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

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

A study of 15N14N isotopic exchange over cobalt molybdenum nitrides

The 14N/15N isotopic exchange pathways over Co3Mo3N, a material of interest as an ammonia synthesis catalyst and for the development of nitrogen transfer reactions, have been investigated. Both the homomolecular and heterolytic exchange processes have been studied, and it has been shown that lattice nitrogen species are exchangeable. The exchange behavior was found to be a strong function of pretreatment with ca. 25% of lattice N atoms being exchanged after 40 min at 600 °C after N2 pretreatment at 700 °C compared to only 6% following similar Ar pretreatment. This observation, for which the potential contribution of adsorbed N species can be discounted, is significant in terms of the application of this material. In the case of the Co6Mo6N phase, regeneration to Co3Mo3N under 15N2 at 600 °C occurs concurrently with 14N15N formation. These observations demonstrate the reactivity of nitrogen in the Co–Mo–N system to be a strong function of pretreatment and worthy of further consideration

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

Suppression of Phase Separation in LiFePO4 Nanoparticles During Battery Discharge

Using a novel electrochemical phase-field model, we question the common belief that LixFePO4 nanoparticles separate into Li-rich and Li-poor phases during battery discharge. For small currents, spinodal decomposition or nucleation leads to moving phase boundaries. Above a critical current density (in the Tafel regime), the spinodal disappears, and particles fill homogeneously, which may explain the superior rate capability and long cycle life of nano-LiFePO4 cathodes.Comment: 27 pages, 8 figure

Solid 4He and the Supersolid Phase: from Theoretical Speculation to the Discovery of a New State of Matter? A Review of the Past and Present Status of Research

The possibility of a supersolid state of matter, i.e., a crystalline solid exhibiting superfluid properties, first appeared in theoretical studies about forty years ago. After a long period of little interest due to the lack of experimental evidence, it has attracted strong experimental and theoretical attention in the last few years since Kim and Chan (Penn State, USA) reported evidence for nonclassical rotational inertia effects, a typical signature of superfluidity, in samples of solid 4He. Since this "first observation", other experimental groups have observed such effects in the response to the rotation of samples of crystalline helium, and it has become clear that the response of the solid is extremely sensitive to growth conditions, annealing processes, and 3He impurities. A peak in the specific heat in the same range of temperatures has been reported as well as anomalies in the elastic behaviour of solid 4He with a strong resemblance to the phenomena revealed by torsional oscillator experiments. Very recently, the observation of unusual mass transport in hcp solid 4He has also been reported, suggesting superflow. From the theoretical point of view, powerful simulation methods have been used to study solid 4He, but the interpretation of the data is still rather difficult; dealing with the question of supersolidity means that one has to face not only the problem of the coexistence of quantum coherence phenomena and crystalline order, exploring the realm of spontaneous symmetry breaking and quantum field theory, but also the problem of the role of disorder, i.e., how defects, such as vacancies, impurities, dislocations, and grain boundaries, participate in the phase transition mechanism.Comment: Published on J. Phys. Soc. Jpn., Vol.77, No.11, p.11101

Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics

Classical theories of chemical kinetics assume independent reactions in dilute solutions, whose rates are determined by mean concentrations. In condensed matter, strong interactions alter chemical activities and create inhomogeneities that can dramatically affect the reaction rate. The extreme case is that of a reaction coupled to a phase transformation, whose kinetics must depend on the order parameter -- and its gradients, at phase boundaries. This Account presents a general theory of chemical kinetics based on nonequilibrium thermodynamics. The reaction rate is a nonlinear function of the thermodynamic driving force (free energy of reaction) expressed in terms of variational chemical potentials. The Cahn-Hilliard and Allen-Cahn equations are unified and extended via a master equation for non-equilibrium chemical thermodynamics. For electrochemistry, both Marcus and Butler-Volmer kinetics are generalized for concentrated solutions and ionic solids. The theory is applied to intercalation dynamics in the phase separating Li-ion battery material Li$_x$FePO$_4$.Comment: research account, 17 two-column pages, 12 figs, 78 refs - some typos corrected Accounts of Chemical Research (2013

