Characterization of Phase Separation and Thermal History Effects in Magnesium Silicate Glass Fibers by Nuclear Magnetic Resonance Spectroscopy

Liquid–liquid immiscibility, leading to the separation of silica-rich and silica-poor domains, is a common phenomenon in binary silicate glasses, but can be difficult to detect and characterize when rapid cooling results in nano-scale domain dimensions. 29Si nuclear magnetic resonance (NMR) spectroscopy can be very useful for detecting such phase separation, because the exclusion of paramagnetic impurity ions from the silica-rich regions can greatly slow their spin-lattice relaxation rates. Properly designed experiments can therefore largely isolate the NMR signals from high-silica and low-silica domains, and thus provide information about their proportions, compositions, and short- to intermediate-range structures. We demonstrate this approach here for fiber glasses that are predominantly magnesium, or calcium-magnesium silicates, with minor contents of alumina. For bulk compositions within the known region of stable liquid immiscibility, phase separation occurs even when extremely rapid cooling yields fibers less than 1 μm in mean diameter. Slower cooling increases the extent of separation, while the addition of small amounts of alumina reduces it.