The potential of chemical bonding to design crystallization and vitrification kinetics

Controlling a state of material between its crystalline and glassy phase has fostered many real-world applications. Nevertheless, design rules for crystallization and vitrification kinetics still lack predictive power. Here, we identify stoichiometry trends for these processes in phase change materials, i.e. along the GeTe-GeSe, GeTe-SnTe, and GeTe-Sb2Te3 pseudo-binary lines employing a pump-probe laser setup and calorimetry. We discover a clear stoichiometry dependence of crystallization speed along a line connecting regions characterized by two fundamental bonding types, metallic and covalent bonding. Increasing covalency slows down crystallization by six orders of magnitude and promotes vitrification. The stoichiometry dependence is correlated with material properties, such as the optical properties of the crystalline phase and a bond indicator, the number of electrons shared between adjacent atoms. A quantum-chemical map explains these trends and provides a blueprint to design crystallization kinetics.

Recycling of Wastes Plastics and Tires from Automotive Industry

Waste tires (granulate) and selected plastics from the automotive industry were evaluated by using the tertiary (pyrolysis) and quaternary (calorimetry) recovering. Pyrolysis is proving to be an environmentally friendly alternative to incineration and inefficient landfilling. Currently, the main challenges for pyrolysis of plastic waste are unavailability and inconsistent quality of feedstock, inefficient and hence costly sorting, and last but not least insufficient regulations around plastic waste management. Waste plastics and tire materials were characterized by TG/DTG analysis, Py-GC/MS analysis and calorimetry. TG analysis of the investigated materials gives the typical decomposition curves of synthetic polymers. The tested samples had the highest rate of weight loss process in the temperature range from 375 °C to 480 °C. Analytical pyrolysis of the tested polymers provided information on a wide variety of organic compounds that were released upon thermal loading of these materials without access to oxygen. Analytical pyrolysis offers valuable information on the spectrum of degradation products and their potential uses. Based on the results of calorimetry, it can be stated that the determined calorific value of selected plastic and rubber materials was ranging from 26.261 to 45.245 MJ/kg depending on the ash content and its composition.

Order–disorder transition of a rigid cage cation embedded in a cubic perovskite

The structure and properties of organic–inorganic hybrid perovskites are impacted by the order–disorder transition, whose driving forces from the organic cation and the inorganic framework cannot easily be disentangled. Herein, we report the design, synthesis and properties of a cage-in-framework perovskite AthMn(N3)3, where Ath+ is an organic cation 4-azatricyclo[2.2.1.02,6]heptanium. Ath+ features a rigid and spheroidal profile, such that its molecular reorientation does not alter the cubic lattice symmetry of the Mn(N3)3− host framework. This order–disorder transition is well characterized by NMR, crystallography, and calorimetry, and associated with the realignment of Ath+ dipole from antiferroelectric to paraelectric. As a result, an abrupt rise in the dielectric constant was observed during the transition. Our work introduces a family of perovskite structures and provides direct insights to the order–disorder transition of hybrid materials.