Phase field modeling of electrochemistry II: Kinetics

The kinetic behavior of a phase field model of electrochemistry is explored for advancing (electrodeposition) and receding (electrodissolution) conditions in one dimension. We described the equilibrium behavior of this model in [J. E. Guyer, W. J. Boettinger, J.A. Warren, and G. B. McFadden, ``Phase field modeling of electrochemistry I: Equilibrium'', cond-mat/0308173]. We examine the relationship between the parameters of the phase field method and the more typical parameters of electrochemistry. We demonstrate ohmic conduction in the electrode and ionic conduction in the electrolyte. We find that, despite making simple, linear dynamic postulates, we obtain the nonlinear relationship between current and overpotential predicted by the classical ``Butler-Volmer'' equation and observed in electrochemical experiments. The charge distribution in the interfacial double layer changes with the passage of current and, at sufficiently high currents, we find that the diffusion limited deposition of a more noble cation leads to alloy deposition with less noble species.Comment: v3: To be published in Phys. Rev. E v2: Attempt to work around turnpage bug. Replaced color Fig. 4a with grayscale 13 pages, 7 figures in 10 files, REVTeX 4, SIunits.sty, follows cond-mat/030817

Auswirkungen von PEN, einem Extrakt aus der Biomasse von Penicillium chrysogenum, auf Pathogene und Pflanzen

Der Ersatz von Kupfer und anderen Pestiziden ist eine der dringlichen Aufgaben der Forschung im biologischen Landbau. Beim direkten Pflanzenschutz stehen fungizid wirkende Substanzen, Biocontrol-Organismen und Pflanzenstärkungsmittel zur Diskussion. Das Konzept der Pflanzenstärkung ist seit langem im biologischen Landbau bekannt. Beispielsweise werden Kompostextrakte, Brennesselextrakte, aber auch kommerzialisierte Produkte aus Reynoutria sachalinensis oder Backpulver eingesetzt. Unter den Resistenzinduktoren (Elicitoren) sind vor allem diejenigen von grossem Interesse, die Resistenz gegen Pathogene auslösen, die ansonsten mit Kupfer bekämpft werden (Tamm, 2000). Der Dünger Agro Biosol (Biochemie GmbH, A-Kundl) weist nebst einer Düngerwirkung auch krankheitsvermindernde Eigenschaften auf. Dies legen Beobachtungen nahe, die bereits in den achtziger Jahren auf Grasflächen gemacht wurden, die mit Fusarium nivale befallen waren. Das aus der Penicillinproduktion gewonnene Trockenmycel ist frei von Penicillin. Agro Biosol enthält 6 % Gesamtstickstoff, 1 % Gesamtphosphor, 1 % Kali, sowie Spurenelemente und Vitamine (Naschberger, pers. Mitteilung). In der Schweiz ist Agro Biosol als Dünger im biologischen Landbau zugelassen (Tamm, Maurer & Alföldi, 2000). E. Mösinger (Sandoz Agro, CH - Witterswil) führte erste Versuche über die krankheitsunterdrückende Wirkung von Agro Biosol durch. Dazu wurde ein Extrakt des Trockenmycels von P. chrysogenum hergestellt, der die Kurzbezeichnung ‚PEN’ erhielt. Diese Untersuchungen von Mösinger und Mitarbeitern wiesen darauf hin, dass PEN an Tomaten und Gurken Resistenz induzieren kann. Ab 1997 wurde das Thema am FiBL weiterverfolgt. Mit den vorliegenden Untersuchungen wurden die Teilziele angestrebt (i) Verifizieren und Charakterisieren der resistenzinduzierenden Eigenschaften von PEN, (ii) Abklären des Potentials für eine Weiterentwicklung von PEN als kommerzialisierbaren Resistenzinduktor und (iii) Charakterisierung der phytotoxischen Eigenschaften von PEN als Ausgangspunkt für die Optimierung von Agro Biosol. Fazit: PEN, der Extrakt von Penicillium chrysogenum, kann bei zahlreichen Wirt- Pathogen-Systemen den Krankheitsbefall markant reduzieren. Dies ist insbesondere bei Krankheitserregern von Interesse, die ansonsten mit biotauglichen Produkten nur schwer kontrollierbar sind. Das Ausgangsmaterial wird als biotauglich eingeschätzt und steht in genügenden Mengen in konstanter Qualität zur Verfügung. Dies sind günstige Voraussetzungen, um einen neuartigen Resistenzinduktor für den biologischen Anbau bis zur Praxisreife zu entwickeln. PEN kann allerdings phytotoxische Effekte auslösen, die eine Praxisanwendung als Resistenzinduktor vorerst ausschliessen. Unsere Forschung hat gegenwärtig zwei Stossrichtungen. Einerseits werden die Effekte von PEN auf die Pflanzenphysiologie untersucht und die involvierten Stoffwechselprozesse detailliert abgeklärt. Andererseits suchen wir nach den aktiven Prinzipien, die für Resistenzinduktion und Phytotoxizität verantwortlich sind

Epitaxial growth in dislocation-free strained alloy films: Morphological and compositional instabilities

