Computational Study of Quenching Effects on Growth Processes and Size Distributions of Silicon Nanoparticles at a Thermal Plasma Tail

In this paper, quenching effects on silicon nanoparticle growth processes and size distributions at a typical range of cooling rates in a thermal plasma tail are investigated computationally. We used a nodal-type model that expresses a size distribution evolving temporally with simultaneous homogeneous nucleation, heterogeneous condensation, interparticle coagulation, and melting point depression. The numerically obtained size distributions exhibit similar size ranges and tendencies to those of experiment results obtained with and without quenching. In a highly supersaturated state, 40–50% of the vapor atoms are converted rapidly to nanoparticles. After most vapor atoms are consumed, the nanoparticles grow by coagulation, which occurs much more slowly than condensation. At higher cooling rates, one obtains greater total number density, smaller size, and smaller standard deviation. Quenching in thermal plasma fabrication is effectual, but it presents limitations for controlling nanoparticle characteristics.

Reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate

The mechanisms involved in the formation/dissociation of methane hydrate confined at the nanometer scale are unraveled using advanced molecular modeling techniques combined with a mesoscale thermodynamic approach. Using atom-scale simulations probing coexistence upon confinement and free energy calculations, phase stability of confined methane hydrate is shown to be restricted to a narrower temperature and pressure domain than its bulk counterpart. The melting point depression at a given pressure, which is consistent with available experimental data, is shown to be quantitatively described using the Gibbs–Thomson formalism if used with accurate estimates for the pore/liquid and pore/hydrate interfacial tensions. The metastability barrier upon hydrate formation and dissociation is found to decrease upon confinement, therefore providing a molecular-scale picture for the faster kinetics observed in experiments on confined gas hydrates. By considering different formation mechanisms—bulk homogeneous nucleation, external surface nucleation, and confined nucleation within the porosity—we identify a cross-over in the nucleation process; the critical nucleus formed in the pore corresponds either to a hemispherical cap or to a bridge nucleus depending on temperature, contact angle, and pore size. Using the classical nucleation theory, for both mechanisms, the typical induction time is shown to scale with the pore volume to surface ratio and hence the pore size. These findings for the critical nucleus and nucleation rate associated with such complex transitions provide a means to rationalize and predict methane hydrate formation in any porous media from simple thermodynamic data.

A New Era in Engineering Plastics: Compatibility and Perspectives of Sustainable Alipharomatic Poly(ethylene terephthalate)/Poly(ethylene 2,5-furandicarboxylate) Blends

The industrialisation of poly(ethylene 2,5-furandicarboxylate) for total replacement of poly(ethylene terephthalate) in the polyester market is under question. Preparation of high-performing polymer blends is a well-established strategy for tuning the properties of certain homopolymers and create tailor-made materials to meet the demands for a number of applications. In this work, the structure, thermal properties and the miscibility of a series of poly(ethylene terephthalate)/poly(ethylene 2,5-furandicarboxylate) (PET/PEF) blends have been studied. A number of thermal treatments were followed in order to examine the thermal transitions, their dynamic state and the miscibility characteristics for each blend composition. Based on their glass transition temperatures and melting behaviour the PET/PEF blends are miscible at high and low poly(ethylene terephthalate) (PET) contents, while partial miscibility was observed at intermediate compositions. The multiple melting was studied and their melting point depression was analysed with the Flory-Huggins theory. In an attempt to further improve miscibility, reactive blending was also investigated.

Characterization of dual nano-size effects of ACC-cellulose nanofibrils on crystallization behavior of hydrophilic poly(vinyl alcohol)

This study attempts to clarify thermodynamic quantification on interaction between poly(vinyl alcohol) (PVA) and wood-derived cellulose nanofibrils (CNFs) obtained by aqueous counter collision (ACC) method. Aqueous mixtures of PVA/ACC-CNFs with various fiber widths were cast as the target materials. The interfacial interactions between the two components were characterized through thermodynamic evaluation of the crystalline PVA component as a probe in the cast mixture. As the result, surface properties of the ACC-CNFs found to reflect on the crystallization behavior of the interacted PVA component, resulting in dual nano-size effects of either diluent or nucleating agent. Melting point depression behaviors of the PVA component indicated that ACC-CNFs with thinner widths induced nucleation effects on PVA crystallization, whereas ACC-CNFs with ca. 100 nm in width encouraged diluent effects on PVA components. It is noted that this trend found to be reverse to the case for PVA/ACC-CNFs of bacterial nanocellulose previously reported.