Structure development in aerogel-processed nanocrystalline alkaline earth oxides as revealed by SANS

Abstract

Nanocrystalline MgO, CaO and SrO were prepared according to a modified aerogel process (AP). Small-angle neutron scattering (SANS) was used to probe the nanoscale structural features of these materials after each stage of the synthetic process, including hydrolysis, supercritical drying and calcining. SANS data were interpreted using a classical analysis involving power-law and Guinier regimes, and by application of the maximum entropy method. Results are compared with previously published structural data based on X-ray diffraction, electron microscopy and gas adsorption. It is found that the gel hydrolysis product suspended in methanol and toluene exhibits rod-like scattering at small length scales. This is consistent with a filiform morphology previously reported for air-dried Mg(OH)2alcogel, yet SANS data for air-dried alcogels tested in this study indicate no evidence for low-dimensional structure on any length scale. A previous assertion of mass fractal structure in the AP aerogels and oxides was not confirmed by the present data. Instead, surface fractal scattering was found to be the most dominant characteristic feature associated with the SANS data for all AP powders examined. Additionally, MgO and CaO exhibited a correlation peak that corresponds to liquid-like ordering at Bragg length scales of 5.9 nm and 20.3 nm, respectively. These values are roughly consistent with previous independent estimates of primary particle size, suggesting that local packing of primary crystallites is facilitated by the calcination/dehydration process. An alternative interpretation treats these features as Guinier scattering regions. Fitting of results using the unified Guinier/power-law equation yields sphere-equivalent radii for the primary particles that are nearly identical to the Bragg lengths calculated from the positions of the maxima. Air-dried alcogels produced very weak maxima that could be interpreted either as correlation peaks or as Guinier regions. No maxima were observed for aerogel samples. Maximum entropy analysis using a spherical shape factor produced interesting but complex results for the calculated volume size distributions of these materials. Overall, the observed trend shows an increase in structural feature size with increasing metal cation size.