Linear nucleation of polymers

The use of high-melting fibres as linear nuclei for quiescent polymeric melts is instrumental in providing the superior mechanical properties of polymeric self-composites. It also has inherent advantages in the elucidation of fundamental aspects of polymeric crystallization and self-organization, not least in allowing systematic microscopic studies of polymeric crystallization from nucleation through to the growth interface. This has demonstrated explicitly that lamellae develop in two distinct ways, for slower and faster growth, depending on whether fold packing has or has not time to order before the next molecular layer is added with only the former leading to banded growth in linear polyethylene. Other gains in understanding concern cellulation and morphological instability, internuclear interference, isothermal lamellar thickening and banded growth being a consequence of the partial relief of initial surface stress. (c) 2006 Elsevier Ltd. All rights reserved.

Self-nucleation and crystallization kinetics of double crystalline poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers

The crystallization kinetics of each constituent of poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers (PPDX-b-PCL) has been determined in a wide composition range by differential scanning calorimetry and compared to that of the equivalent homopolymers. Spherulitic growth rates were also measured by polarized optical microscopy while atomic force microscopy was employed to reveal the morphology of one selected diblock copolymer. It was found that crystallization drives structure formation and both components form lamellae within mixed spherulitic superstructures. The overall isothermal crystallization kinetics of the PPDX block at high temperatures, where the PCL is molten, was determined by accelerating the kinetics through a previous self-nucleation procedure. The application of the Lauritzen and Ho. man theory to overall growth rate data yielded successful results for PPDX and the diblock copolymers. The theory was applied to isothermal overall crystallization of previously self-nucleated PPDX ( where growth should be the dominant factor if self-nucleation was effective) and the energetic parameters obtained were perfectly matched with those obtained from spherulitic growth rate data of neat PPDX. A quantitative estimate of the increase in the energy barrier for crystallization of the PPDX block, caused by the covalently bonded molten PCL as compared to homo-PPDX, was thus determined. This energy increase can dramatically reduce the crystallization rate of the PPDX block as compared to homo-PPDX. In the case of the PCL block, both the crystallization kinetics and the self-nucleation results indicate that the PPDX is able to nucleate the PCL within the copolymers and heterogeneous nucleation is always present regardless of composition. Finally, preliminary results on hydrolytic degradation showed that the presence of relatively small amounts of PCL within PPDX-bPCL copolymers substantially retards hydrolytic degradation of the material in comparison to homo-PPDX. This increased resistance to hydrolysis is a complex function of composition and its knowledge may allow future prediction of the lifetime of the material for biomedical applications.

Vacuum-induced bubble formation in liquid-tempered chocolate

Bubble inclusion is one of the fastest growing operations practiced in the food industry. A variety of aerated foods is currently available in supermarkets, and newer products are emerging all the time. This paper aims to combine knowledge on chocolate aeration with studies performed on bubble formation and dispersion characteristics. More specifically, we have investigated bubble formation induced by applying vacuum. Experimental methods to determine gas hold-up (volume fraction of air), bubble section distributions along specific planes, and chocolate rheological properties are presented. This study concludes that decreasing pressures elevate gas hold-up values due to an increase in the number of bubble nuclei being formed and release of a greater volume of dissolved gases. Furthermore, bubbles are observed to be larger at lower pressures for a set amount of gas because the internal pressure needs to be in equilibrium with the surrounding pressures. Temperature-induced changes to the properties of the chocolate have less of an effect on bubble formation. On the other hand, when different fats and emulsifiers are added to a standard chocolate recipe, milk fat was found to increase, significantly, the gas hold-up values and the mean bubble-section diameters. It is hypothesized that this behavior is related to the way milk fats, which contain different fatty acids to cocoa butter, crystallize and influence the setting properties of the final product. It is highlighted that apparent viscosity values at low shear rate, as well as setting behavior, play an important role in terms of bubble formation and entrainment.

