Effect of sodium pyrophosphate and understanding microstructure of aqueous LAPONITE dispersion using dissolution study.

In this work, we investigate the physical origin of ergodicity breaking in an aqueous colloidal dispersion of synthetic hectorite clay, LAPONITE, by performing dissolution and rheological experiments with monovalent salt and tetrasodium pyrophosphate solution. We also study the effect of pH and nature of interface, nitrogen and paraffin oil on the same. Dissolution experiments carried out for dispersions with both the interfaces show similar results. However, for samples with a nitrogen interface, all the effects are observed to get expedited in time compared to a paraffin oil interface. When kept in contact with water, 1.5 wt.% and 2.8 wt.% colloidal dispersion at pH 10 swells at small ages, while it does not swell at large ages. The solution of tetrasodium pyrophosphate, interestingly, dissolves the entire colloidal dispersion sample with pH 10 irrespective of the concentration of clay. Experiments carried out on colloidal dispersions prepared in water having pH 13 demonstrate no effect of water as well as sodium pyrophosphate solution on the same suggesting a possibility of the presence of negative charge on edge at that pH. We believe that all the behaviors observed for samples at pH 10 can be explained by an attractive gel microstructure formed by edge-to-face contact. Furthermore, the absence of swelling in old colloidal dispersion at pH 10 and dissolution of the same by sodium pyrophosphate solution cannot be explained by merely repulsive interactions. This behavior suggests that attractive interactions originating from edge-to-face contact play an important role in causing ergodicity breaking in the colloidal dispersions at pH 10 at all the ages irrespective of the clay concentration. We further substantiate the presence of a fractal network structure formed by interparticle edge-face association using rheological tools and cryo-TEM imaging. We also conduct a comprehensive study of the effect of tetrasodium pyrophosphate on the sol-gel transition of LAPONITE dispersion.