We map out the solid-state morphologies formed by model soft-pearl-necklace polymers as a function of chain stiffness, spanning the range from fully flexible to rodlike chains. The ratio of Kuhn length to bead diameter (lK/r0) increases monotonically with increasing bending stiffness kb and yields a one-parameter model that relates chain shape to bulk morphology. In the flexible limit, monomers occupy the sites of close-packed crystallites while chains retain random-walk-like order. In the rodlike limit, nematic chain ordering typical of lamellar precursors coexists with close-packing. At intermediate values of bending stiffness, the competition between random-walk-like and nematic chain ordering produces glass-formation; the range of kb over which this occurs increases with the thermal cooling rate |Ṫ| implemented in our molecular dynamics simulations. Finally, values of kb between the glass-forming and rodlike ranges produce complex ordered phases such as close-packed spirals. Our results should provide a useful initial step in a coarse-grained modeling approach to systematically determining the effect of chain stiffness on the crystallization-vs-glass-formation competition in both synthetic and colloidal polymers.

Two common techniques of thermal analysis, Differential Scanning Calorimetry (DSC) and Cooling/Heating Curve Thermal Analysis (CCTA), based on different signal collected and utilizing samples with a weight difference of three orders of magnitude, were used to assess the solidification and melting behavior of Al-Ce binary alloys, containing from 5 to 20 wt. % Ce. Thermal analysis was accompanied by microscopic observations of solidified structures. For heating/cooling rates of 0.2–0.4 °C/s, temperatures of eutectic transformation L ↔ Al + Al11Ce3 in the Al-10Ce alloy along with additional proeutectic reactions L ↔ Al in the Al-5Ce hypoeutectic alloy and L ↔ Al11Ce3 in Al-15Ce and Al-20Ce hypereutectic alloys, were determined. Although there was a general agreement in major transformations, registered by DSC and CCTA during melting and solidification, differences in the reaction temperature determined exceeded the typical measurement errors for each technique. In addition, DSC and CCTA exhibited differences in detecting some proeutectic reactions and minor non-equilibrium effects, accompanying the eutectic transformation. Some factors that could contribute to differences observed and their implications for engineering practice were discussed.

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While Ni-YSZ (yttria-stabilized zirconia) cermets have excellent properties for use as solid oxide fuel cell (SOFC) anodes, they are susceptible to performance loss in the presence of sulfur (S) in the fuel stream. In this work, we have electrochemically determined the extent of poisoning and recovery of Ni-YSZ electrolytesupported half-cells in 5 ppm H 2 S (in H 2 ) between 600 and 850°C, comparing these results with S adsorption/removal data obtained using TGA. It is shown by both approaches that the coverage of Ni by adsorbed S species (S ads ) increases as the temperature decreases, as expected. However, the extent of S ads coverage, determined from performance loss, is significantly less than predicted from the mass gain during S adsorption. Furthermore, anodes exposed to H 2 S at 600°C show an unusual irreversible S poisoning effect when polarized at 250 mV, not seen in TGA experiments.