Shape memory polymers based on uniform aliphatic urethane networks

Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, to form amorphous networks with very uniform supermolecular structures, which can be used as photo‐thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N′,N′‐tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3‐butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34–153°C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T_g. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Implications of variable fluid resistance caused by start-up flow in microfluidic networks

Electrical circuit analogies are often used to design microfluidic systems because they simplify device design, providing simple relationships between fluid flow rate, driving forces, and channel dimensions. However, such approximations often significantly overestimate flow rates in situations where start-up energy losses from establishing kinetic head are similar in magnitude to the energy required to overcome viscous shear stresses, as is often the case within complex microfluidic networks. These reduced flows can be more accurately predicted within an electrical analogy framework that accounts for the nonlinear flow resistance generated on the transient regime of start-up flow. In this work, standard flow resistance expressions are modified to account for such effects, and the onset of nonlinear resistance is predicted by a dimensionless parameter, $\xi = Re\frac{D}{L},$ which is dependent on the Reynolds number and the channel length. As a demonstration, variable fluid resistance is shown to dramatically affect the flow performance of common microfluidic units such as T-junctions and serpentine channels, and the change in performance is accurately predicted. Experimental and theoretical analysis of T-junctions further shows that variable flow resistance causes the ratio of flows through the junction to converge toward unity with respect to an increasing total flow rate. In addition, serpentine channels are shown to exaggerate these start-up effects, owing to compounded energetic demand associated with changing a flow’s direction. As a result, serpentine channels cause the ratio of flow rates exiting a T-junction to diverge from unity with respect to an increasing flow rate.     

Electrocatalyst materials for fuel cells based on the polyoxometalates—K7 or H7[(P2W17O61)Fe(H2O)] and Na12 or H12[(P2W15O56)2Fe4(H2O)2]

Free acids of the iron substituted heteropoly acids (HPA), H₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (HFe1) and H₁₈[(P₂W₁₅O₅₆)₂Fe^III₂(H₂O)₂] (HFe2) were prepared from the salts K₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (KFe1) and Na₁₂[(P₂W₁₅O₅₆)₂Fe^III₄(H₂O)₂] (NaFe4), respectively. The iron-substituted HPA were adsorbed on to XC-72 carbon based GDLs to form HPA doped GDEs after water washing with HPA loadings of ca. 1 μmol. The HPA was detected throughout the GDL by EDX. Solution electrochemistry of the free acids are reported for the first time in sulfate buffer, pH 1-3. The hydrogen oxidation reaction was catalyzed by KFe1 at 0.33 V, with an exchange current density of 38 mA/cm². Moderate activity for the oxygen reduction reaction was observed for the iron substituted HPA, which was dramatically improved by selectively removing oxygen atoms from the HPA by cycling the fuel cell cathode under N₂ followed by reoxidation to give a restructured oxide catalyst. The nanostructured oxide achieved an OCV of 0.7 V with a Tafel slope of 115 mV/decade. Cycling the same catalysts in oxygen resulted in an improved catalyst/ionomer/carbon configuration with a slightly higher Tafel slope, 128 mV/decade but a respectable current density of 100 mA/cm² at 0.2 V.     

Microstructure and Mechanical Properties of Mullite–Silicon Carbide Composites

Mullite-SiC-whisker composites were prepared by powder processing using two commercial SiC whiskers. These composites were prepared by sintering rather than hot-pressing. A mulliteSlC-powder composite and a base line mallite material were also prepared for comparison with the two whisker composite materials. Fracture toughness measurements showed significant enhancement in only one of the whisker composite materials. The microstructure of the four materials was examined by scanning electron microscopy and transmission electron microscopy to assist in the explanation of the mechanical behavior of these composites. The examinations suggested that most of the toughening results from second-phase particles, with only limited toughening from effects associated with whiskers per se. In one case, higher toughness was partially associated with the formation of sialon phase by reaction with the whiskers and the furnace environment.     

Manufacturing Processes for Long-Life Gas Turbines

Dual-alloy turbine wheels produced by solid-state diffusion bonding of vacuum investment cast blade rings of one superalloy to preconsolidated powder metal hubs of a second superalloy have the long cyclic lives characteristic of wrought or powder superalloys combined with the high creep strength and net-shape blades characteristic of cast superalloys. A wide variety of superalloys and turbine configurations are compatible with this technology. Improved temperature capability turbine blades and vanes of the MAR-M 247 alloy made by directional solidification casting processes are now in volume production for Garrett gas turbines. Single-crystal alloys derivative to MAR-M 247 further extend the temperature capability of turbine blades and have been successfully engine tested. These blades are produced by a relatively simple modification of the processes used to manufacture directionally solidified blades.     

Do Management Actions to Restore Rare Habitat Benefit Native Fish Conservation? Distribution of Juvenile Native Fish Among Shoreline Habitats of the Colorado River

Many management actions in aquatic ecosystems are directed at restoring or improving specific habitats to benefit fish populations. In the Grand Canyon reach of the Colorado River, experimental flow operations as part of the Glen Canyon Dam Adaptive Management Program have been designed to restore sandbars and associated backwater habitats. Backwaters can have warmer water temperatures than other habitats, and native fish, including the federally endangered humpback chub Gila cypha, are frequently observed in backwaters, leading to a common perception that this habitat is critical for juvenile native fish conservation. However, it is unknown how fish densities in backwaters compare with that in other habitats or what proportion of juvenile fish populations reside in backwaters. Here, we develop and fit multi‐species hierarchical models to estimate habitat‐specific abundances and densities of juvenile humpback chub, bluehead sucker Catostomus discobolus, flannelmouth sucker Catostomus latipinnis and speckled dace Rhinichthys osculus in a portion of the Colorado River. Densities of all four native fish were greatest in backwater habitats in 2009 and 2010. However, backwaters are rare and ephemeral habitats, so they contain only a small portion of the overall population. For example, the total abundance of juvenile humpback chub in this study was much higher in talus than in backwater habitats. Moreover, when we extrapolated relative densities based on estimates of backwater prevalence directly after a controlled flood, the majority of juvenile humpback chub were still found outside of backwaters. This suggests that the role of controlled floods in influencing native fish population trends may be limited in this section of the Colorado River. Copyright © 2014 John Wiley & Sons, Ltd.     

