The effect of scatter of polymer chain length on strength

A polymer network fractures by breaking covalent bonds, but the experimentally measured strength of the polymer network is orders of magnitude lower than the strength of covalent bonds. We investigate the effect of statistical variation of the number of links in polymer chains on strength using a parallel chain model. Each polymer chain is represented by a freely-jointed chain, with a characteristic J-shaped force–extension curve. The chain carries entropic forces for most of the extension and carries covalent forces only for a narrow range of extension. The entropic forces are orders of magnitude lower than the covalent forces. Chains with a statistical distribution of the number of links per chain are pulled between two rigid parallel plates. Chains with fewer links attain covalent forces and rupture at smaller extensions, while chains with more links still carry entropic forces. We compute the applied force on the rigid plates as a function of extension and define the strength of the parallel chain model by the maximum force divided by the total number of chains. With the J-shaped force–extension curve of each chain, even a small scatter in the number of links per chain greatly reduces the strength of the parallel chain model. We further show that the strength of the parallel chain model relates to the scatter in the number of links per chain according to a power law.