticles, which can be dissolved in organic and polymeric matrices upon modification. The modified nanorods have the ability to form liquid crystalline phases, which behave similar to low molecular liquid crystals with a reversible clearing behaviour. These liquid crystalline phases could also be obtained in hole conducting matrices. For a macroscopic orientation of the nanorods, electric fields were applied and a switching (in analogy to known liquid crystals) to a homeotropic orientation was observed.rnBy introduction of dye molecules in the anchor block of a hole conducting block copolymer, all essential components of a solar cell can be combined in a single particle. Light absorption of the dye induces the injection of electrons into the particles, followed by a charging, that was monitored by a special AFM technique.rnLight emitting nanocrystals were functionalized analogously with a hole transporting polymer. The stability of the particles could be enhanced by the sterically stabilizing polymer corona and the particles showed improved properties in terms of processing. We applied these hybrid materials in light emitting devices, which showed better characteristics due to an improved hole injection and well dispersed emitting particles in the active device layer.rnThe work shows the broad spectrum of properties and applications based on the synergistic effects in hybrid and composite materials.

Multifunctional polyether architectures : versatile materials for surface attachment and functionalization

Chapter 1 of this thesis comprises a review of polyether polyamines, i.e., combinations of polyether scaffolds with polymers bearing multiple amino moieties. Focus is laid on controlled or living polymerization methods. Furthermore, fields in which the combination of cationic, complexing, and pH-sensitive properties of the polyamines and biocompatibility and water-solubility of polyethers promise enormous potential are presented. Applications include stimuli-responsive polymers with a lower critical solution temperature (LCST) and/or the ability to gel, preparation of shell cross-linked (SCL) micelles, gene transfection, and surface functionalization.rnIn Chapter 2, multiaminofunctional polyethers relying on the class of glycidyl amine comonomers for anionic ring-opening polymerization (AROP) are presented. In Chapter 2.1, N,N-diethyl glycidyl amine (DEGA) is introduced for copolymerization with ethylene oxide (EO). Copolymer microstructure is assessed using online 1H NMR kinetics, 13C NMR triad sequence analysis, and differential scanning calorimetry (DSC). The concurrent copolymerization of EO and DEGA is found to result in macromolecules with a gradient structure. The LCSTs of the resulting copolymers can be tailored by adjusting DEGA fraction or pH value of the environment. Quaternization of the amino moieties by methylation results in polyelectrolytes. Block copolymers are used for PEGylated gold nanoparticle formation. Chapter 2.2 deals with a glycidyl amine monomer with a removable protecting group at the amino moiety, for liberation of primary amines at the polyether backbone, which is N,N-diallyl glycidyl amine (DAGA). Its allyl groups are able to withstand the harsh basic conditions of AROP, but can be cleaved homogeneously after polymerization. Gradient as well as block copolymers poly(ethylene glycol)-PDAGA (PEG-PDAGA) are obtained. They are analyzed regarding their microstructure, LCST behavior, and cleavage of the protecting groups. rnChapter 3 describes applications of multi(amino)functional polyethers for functionalization of inorganic surfaces. In Chapter 3.1, they are combined with an acetal-protected catechol initiator, leading to well-defined PEG and heteromultifunctional PEG analogues. After deprotection, multifunctional PEG ligands capable of attaching to a variety of metal oxide surfaces are obtained. In a cooperative project with the Department of Inorganic and Analytical Chemistry, JGU Mainz, their potential is demonstrated on MnO nanoparticles, which are promising candidates as T1 contrast agents in magnetic resonance imaging. The MnO nanoparticles are solubilized in aqueous solution upon ligand exchange. In Chapter 3.2, a concept for passivation and functionalization of glass surfaces towards gold nanorods is developed. Quaternized mPEG-b-PqDEGA diblock copolymers are attached to negatively charged glass surfaces via the cationic PqDEGA blocks. The PEG blocks are able to suppress gold nanorod adsorption on the glass in the flow cell, analyzed by dark field microscopy.rnChapter 4 highlights a straightforward approach to poly(ethylene glycol) macrocycles. Starting from commercially available bishydroxy-PEG, cyclic polymers are available by perallylation and ring-closing metathesis in presence of Grubbs’ catalyst. Purification of cyclic PEG is carried out using α-cyclodextrin. This cyclic sugar derivative forms inclusion complexes with remaining unreacted linear PEG in aqueous solution. Simple filtration leads to pure macrocycles, as evidenced by SEC and MALDI-ToF mass spectrometry. Cyclic polymers from biocompatible precursors are interesting materials regarding their increased blood circulation time compared to their linear counterparts.rnIn the Appendix, A.1, a study of the temperature-dependent water-solubility of polyether copolymers is presented. Macroscopic cloud points, determined by turbidimetry, are compared with microscopic aggregation phenomena, monitored by continuous wave electron paramagnetic resonance (CW EPR) spectroscopy in presence of the amphiphilic spin probe and model drug (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). These thermoresponsive polymers are promising candidates for molecular transport applications. The same techniques are applied in Chapter A.2 to explore the pH-dependence of the cloud points of PEG-PDEGA copolymers in further detail. It is shown that the introduction of amino moieties at the PEG backbone allows for precise manipulation of complex phase transition modes. In Chapter A.3, multi-hydroxyfunctional polysilanes are presented. They are obtained via copolymerization of the acetal-protected dichloro(isopropylidene glyceryl propyl ether)methylsilane monomer. The hydroxyl groups are liberated through acidic work-up, yielding versatile access to new multifunctional polysilanes.

