The evolution and the origin of “solid-like state” in molten polymer/clay nanocomposites are studied. Using polypropylene/clay hybrid (PPCH) with sufficient maleic anhydride modified PP (PP-MA) as compatibilizer

well exfoliation yet solid-like state was achieved after annealing in molten state. Comprehensive linear viscoelasticity and non-linear rheological behaviors together with WAXD and TEM are studied on PPCH at various dispersion stages focusing on time

temperature and deformation dependencies of the “solid-like” state in molten nanocomposites. Based on these

it is revealed that the solid-structure is developed gradually along with annealing through the stages of inter-layer expansion by PP-MA

the diffusion and association of exfoliated silicate platelets

the formation of band/chain structure and

finally

a percolated clay associated network

which is responsible for the melt rigidity or solid-like state. The network will be broken down by melt frozen/crystallization and weakened at large shear or strong flow and

even more surprisingly

may be disrupted by using trace amount of silane coupling agent which may block the edge interaction of platelets. The solid-like structure causes characteristic non-linear rheological behaviors

e.g. residual stress after step shear

abnormal huge stress overshoots in step flows and

most remarkably

the negative first normal stress functions in steady shear or step flows. The rheological and structural arguments challenge the existing models of strengthened entangled polymer network by tethered polymer chains connecting clay particles or by chains in confined melts or frictional interaction among tactoids. A scheme of percolated networking of associated clay platelets

which may in band form of edge connecting exfoliated platelets

is suggested to explain previous experimental results.