Strain-Induced Orientation of Host Rings that Determines the Sliding of Guest Polymers and Plasticity of Glassy Polyrotaxane

The unique motility of mechanically interlocked polymers enables their mechanical properties to profoundly transform. This property has been exploited less in glassy materials than in rubbery materials. This study demonstrated that in the glassy state the rings must orient before sliding and clarified the requisite structural changes by the synchrotron microbeam X-ray diffraction mapping of a ductile cyclodextrin (CD)-based glassy polyrotaxane. After inducing neck formation and propagation by uniaxial tension, the strain-localized area was scanned, elucidating how the CD orientation and its correlation distance change. As necking approaches and local strain increases, the CD rotational axis orients considerably in the tensile direction. Near the neck inflection point, polymer sliding triggers a sudden structural transformation, forming a phase-separated structure between the CDs and polymers that toughens the neck. This strain-induced orientation preceding sliding appears to facilitate sliding. In the rubbery state, host molecules can orient freely with the guest polymer orientation, but glassy materials must be designed to facilitate host orientation to enable guest sliding with minimum molecular friction.