A regularized graph layout framework for dynamic network visualization

Many real-world networks, including social and information networks, are dynamic structures that evolve over time. Such dynamic networks are typically visualized using a sequence of static graph layouts. In addition to providing a visual representation of the network structure at each time step, the sequence should preserve the mental map between layouts of consecutive time steps to allow a human to interpret the temporal evolution of the network. In this paper, we propose a framework for dynamic network visualization in the on-line setting where only present and past graph snapshots are available to create the present layout. The proposed framework creates regularized graph layouts by augmenting the cost function of a static graph layout algorithm with a grouping penalty, which discourages nodes from deviating too far from other nodes belonging to the same group, and a temporal penalty, which discourages large node movements between consecutive time steps. The penalties increase the stability of the layout sequence, thus preserving the mental map. We introduce two dynamic layout algorithms within the proposed framework, namely dynamic multidimensional scaling and dynamic graph Laplacian layout. We apply these algorithms on several data sets to illustrate the importance of both grouping and temporal regularization for producing interpretable visualizations of dynamic networks.     

Radiometric normalization and image mosaic generation of ASTER thermal infrared data: An application to extensive sand sheets and dune fields

Data from the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) have a significant advantage over previous datasets because of the combination of high spatial resolution (15-90 m) and enhanced multispectral capabilities, particularly in the thermal infrared (TIR) atmospheric window (8-12 μm) of the Earth where common silicate minerals are more easily identified. However, the 60 km swath width of ASTER can limit the effectiveness of accurately tracing large-scale features, such as eolian sediment transport pathways, over long distances. The primary goal of this paper is to describe a method for generating a seamless and radiometrically accurate ASTER TIR mosaic of atmospherically corrected radiance and from that, extract surface emissivity for arid lands, specifically, sand seas. The Gran Desierto in northern Sonora, Mexico was used as a test location for the radiometric normalization technique because of past remote sensing studies of the region, its compositional diversity, and its size. A linear approach was taken to transform adjacent image swaths into a direct linear relationship between image acquisition dates. Pseudo-invariant features (PIFs) were selected using a threshold of correlation between radiance values, and change-pixels were excluded from the linear regression used to determine correction factors. The degree of spectral correlation between overlapping pixels is directly related to the amount of surface change over time; therefore, the gain and offsets between scenes were based only on regions of high spectral correlation. The result was a series of radiometrically normalized radiance-at-surface images that were combined with a minimum of image edge seams present. These edges were subsequently blended to create the final mosaic. The advantages of this approach for TIR radiance (as opposed to emissivity) data include the ability to: (1) analyze data acquired on different dates (with potentially very different surface temperatures) as one seamless compositional dataset; (2) perform decorrelation stretches (DCS) on the entire dataset in order to identify and discriminate compositional units; and (3) separate brightness temperature from surface emissivity for quantitative compositional analysis of the surface, reducing seam-line error in the emissivity mosaic. The approach presented here is valid for any ASTER-related study of large geographic regions where numerous images spanning different temporal and atmospheric conditions are encountered.     

Multi-rate model predictive control of particle size distribution in a semibatch emulsion copolymerization reactor

A multi-rate model predictive controller algorithm is presented for the in-batch closed-loop control of the full particle size distribution (PSD) in a semibatch emulsion copolymerization system. The lack of frequent measurements of the PSD and the measurement delay of these measurements are addressed through the use of frequent density measurements from which the current conditions of the system are estimated. The high dimensionality of the discretized full PSD is reduced by the use of model order reduction based on principal component analysis. This method effectively reduces the size of the problem while preserving the main characteristics of the population balance system. Disturbances that perturb the surfactant and monomer amounts inside the semibatch vinyl acetate–butyl acrylate reactor are considered to demonstrate the performance of the proposed control algorithm.     

Effect of pressure on three catalytic partial oxidation reactions at millisecond contact times

The effects of pressure on reactant conversion and product selectivities in three catalytic oxidation systems have been examined at pressures between 1 and > 5 atm. Reaction was sustained autothermally near adiabatic operating conditions at temperatures of 1000°C with residence times over the noble metal catalysts between 10^–4 and 10^–2 s. The three systems investigated were (1) HCN synthesis over Pt-10% Rh gauze catalysts, (2) methane oxidation to synthesis gas (CO and H₂) over rhodium-coated monoliths, and (3) ethane conversion to ethylene over platinum-coated monoliths. We find that selectivities in all three reactions do not change dramatically with approximately a five-fold increase in pressure. This strongly suggests that free radical homogeneous chain reactions are not significant in these processes and that they can be operated reliably above atmospheric pressure. For the synthesis of HCN over Pt-10% Rh gauzes, the selectivity to HCN can be maintained above 0.75 at pressures up to 5.5 atm. Selectivities to synthesis gas (CO and H₂) from a methane-air mixture over a Rh-coated foam monolith at pressures up to 5.5 atm were maintained above 0.90. Over a Pt-coated foam monolith, the selectivity to ethylene from ethane-air and ethane-O₂ mixtures was independent of pressure up to 6.5 atm and conversion rose slightly although it was necessary to maintain constant velocity and residence time over the catalyst to avoid carbon formation.This research was supported by DOE under Grant No. DE-FG02-88ER13878.