Two-Phase Flow In Microchannels: Morphology And Interface Phenomena

The existence and morphology, as well as the dynamics of micro-scale gas-liquid interfaces is investigated numerically and experimentally. These studies can be used to assess liquid management issues in microsystems such as PEMFC gas flow channels, and are meant to open new research perspectives in two-phase flow, particularly in film deposition on non-wetting surfaces. For example the critical plug volume data can be used to deliver desired length plugs, or to determine the plug formation frequency. The dynamics of gas-liquid interfaces, of interest for applications involving small passages (e.g. heat exchangers, phase separators and filtration systems), was investigated using high-speed microscopy - a method that also proved useful for the study of film deposition processes. The existence limit for a liquid plug forming in a mixed wetting channel is determined by numerical simulations using Surface Evolver. The plug model simulate actual conditions in the gas flow channels of PEM fuel cells, the wetting of the gas diffusion layer (GDL) side of the channel being different from the wetting of the bipolar plate walls. The minimum plug volume, denoted as critical volume is computed for a series of GDL and bipolar plate wetting properties. Critical volume data is meant to assist in the water management of PEMFC, when corroborated with experimental data. The effect of cross section geometry is assessed by computing the critical volume in square and trapezoidal channels. Droplet simulations show that water can be passively removed from the GDL surface towards the bipolar plate if we take advantage on differing wetting properties between the two surfaces, to possibly avoid the gas transport blockage through the GDL. High speed microscopy was employed in two-phase and film deposition experiments with water in round and square capillary tubes. Periodic interface destabilization was observed and the existence of compression waves in the gas phase is discussed by taking into consideration a naturally occurring convergent-divergent nozzle formed by the flowing liquid phase. The effect of channel geometry and wetting properties was investigated through two-phase water-air flow in square and round microchannels, having three static contact angles of 20, 80 and 105 degrees. Four different flow regimes are observed for a fixed flow rate, this being thought to be caused by the wetting behavior of liquid flowing in the corners as well as the liquid film stability. Film deposition experiments in wetting and non-wetting round microchannels show that a thicker film is deposited for wetting conditions departing from the ideal 0 degrees contact angle. A film thickness dependence with the contact angle theta as well as the Capillary number, in the form h_R ~ Ca^(2/3)/ cos(theta) is inferred from scaling arguments, for contact angles smaller than 36 degrees. Non-wetting film deposition experiments reveal that a film significantly thicker than the wetting Bretherton film is deposited. A hydraulic jump occurs if critical conditions are met, as given by a proposed nondimensional parameter similar to the Froude number. Film thickness correlations are also found by matching the measured and the proposed velocity derived in the shock theory. The surface wetting as well as the presence of the shock cause morphological changes in the Taylor bubble flow.

Surface Deformations as Indicators of Deep Ebullition Fluxes in a Large Northern Peatland

Peatlands deform elastically during precipitation cycles by small (+/- 3 cm) oscillations in surface elevation. In contrast, we used a Global Positioning System network to measure larger oscillations that exceeded 20 cm over periods of 4 - 12 hours during two seasonal droughts at a bog and fen site in northern Minnesota. The second summer drought also triggered 19 depressuring cycles in an overpressured stratum under the bog site. The synchronicity between the largest surface deformations and the depressuring cycles indicates that both phenomena are produced by the episodic release of large volumes of gas from deep semi-elastic compartments confined by dense wood layers. We calculate that the three largest surface deformations were associated with the release of 136 g CH4 m(-2), which exceeds by an order of magnitude the annual average chamber fluxes measured at this site. Ebullition of gas from the deep peat may therefore be a large and previously unrecognized source of radiocarbon depleted methane emissions from northern peatlands.

