Silica gardens consist of hollow tubular structures that form from salt crystals seeded into silicate solution. We investigate the structure and elemental composition of these tubes in the context of a recently developed experimental model that allows quantitative analyses based on predetermined reactant concentrations and flow rates. In these experiments, cupric sulfate solution is injected into large volumes of waterglass. The walls of the resulting tubular structures have a typical width of 10 microm and are gradient materials. Micro-Raman spectroscopy along with energy dispersive X-ray fluorescence data identify amorphous silica and copper(ii) hydroxide as the main compounds within the inner and outer tube surfaces, respectively. Upon heating the blueish precipitates to approximately 150 degrees C, the material turns black as copper(ii) hydroxide decomposes to copper(ii) oxide. Moreover, we present high resolution transmission electron micrographs that reveal polycrystalline morphologies.
Numerous types of reaction-precipitation systems involve the growth of tubular structures similar to those formed in "silica gardens". As a model case for this phenomenon, we investigate the rapid growth of hollow tubes in the reaction between sodium silicate and cupric sulfate. The latter solution is injected hydrodynamically at constant flow rates of 1-20 mL h(-1) into a large reservoir of waterglass. In this study, the growth is templated and guided by single, buoyant gas bubbles. The resulting tubes can be several decimetres long and have constant radii in the range of 100-600 microm. Systematic measurements show that bubble size governs the tube radius. According to this radius, the system selects its growth velocity following volume conservation of the injected solution. Moreover, scanning electron microscopy reveals intricate ring patterns on the tube walls. We also show evidence for the existence of a minimal and a maximal tube radius. Finally, we report an intriguing collapse of tubes created at high silicate concentrations, which yields twisted ribbon-like structures. Critical radii and tube collapse are discussed in terms of simple competing forces.
The flow injection of sodium silicate solution into a large reservoir of lighter cupric sulfate solution creates single, downward growing precipitation tubes. These hollow structures have diameters in the range of 0.8-2.4 mm and can grow several centimeters in length. Four distinct growth regimes are observed, and their stability in terms of flow rate and cupric sulfate concentration is investigated. Three of these growth regimes resemble behavior reported earlier for the injection of cupric sulfate into silicate solution. However the "reverse" conditions studied here reveal one distinctly different regime in which tube growth is limited by repetitive fracturing. The lengths of the broken-off tube segments and the times between subsequent break-off events can be described by log-normal distributions.
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