Interfacial nanorheology: probing molecular mobility in mesoscopic polymeric systems

Abstract

Investigating the finite size limited structural relaxations in mesoscopic polymer systems is central to nanotechnological applications involving thin films, complex structures, and nanoscale phase-separated systems; for example, polymer electrolyte membranes, optoelectronic devices, and ultrahigh-density thermomechanical data storage (terabit recording). In such systems, bulk statistical averaging and continuum models are jeopardized. Interfacial constraints lead to bulk-deviating molecular dynamics and dictate material and transport properties. The objective of this dissertation is to provide insight to the exotic mesoscopic behaviors in thin films by developing novel rheological and tribological analytical methods based on scanning probe microscopy (SPM). Activation energies are deduced for the molecular motions associated with internal friction dissipation, and the temperature resolved length scale for cooperative motion during the glass transition is directly obtained for polystyrene. These results confirm the dynamical heterogeneity of the glass transition and reveal a crossover from intra- to inter-molecular relaxation in the transition regime. The impact of dimensional constraints on molecular mobility in ultrathin polymer films is explored through interfacial glass-transition profiles. With these profiles, a structural model of the rheological changes near interfacial boundaries is constructed as function of molecular weight and crosslinking density. The manifestation of interfacial constraints in nanotechnological applications is illustrated for thermomechanical recording, where rheological gradients near the substrate dictate the contact pressure and strain shielding at the substrate compromises film stability. A foundation for the critical aspects of interfacial stability is developed, and mechanically graded interfaces and modulus-matching techniques are explored as a means of improving the stability, durability, and stress transmission characteristics of the polymer-substrate interface in thermomechanical recording and the titanium-bone interface in human artificial hip implants.