Effect of chain stiffness and entanglements on the elastic behavior of end-linked elastomers.
The effect of chain stiffness and entanglements on the elastic behavior and microscopic structure of cross-linked polymer networks was studied using Monte Carlo simulations. We investigated the behavior of entangled and entanglement-free networks at various degrees of chain stiffness and densities. Based on previous results that indicated that trapped entanglements prevent strain-induced order-disorder transitions in semiflexible chain networks, we prepared the entangled networks by end-linking the chains in very dilute conditions so as to minimize the extent of trapped entanglements. We also considered the entanglement-free case by using a "diamond" structure. We found that the presence of even a very small amount of trapped entanglements is enough to prevent a discontinuous strain-induced transition to an ordered phase. In these mildly entangled networks, a nematiclike order is eventually attained at high extensions but the elastic response remains continuous and the cross-links remain uniformly distributed through the simulation box. The entanglement-free diamond networks on the other hand show discontinuities in their stress-strain data. Networks at higher densities exhibit a more stable ordered phase and show an unusual staircaselike stress-strain curve. This is the result of a stepwise extension mechanism in which the chains form ordered domains that exclude the cross-links. Extension is achieved by increasing the number of these ordered domains in the strain direction. Cross-links aggregate in the spaces between these ordered domains and form periodic bands. Each vertical upturn in the stress-strain data corresponds to the existence of an integer number of ordered domains. This stepwise elastic behavior is found to be similar to that exhibited by some tough natural materials.
Bhawe
Dhananjay M
DM
School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, New York 14853, USA.
Cohen
Claude
C
Escobedo
Fernando A
FA
D016880:Anisotropy; D003460:Crystallization; D004548:Elasticity; D020724:Elastomers; D050866:Liquid Crystals; D008956:Models, Chemical; D015233:Models, Statistical; D008962:Models, Theoretical; D008968:Molecular Conformation; D016012:Poisson Distribution; D011108:Polymers / Q000737:chemistry*; D012212:Rheology
D020724:Elastomers; D011108:Polymers; C422409:liquid crystal polymer