Investigation of sol-gel transition by rheological methods. Part II. Results and discussion

In this work rheological studies of the gelling process were carried out. We have developed a measuring system for studying the rheology of the gelation process. It consisted of several measuring cells of the Weiler-Rebinder type, system for automatic regulation of the composition of the medium and thermostabilization system. This complex is designed to measure the dependence of the value of the ultimate shear stress as a function of time, from the start of the sol-gel transition to the complete conversion of the sol to the gel. The developed device has a wide range of measured values of critical shear stresses t0 = (0,05÷50000) Dyne/cm2. Using the developed instrument, it was possible to establish the shape of the initial section of the curve t0 = f(t) and develop a methodology for more accurate determination of gelation time. The developed method proved that the classical method for determining the start time of the sol-gel transition using the point of intersection of the tangent to the linear part of the rheological curve t0 = f(t), gives significantly distorted results. A new phenomenon has been discovered: the kinetic curves in the coordinates of the Avrami-Erofeev-Bogolyubov equation have an inflection point which separates the kinetic curve into two parts, the initial and the final. It was found that the constant k in the Avrami-Erofeev-Bogolyubov equation does not depend on the temperature and is the same for both the initial and final parts of the kinetic curve. It depends only on the chemical nature of the reacting system. It was found that for the initial section of the kinetic curves, the value of the parameter n in the Avrami-Erofeev-Bogolyubov equation was n = 23,4±2,8 and, unlike the final section of the rheological curve, does not depend on temperature. A large value of this parameter can be interpreted as the average number of directions of growth of a fractal aggregate during its growth. The value of this parameter depends on the chemical nature of the sol particles participating in the gelling process. This behavior of the kinetic curves is due to a change in the mechanism of the process and a decrease in the number of possible directions for the growth of fractal aggregates. At the same time the process of aggregate growth gradually shifts from three-dimensional growth to twodimensional surface geometry, and even to a one-dimensional linear geometry. This phenomenon is due to steric hindrance arising from the aggregation of the remaining particles of sol in the formed gel. Based on rheological measurements, a sol-gel transition can be classified as a Second-order phase transition.