Effect of Dilution on the Crystallization Kinetics of Neodymium-Based Rare Earth Polybutadiene Rubber

The crystallization behavior of neodymium-based rare earth polybutadiene rubber (Nd-BR) is studied in the presence of small-molecule treated distillate aromatic extract (TDAE) and high-molecular-weight polybutadiene-isoprene copolymer rubber (BIR). Pronounced inhibitory effects on the crystallization of Nd-BR are exhibited by both materials, as evidenced by reductions in the crystallization temperature (T_c), melting point (T_m), and corresponding enthalpy change. It is found that, at equal concentrations, a greater influence on the crystallization rate is exerted by TDAE oils, whereas nucleation inhibition is more potently affected by BIR. Incomplete crystallization during cooling is exhibited by Nd-BR when the TDAE oil concentration reaches 40 parts per hundreds of rubber (PHR) (31 wt.%), or BIR achieves a 60 wt.% concentration; subsequently, a noticeable cold crystallization phenomenon is observed upon heating. Insights into the isothermal crystallization kinetics are offered by the data, which reveal that the Avrami index n value for Nd-BR predominantly ranges between 2.5 and 3.0. A decrease in the n value is induced by a small amount of TDAE oil, while a noticeable decline in the n value is observed only when the BIR concentration is 60 wt.%. A correlation between the crystallization activation energy, the concentration of TDAE oil and BIR, and the crystallization temperature is established; a negative activation energy is recorded, and a decrease in the crystallization rate is noted when both concentrations are low and the crystallization temperature exceeds -50 °C. In contrast, positive activation energy and an increase in the crystallization rate are observed when the BIR concentration reaches 60%, and the crystallization temperature resides between -50 °C and -70 °C.