Bubble-included chocolate: relating structure with sensory response

Bubbles impart a very unique texture, chew, and mouth feel to foods. However, little is known about the relationship between structure of such products and consumer response in terms of mouth-feel and eating experience. The objective of this article is to investigate the sensory properties of 4 types of bubble-containing chocolates, produced by using different gases: carbon dioxide, nitrogen, nitrous oxide, and argon. The structure of these chocolates were characterized in terms of (1) gas hold-up values determined by density measurements and (2) bubble size distribution which was measured by undertaking an image analysis of X-ray microtomograph sections. Bubble size distributions were obtained by measuring bubble volumes after reconstructing 3D images from the tomographic sections. A sensory study was undertaken by a nonexpert panel of 20 panelists and their responses were analyzed using qualitative descriptive analysis (QDA). The results show that chocolates made from the 4 gases could be divided into 2 groups on the basis of bubble volume and gas hold-up: the samples produced using carbon dioxide and nitrous oxide had a distinctly higher gas hold-up containing larger bubbles in comparison with those produced using argon and nitrogen. The sensory study also demonstrated that chocolates made with the latter were perceived to be harder, less aerated, slow to melt in the mouth, and having overall flavor intensity. These products were further found to be creamier than the chocolates made by using carbon dioxide and nitrous oxide; the latter sample also showed a higher intensity of cocoa flavor.

Ice nucleation on a model hexagonal surface

The adsorption of water on a model hexagonal surface has been studied using accurate intermolecular potentials. The structure and binding energies of single molecules, clusters, and adlayers are obtained. The limiting case of weak, nondirectional surface-water interactions presented here is compared with other cases involving water-water and water-surface interactions of a similar magnitude (partial templating) and dominating water-surface interactions (perfect templating) from the literature. None of these models is conducive to the nucleation of ice, each for different reasons.Wecommenton the requirements for a good ice-nucleating surface.

Contact angle of a hemispherical bubble: an analytical approach

We have calculated the equilibrium shape of the axially symmetric Plateau border along which a spherical bubble contacts a flat wall, by analytically integrating Laplace’s equation in the presence of gravity, in the limit of small Plateau border sizes. This method has the advantage that it provides closed-form expressions for the positions and orientations of the Plateau border surfaces. Results are in very good overall agreement with those obtained from a numerical solution procedure, and are consistent with experimental data. In particular we find that the effect of gravity on Plateau border shape is relatively small for typical bubble sizes, leading to a widening of the Plateau border for sessile bubbles and to a narrowing for pendant bubbles. The contact angle of the bubble is found to depend even more weakly on gravity.

Liquid-vapour homogenisation of fluid inclusions in stalagmites: Evaluation of a new thermometer for paleoclimate research

We present a new approach to determine palaeotemperatures (mean annual surface temperatures) based on measurements of the liquid–vapour homogenisation temperature of fluid inclusions in stalagmites. The aim of this study is to explore the potential and the limitations of this new palaeothermometer and to develop a reliable methodology for routine applications in palaeoclimate research. Therefore, we have investigated recent fluid inclusions from the top part of actively growing stalagmites that have formed at temperatures close to the present-day cave air temperature. A precondition for measuring homogenisation temperatures of originally monophase inclusions is the nucleation of a vapour bubble by means of single ultra-short laser pulses. Based on the observed homogenisation temperatures (Th(obs)) and measurements of the vapour bubble diameter at a known temperature, we calculated stalagmite formation temperatures (Tf) by applying a thermodynamic model that takes into account the effect of surface tension on liquid–vapour homogenisation. Results from recent stalagmite samples demonstrate that calculated stalagmite formation temperatures match the present-day cave air temperature within ± 0.2 °C. To avoid artificially induced changes of the fluid density we defined specific demands on the selection, handling and preparation of the stalagmite samples. Application of the method is restricted to stalagmites that formed at cave temperatures greater than ~ 9–11 °C.

Speculative bubble spillovers across regional housing markets

In this paper we determine whether speculative bubbles in one region in the United States can lead bubbles to form in others. We first apply a regime-switching model to determine whether speculative bubbles existed in the U.S. regional residential real estate markets. Our findings suggest that the housing markets in five of the nine census divisions investigated were characterized by speculative bubbles. We then examine the extent to which bubbles spill over between neighboring and more distant regions, finding that the transmission of speculative bubbles and nonfundamentals between regions is multidirectional and does not depend on contiguity or distance