Structural Modifications to Polystyrene via Self-Assembling Molecules


  • This work was supported by the U.S. Air Force Office of Scientific Research under Award No. F49620-00-1-283/P0002, the U.S. Army Research Office under Award No. DAAG55-97-1-0126, and the U.S. Department of Energy under Award No. DE-FG02-00ER45810/A001. The authors wish to recognize Yau-Ru Chen, Thang Bui, and Mark Seniw at Northwestern University for providing technical assistance and are thankful for useful discussions with Prof. Edward Kramer of the University of California at Santa Barbara.


We have previously reported that small quantities of self-assembling molecules known as dendron rodcoils (DRCs) can be used as supramolecular additives to modify the properties of polystyrene (PS). These molecules spontaneously assemble into supramolecular nanoribbons that can be incorporated into bulk PS in such a way that the orientation of the polymer is significantly enhanced when mechanically drawn above the glass-transition temperature. In the current study, we more closely evaluate the structural role of the DRC nanoribbons in PS by investigating the mechanical properties and deformation microstructures of polymers modified by self-assembly. In comparision to PS homopolymer, PS containing small amounts (≤ 1.0 wt.-%) of self-assembling DRC molecules exhibit greater Charpy impact strengths in double-notch four-point bending and significantly greater elongations to failure in uniaxial tension at 250 % prestrain. Although the DRC-modified polymer shows significantly smaller elongations to failure at 1000 % prestrain, both low- and high-prestrain specimens maintain tensile strengths that are comparable to those of the homopolymer. The improved toughness and ductility of DRC-modified PS appears to be related to the increased stress whitening and craze density that was observed near fracture surfaces. However, the mechanism by which the self-assembling DRC molecules toughen PS is different from that of conventional additives. These molecules assemble into supramolecular nanoribbons that enhance polymer orientation, which in turn modifies crazing patterns and improves impact strength and ductility.