Tubular Structures of Calcium Carbonate: Formation,Characterization, and Implications in Natural Mineral Environments

Chemical gardens are self-assembled tubular precipitates formed by a combination of osmosis, buoyancy, and chemical reaction, and thought to be capable of catalyzing prebiotic condensation reactions. In many cases, the tube wall is a bilayer structure with the properties of a diaphragm and/or a membrane. The interest in silica gardens as microreactors for materials science has increased over the past decade because of their ability to create long-lasting electrochemical potential. In this study, we have grown single macroscopic tubes based on calcium carbonate and monitored their time-dependent behavior by in situ measurements of pH, ionic concentrations inside and outside the tubular membranes, and electrochemical potential differences. Furthermore, we have characterized the composition and structure of the tubular membranes by using ex situ X-ray diffraction, infrared and Raman spectroscopy, as well as scanning electron microscopy. Based on the collected data, we propose a physicochemical mechanism for the formation and ripening of these peculiar CaCO₃ structures and compare the results to those of other chemical garden systems. We find that the wall of the macroscopic calcium carbonate tubes is a bilayer of texturally distinct but compositionally similar calcite showing high crystallinity. The resulting high density of the material prevents macroscopic calcium carbonate gardens from developing significant electrochemical potential differences. In the light of these observations, possible implications in materials science and prebiotic (geo)chemistry are discussed.     

Electrical resistance of platinum wires during annealing and quenching in air and helium

Electrical resistance of platinum wires annealed and quenched in air and helium was measured. No irreversible changes of the electrical resistance were observed in specimens treated in helium, however, these changes were appreciable in specimens treated in air. By measurement at two temperatures the total change was divided into the change of the electrical resistivity and the change of geometrical dimensions. The changes of geometrical dimensions were interpreted in terms of the oxidation of platinum and the activation energy of oxidation of platinum was determined asE=(1.79±0.04) eV.     

Adsorption pattern of mixtures of trimethylammonium-modified hydroxyethylcellulose and sodium dodecyl sulfate at solid-liquid interfaces

We studied mixtures of aqueous solutions of cationic hydroxyethylcellulose JR400 polymer and anionic sodium dodecyl sulfate using dynamic light scattering and atomic force microscopy (AFM). A ternary phase diagram was established showing three interesting realms of the polymer-surfactant-water mixture: a preprecipitation area of lowered viscosity (polymer excess) compared to the pure polymer solution, a postprecipitation area (resolubilization at surfactant excess), and highly diluted samples with a stoichiometrical surfactant-polymer ratio close to that of maximum precipitation. Samples with various compositions representing these areas were imaged by atomic force microscopy on mica and on hydrophobically modified silica in contact mode. A correlation between light scattering data concerning particle size and, more important, structuring in the bulk on one hand and AFM images on the other hand was observed. It was revealed that the influence of surface properties is of less importance for adsorption, compared to the influence of the mixture in the bulk, provided that the mixture is prepared prior to adsorption.