Formation of Azobenzenes and Azoxybenzenes from the Aqueous Reactions of Anilines and Ozone

Azobenzenes and azoxybenzenes are two of the products identified from the aqueous reaction of anilines with ozone. Aniline concentration and functional groups on the benzene ring of aniline affected the amount of azobenzenes and azoxybenzenes formed; (1) decreasing the aniline concentration significantly increased azobenzene formation, and (2) electron-withdrawing groups increased the formation of its related azobenzene and azoxybenzene, whereas electron-donating groups had the opposite effect.     

Transient and steady-state deformations and breakup of dispersed-phase droplets of immiscible polymer blends in steady shear flow

Transient and steady-state deformations and breakup of viscoelastic polystyrene droplets dispersed in viscoelastic high-density polyethylene matrices were observed in a simple steady shear flow between two transparent parallel disks. By separately varying the elasticities of the individual blend components, the matrix shear viscosity, and the viscosity ratio, their effects on the transient deformation, steady-state droplet size, and the breakup sequence were determined. After the startup of a steady shear flow, the viscoelastic droplet initially exhibits oscillations of its length in the flow direction, but eventually stretches preferentially in the vorticity direction. We find that at fixed capillary number, the oscillation amplitude decreases with increasing droplet elasticity, while the oscillation period depends primarily on, and increases with, the viscosity ratio. At steady-state, the droplet length along the vorticity direction increases with increasing capillary number, viscosity ratio, and droplet elasticity. Remarkably, at a viscosity ratio of unity, the droplets remain in a nearly undeformed state as the capillary number is varied between 2 and 8, apparently because under these conditions a tendency for the droplets to widen in the vorticity direction counteracts their tendency to stretch in the flow direction. When a critical capillary number, Ca_c, is exceeded, the droplet finally stretches in the vorticity direction and forms a string which becomes thinner and finally breaks up, provided that the droplet elasticity is sufficiently high. For a fixed matrix shear stress and droplet elasticity, the steady-state deformation along the vorticity direction and the critical capillary number for breakup both increase with increasing viscosity ratio.     

Model for reaction‐assisted polymer dissolution in LIGA

A new chemically oriented mathematical model for the development step of the LIGA process is presented (LIGA is an acronym for the German words Lithographie, Galvanoformung, and Abformung). The key assumption is that the developer can react with the polymeric resist material to increase the solubility of the latter, thereby partially overcoming the need to reduce the polymer size. The ease with which this reaction takes place is assumed to be determined by the number of side‐chain scissions that occur during the X‐ray exposure phase of the process. The dynamics of the dissolution process are simulated by the solution of the reaction diffusion equations for this three‐component, two‐phase system, the three species being the unreacted and reacted polymers and the solvent. The mass fluxes are described by multicomponent diffusion (Stefan–Maxwell) equations, and the chemical potentials are assumed to be given by the Flory–Huggins theory. Sample calculations are used to determine the dependence of the dissolution rate on key system parameters such as the reaction rate constant, polymer size, solid‐phase diffusivity, and Flory–Huggins interaction parameters. A simple photochemistry model is used to relate the reaction rate constant and the polymer size to the absorbed X‐ray dose. The resulting formula for the dissolution rate as a function of the dose and temperature is fit to an extensive experimental database to evaluate a set of unknown global parameters. The results suggest that reaction‐assisted dissolution is very important at low doses and low temperatures, the solubility of the unreacted polymer being too small for it to be dissolved at an appreciable rate. However, at high doses or at higher temperatures, the solubility is such that the reaction is no longer needed, and dissolution can take place via the conventional route. These results provide an explanation for the observed dependences of both the rate of dissolution and its activation energy on the absorbed dose. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 25–37, 2005     

Influence of a high‐head dam as a dispersal barrier to fish community structure of the Upper Mississippi River