The mechanisms of stability or instability in the strained alloy film growth are of intense current interest to both theorists and experimentalists. We consider dislocation-free, coherent, growing alloy films which could exhibit a morphological instability without nucleation. We investigate such strained films by developing a nonequilibrium, continuum model and by performing a linear stability analysis. The couplings of film-substrate misfit strain, compositional stress, deposition rate, and growth temperature determine the stability of film morphology as well as the surface spinodal decomposition. We consider some realistic factors of epitaxial growth, in particular the composition dependence of elastic moduli and the coupling between top surface and underlying bulk of the film. The interplay of these factors leads to new stability results. In addition to the stability diagrams both above and below the coherent spinodal temperature, we also calculate the kinetic critical thickness for the onset of instability as well as its scaling behavior with respect to misfit strain and deposition rate. We apply our results to some real growth systems and discuss the implications related to some recent experimental observations.Comment: 26 pages, 13 eps figure

Phase field modeling of electrochemistry I: Equilibrium

A diffuse interface (phase field) model for an electrochemical system is developed. We describe the minimal set of components needed to model an electrochemical interface and present a variational derivation of the governing equations. With a simple set of assumptions: mass and volume constraints, Poisson's equation, ideal solution thermodynamics in the bulk, and a simple description of the competing energies in the interface, the model captures the charge separation associated with the equilibrium double layer at the electrochemical interface. The decay of the electrostatic potential in the electrolyte agrees with the classical Gouy-Chapman and Debye-H\"uckel theories. We calculate the surface energy, surface charge, and differential capacitance as functions of potential and find qualitative agreement between the model and existing theories and experiments. In particular, the differential capacitance curves exhibit complex shapes with multiple extrema, as exhibited in many electrochemical systems.Comment: v3: To be published in Phys. Rev. E v2: Added link to cond-mat/0308179 in References 13 pages, 6 figures in 15 files, REVTeX 4, SIUnits.sty. Precedes cond-mat/030817

Capillary condensation in disordered porous materials: hysteresis versus equilibrium behavior

We study the interplay between hysteresis and equilibrium behavior in capillary condensation of fluids in mesoporous disordered materials via a mean-field density functional theory of a disordered lattice-gas model. The approach reproduces all major features observed experimentally. We show that the simple van der Waals picture of metastability fails due to the appearance of a complex free-energy landscape with a large number of metastable states. In particular, hysteresis can occur both with and without an underlying equilibrium transition, thermodynamic consistency is not satisfied along the hysteresis loop, and out-of-equilibrium phase transitions are possible.Comment: 4 pages, 4 figure

A new echocardiographic model for quantifying three-dimensional endocardial surface area

A new technique for quantitatively mapping the three-dimensional left ventricular endocardial surface was developed, using measurements from standard cross-sectional echocardiographic images. To validate the accuracy of this echocardiographic mapping technique in an animal model, the endocardial areas of 15 excised canine ventricles were calculated using measurements made from echocardiographic studies of the hearts and compared with areas determined with latex casts of the same ventricles. Close correlation (r = 0.87, p < 0.001) between these two measures of endocardial area provided preliminary confirmation of the accuracy of the maps.To further characterize the mapping algorithm, it was translated into computer format and used to map the surfaces of idealized hemiellipsoids. Areas measured with this mapping technique closely approximated the actual areas of idealized surfaces with a wide spectrum of shapes; maps were particularly accurate for ellipsoids with shapes similar to those of undistorted human ventricles. Also, the accuracies of area calculations were relatively insensitive to deviation from the assumed positions of the echocardiographic short-axis planes. Finally, although the accuracy of the mapping technique improved as data from more transverse planes were added, the procedure proved reliable for estimating surface areas when data from only three planes were used. These studies confirm the accuracy of the echocardiographic mapping technique, and they suggest that the resulting planar plots might be useful as templates for localizing and quantifying the overall extent of abnormal wall motion

Stress-driven instability in growing multilayer films

We investigate the stress-driven morphological instability of epitaxially growing multilayer films, which are coherent and dislocation-free. We construct a direct elastic analysis, from which we determine the elastic state of the system recursively in terms of that of the old states of the buried layers. In turn, we use the result for the elastic state to derive the morphological evolution equation of surface profile to first order of perturbations, with the solution explicitly expressed by the growth conditions and material parameters of all the deposited layers. We apply these results to two kinds of multilayer structures. One is the alternating tensile/compressive multilayer structure, for which we determine the effective stability properties, including the effect of varying surface mobility in different layers, its interplay with the global misfit of the multilayer film, and the influence of asymmetric structure of compressive and tensile layers on the system stability. The nature of the asymmetry properties found in stability diagrams is in agreement with experimental observations. The other multilayer structure that we study is one composed of stacked strained/spacer layers. We also calculate the kinetic critical thickness for the onset of morphological instability and obtain its reduction and saturation as number of deposited layers increases, which is consistent with recent experimental results. Compared to the single-layer film growth, the behavior of kinetic critical thickness shows deviations for upper strained layers.Comment: 27 pages, 11 figures; Phys. Rev. B, in pres