First thoughts on surface tonal patterns in Amawaka, a Panoan language of Peru and Brazil

Amawaka ([ɑmɨ̃ˈwɐkɑ]) is a highly endangered and underdocumented tonal language of the Headwaters (Fleck 2011) subgroup of the Panoan family in the Southwest Amazon Basin, spoken by approximately 200 people. Undocumented phonetic and phonological phenomena of Amawaka include its tonal structure, both in terms of surface realizations and the patterns underlying these realizations. Original audiovisual data from the author’s fieldwork in various Amawaka communities at the Peru-Brazil border will illuminate the as-yet obscure tonal systematicity of the language. Unlike other elements, monosyllabic bimoraic phonological nominal words with long vowels display variation in their surface realization. All the words with the open back unrounded /ɑ/, like /ˈkɑ̀:/ (patarashca, a traditional Amazonian dish), /ˈnɑ̀:/ “mestizo” etc. [with the exception of /ˈtɑ:/ “reed”, which surfaces with either a H or L tone] bear a low tone in isolation. This realization contrasts with all the encountered nominal monosyllables with vowels from the close and close-mid front and central spectrum /i, ɘ, ɨ, ɨ̃/, which clearly surface as high tone words in isolation, for example /ˈmɨ̃́:/ (a clay-lick for animals), /ˈwí:/ “Anopheles, spp. mosquito”. Monosyllables with close-mid back rounded /o/ have a less restrictive pitch that varies among speakers from low to high realizations, and sometimes even across the speech tokens from an individual speaker, e.g. /wó:/ or /wō:/ “hair”, /ɧō:/ or /ɧò:/ (a type of tarantula). Phrasal tonal phonology is more complex, when these three kinds of monosyllables appear in larger noun phrases. Some retain the same surface tones as their isolation form, while others seem to vary freely in their surface realization, e.g. /ˈtɘ́:.nɑ̀:/ or /ˈtɘ́:.nɑ́:/ ‘one mestizo’. Yet other monosyllables, e.g. /mɑ̀:/, exhibit a falling tone when preceded by a H syllable, suggesting probably latent tone sandhi phenomena, e.g /ˈtɘ́:.mɑ̂:/ (one clay-lick for parrots). In disyllabic, trisyllabic and quadrisyllabic nouns, tonal and stress patterns generally seem to be more consistent and tend to be retained both in isolation and in larger intonational phrases. Disyllabic nouns, for instance, surface as L-H or L-L when a glottal stop is in coda position. The association of L with a glottal stop is a feature that occurs in other Panoan languages as well, like Capanahua (Loos 1969), and more generally it is an areal feature, found in other parts of Amazonia (Hyman 2010). So, tone has significant interactions with the glottal stop and glottalization, which generally co-occurs with L. The data above suggest that the underlying tonal system of Amawaka is much more complex than the privative one-tone analysis (/H/ vs. Ø, i.e. lack of tone) that was proposed by Russell and Russell (1959). Evidence from field data suggests either an equipollent (Hyman 2010) two-tone opposition between /H/ and /L/, or a hybrid system, with both equipollent and privative features; that is, /H/ vs. /L/ vs. either Ø or /M/. This first systematic description of Amawaka tone, in conjunction with ongoing research, is poised to address broader questions concerning interrelationships between surface/underlying tone and other suprasegmental features, such as nasality, metrical stress, and intonation. References Fleck, David W. 2011. Panoan languages and linguistics. In Javier Ruedas and David W. Fleck (Eds.), Panoan Histories and Interethnic Identities, To appear. Hyman, Larry. 2010. Amazonia and the typology of tone systems. Presented at the conference Amazonicas III: The structure of the Amazonian languages. Bogotá. Loos, Eugene E. 1969. The phonology of Capanahua and its grammatical basis. Norman: SIL and U. Oklahoma. Russell, Robert & Dolores. 1959. Syntactotonemics in Amahuaca (Pano). Série Lingüistica Especial, 128-167. Publicaçoes do Museu Nacional, Rio de Janeiro, Brasil.