In river systems, high‐head dams may increase the distance‐decay of fish community similarity by creating nearly impermeable dispersal barriers to certain species from upstream reaches. Substantial evidence suggests that migratory species are impacted by dams, and most previous studies in stream/river networks have focused on small streams and headwaters. Here, we assess whether a high‐head dam (Lock and Dam 19; LD 19) on a large river, the Upper Mississippi River (UMR), substantially alters fish community structure relative to variability expected to occur independent of the dam's effect as a fish dispersal barrier. Using fish catch per unit effort data, we modelled the distance‐decay function for the UMR fish community and then estimated the similarity that would be expected to occur across LD19 and compared it with measured similarity. Measured similarity in the fish community above and below LD19 was close to the expected value based on the distance‐decay function, suggesting LD19 does not create an abrupt transition in the fish community. Although some migratory fish species no longer occur above LD19 (e.g., skipjack herring, Alosa chrysochloris), these species do not occur in high abundance below the dam and so do not drive variation in fish community structure. Instead, much of the variation in species structure is driven by the loss/gain of species across the latitudinal gradient. Lock and Dam 19 does not appear to be a clear transition point in the river's fish community, although it may function as a meaningful barrier for particular species (e.g., invasive species) and warrant future attention from a management perspective.     

Braess’s Paradox for Flows over Time

We study the properties of Braess’s paradox in the context of the model of congestion games with flow over time introduced by Koch and Skutella. We compare them to the well known properties of Braess’s paradox for Wardrop’s model of games with static flows. We show that there are networks which do not admit Braess’s paradox in Wardrop’s model, but which admit it in the model with flow over time. Moreover, there is a topology that admits a much more severe Braess’s ratio for this model. Further, despite its symmetry for games with static flow, we show that Braess’s paradox is not symmetric for flows over time. We illustrate that there are network topologies which exhibit Braess’s paradox, but for which the transpose does not. Finally, we conjecture a necessary and sufficient condition of existence of Braess’s paradox in a network, and prove the condition of existence of the paradox either in the network or in its transpose.     

Interfacial Connections between Organic Perovskite/n+ Silicon/Catalyst that Allow Integration of Solar Cell and Catalyst for Hydrogen Evolution from Water

The rapidly increasing solar conversion efficiency (PCE) of hybrid organic–inorganic perovskite (HOIP) thin-film semiconductors has triggered interest in their use for direct solar-driven water splitting to produce hydrogen. However, application of these low-cost, electronic-structure-tunable HOIP tandem photoabsorbers has been hindered by the instability of the photovoltaic-catalyst-electrolyte (PV+E) interfaces. Here, photolytic water splitting is demonstrated using an integrated configuration consisting of an HOIP/n⁺silicon single junction photoabsorber and a platinum (Pt) thin film catalyst. An extended electrochemical (EC) lifetime in alkaline media is achieved using titanium nitride on both sides of the Si support to eliminate formation of insulating silicon oxide, and as an effective diffusion barrier to allow high-temperature annealing of the catalyst/TiO₂-protected-n⁺silicon interface necessary to retard electrolytic corrosion. Halide composition is examined in the (FA_1-xCs_x)PbI₃ system with a bandgap suitable for tandem operation. A fill factor of 72.5% is achieved using a Spiro-OMeTAD-hole-transport-layer (HTL)-based HOIP/n⁺Si solar cell, and a high photocurrent density of −15.9 mA cm⁻² (at 0 V vs reversible hydrogen electrode) is attained for the HOIP/n⁺Si/Pt photocathode in 1 m NaOH under simulated 1-sun illumination. While this thin-film design creates stable interfaces, the intrinsic photo- and electro-degradation of the HOIP photoabsorber remains the main obstacle for future HOIP/Si tandem PEC devices.     

Second Sound Measurements Near the Tricritical Point in 3He-4He Mixtures

In this paper we discuss a pulsed second sound experiment, aimed at determining accurately the critical exponent , and the predicted logarithmic correction to scaling, for the superfluid density along a tricritical path in the ³ He- ⁴ He phase diagram. We present an accurate estimate for the limits for closest approach to the tricritical point, as set by gravitationally induced sample inhomogeneities and finite size effects, and discuss some of the complications associated with measurements close to the tricritical point.