In this work, the same formulations of Nano-Silica/intumescent fire retardant polypropylene nanocomposites were prepared via a novel vane extruder and a tri-screw extruder, which represented elongational flow field and shearing flow field, respectively. Not only the synergistic combustion mechanisms of Kissinger method and Flynn-Wall-Ozawa method were revealed, but also the combustion effect and efficiency were compared. Both two methods proved specimens that processed by TE exhibited higher thermal stability. The smaller aggregates of physical initial Nano-Silica, the better dispersivity of aggregates in specimens that processed by VE. Such property broke the compactness degree of char layer.