Interfaces play an important role in modifying the dynamics of polymers confined to the nanoscale. Here, we demonstrate that the distance over which an interface suppresses molecular mobility in poly(styrene) thin films can be systematically increased by tens of nanometers by controlling the chain conformation, i.e., height of loops in irreversibly adsorbed nanolayers. These effects arise from topological interaction between adsorbed and neighboring un-adsorbed chains, respectively, which increase their motional coupling to facilitate the propagation of suppressed dynamics originating at the interface, thus highlighting the ability to manipulate interfacial effects by local conformation of chains in adsorbed nanolayers.

Crystallization is an important property of polymeric materials. In conventional viewpoint, the transformation of disordered chains into crystals is usually a spatially homogeneous process (i.e., it occurs simultaneously throughout the sample), that is, the crystallization rate at each local position within the sample is almost the same. Here, we show that crystallization of ultra-thin poly(ethylene terephthalate) (PET) films can occur in the heterogeneous way, exhibiting a stepwise crystallization process. We found that the layered distribution of glass transition dynamics of thin film modifies the corresponding crystallization behavior, giving rise to the layered distribution of the crystallization kinetics of PET films, with an 11-nm-thick surface layer having faster crystallization rate and the underlying layer showing bulk-like behavior. The layered distribution in crystallization kinetics results in a particular stepwise crystallization behavior during heating the sample, with the two cold-crystallization temperatures separated by up to 20 K. Meanwhile, interfacial interaction is crucial for the occurrence of the heterogeneous crystallization, as the thin film crystallizes simultaneously if the interfacial interaction is relatively strong. We anticipate that this mechanism of stepwise crystallization of thin polymeric films will allow new insight into the chain organization in confined environments and permit independent manipulation of localized properties of nanomaterials.

The question of how to scale the mobility gradient of polymer chains near a substrate in supported ultrathin polymer films is a great challenge. In this paper, a mobility gradient of poly­(ethylene terephthalate) (PET) chains near a substrate is characterized by cold crystallization. We found that either decreasing the PET film thickness or increasing the absorbed layer thickness consistently reveals three characteristic film thicknesses, which are all linearly dependent on the adsorbed-layer thickness. At the first thickness, the low-temperature peak of the top surface crystallization starts to shift toward the high-temperature peak of the bulk-like polymer crystallization; at the second thickness, it arrives there; and at the third thickness, crystallization is completely suppressed. The three kinds of film thicknesses characterize the depth profile of the local dynamics, reflecting the long-range effects of the substrate, which could be scaled by the thickness of the adsorbed layer.

Thin amorphous poly­(ethylene terephthalate) (PET) films covered with/without a crystallized surface layer were prepared onto silicon wafers. In the former and latter cases, the surface mobility in the film was depressed and enhanced, respectively. The glass transition temperature (T g) of the amorphous PET film decreased with the reduction of the film thickness, exhibiting a remarkable nanoconfinement effect. However, once the surface region of the thin film was crystallized, or frozen in terms of the segmental motion, T g of the films recovered to that of the bulk. Concurrently, the apparent activation energy of the segmental motion in the surface-crystallized film was in good accordance with the bulk value as well. These results make it clear that the mobility in the surface region plays an essential role in the glass transition of the thin films.