A rubber compound containing butadiene rubber (BR), natural rubber (NR), and carbon black was investigated by thermomechanical analysis (TMA). A difference in dynamics of the formation of molecular and topological structures of a vulcanizate were found to be dependent on the mixing technology and curing time. Separation of the topological structure of cured rubber into two blocks with differing transition temperatures was visible after 20 min of vulcanization, when a share of a low-temperature block is minimal and (M) over bar(n(n)) reaches a stable value of about 2400. A low-temperature block had a predominant concentration of covalent branching junctions, independent of the mixing procedures, whereas the high-temperature block had covalent and topological junctions in concentrations that were dependent on the mixing method. For curing times longer than 20 min, the characteristic changes in values of (M) over bar(n(n)) are dependent on the procedure of rubber compound mixing. After additional homogenization of compounds and vulcanization, the rubbers are characterized by a diblock structure with the same qualitative structure of the branching junctions as for nonhomogenized ones. In some cases, the homogenization increases the relative concentration of the covalent junctions in the high-temperature block. When a preblend of BR and carbon black was prepared first, and then mixed with NR, this technology makes rubber compounds less sensitive to additional homogenization during further processing. A mechanism of creation and transformation of rubber- carbon black junctions during compounding and vulcanization of rubber compounds with two raw rubbers that differed in adsorption ability was proposed. (C) 2000 John Wiley & Sons, Inc.