Egyptian Satirical Graphics on Social Media after the Arab Spring

This paper investigates Egyptian digital forms of satirical graphics mostly published on Social Media by cartoonists and amateurs after the Arab Spring. These include: webcomics memes, and Graphic Interchange Format (GIF). The paper will focus on two Facebook pages as a case study: Asa7be Sarcasm Society and Islam Gawish's Elwarka/The Paper. With this aim in mind, I will show how these forms of political satire incorporate, cinema, theatre, religion, western elements and pan-Arabism to express a political view in a creative manner to appeal to a more diverse and broad audience. The first part of the paper provides a brief discussion of Arabic/Egyptian satire with specific reference to political cartoons and Egyptian youth activism on social media (specifically Facebook). It will also introduce the concept of satirical graphics and some of its concrete applications. The second part describes the methodology and provides an analysis of the case study

Just compensation? The price of death and injury after the Rana Plaza garment factory collapse

The 2013 collapse of the Rana Plaza factory building in Dhaka, Bangladesh was the most deadly disaster in garment manufacturing history, with at least 1,134 people killed and hundreds injured. In 2015, injured workers and the families of those killed received compensation from global apparel brands through a $30 million voluntary initiative known as the Rana Plaza Arrangement. Overseen by the International Labour Organization (ILO), the Rana Plaza Arrangement awarded payments to survivors using a pricing formula developed by a diverse team of ‘stakeholders’ that included labour groups, multinational apparel companies, representatives of the Bangladesh government and local employers, and ILO actuaries. This article draws from anthropological scholarship on the ‘just price’ to explore how a formula for pricing death and injury became both the means and form of a fragile political settlement in the wake of a shocking and widely publicised industrial disaster. By unpacking the complicated ‘ethics of a formula’ (Ballestero 2015), I demonstrate how the project of creating a just price involves not two sets of values (ethical and financial) but rather multiple, competing values. This article argues for recognition of the persistence and power of these competing values, showing how they variously strengthen and undermine the claim that justice was served by the Rana Plaza Arrangement. This analysis reveals the deficiencies of counterposing ‘morality’ and ‘economy’ in the study of price by reflecting upon all elements of price as situated within political economy and history

Perinatal Tobacco Smoke Exposure Increases Vascular Oxidative Stress and Mitochondrial Damage in Non-Human Primates

Epidemiological studies suggest that events occurring during fetal and early childhood development influence disease susceptibility. Similarly, molecular studies in mice have shown that in utero exposure to cardiovascular disease (CVD) risk factors such as environmental tobacco smoke (ETS) increased adult atherogenic susceptibility and mitochondrial damage; however, the molecular effects of similar exposures in primates are not yet known. To determine whether perinatal ETS exposure increased mitochondrial damage, dysfunction and oxidant stress in primates, archived tissues from the non-human primate model Macaca mulatta (M. mulatta) were utilized. M. mulatta were exposed to low levels of ETS (1 mg/m3 total suspended particulates) from gestation (day 40) to early childhood (1 year), and aortic tissues were assessed for oxidized proteins (protein carbonyls), antioxidant activity (SOD), mitochondrial function (cytochrome oxidase), and mitochondrial damage (mitochondrial DNA damage). Results revealed that perinatal ETS exposure resulted in significantly increased oxidative stress, mitochondrial dysfunction and damage which were accompanied by significantly decreased mitochondrial antioxidant capacity and mitochondrial copy number in vascular tissue. Increased mitochondrial damage was also detected in buffy coat tissues in exposed M. mulatta. These studies suggest that perinatal tobacco smoke exposure increases vascular oxidative stress and mitochondrial damage in primates, potentially increasing adult disease susceptibility