Juping Yang

Studies on the effects of the alkyl group on the surface segregation of poly(n-alkyl methacrylate) end-capped 2-perfluorooctylethyl methacrylate films.

The effects of the alkyl group on the surface segregation of poly(n-alkyl methacrylate) end-capped with various numbers of units of 2-perfluorooctylethyl methacrylate (FMA) (PnAMA-ec-PFMA) were investigated by differential scanning calorimetry, angle-resolved XPS analysis, contact angle measurements, and X-ray diffraction (XRD). The results show that with similar numbers of FMA units at the polymer chain end the extent of fluorine segregation (Q) increased with increasing the number of carbon atoms in the side n-alkyl chains of poly(n-alkyl methacrylate). The surface fluorine content within 5 nm deep of the film of poly(n-octadecyl methacrylate) end-capped with one FMA unit (PODMA(160)-ec-PFMA(1.0)) was 208-fold higher than that of the bulk level. These observed differences in Q values were found due to the aggregate structure of the end-capped polymers in the solution, the flexibility, and the crystallinity of the n-alkyl side chains. When the nonfluorinated block was completely amorphous, the molecular aggregate structure of the end-capped polymers in the solution played an important role in the surface segregation of the fluorinated moieties on the resulting film. However, when the nonfluorinated block was crystalline, crystallinity would enhance greatly the segregation of the fluorinated moieties.

Stepwise crystallization and the layered distribution in crystallization kinetics of ultra-thin poly(ethylene terephthalate) film

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.

Relationship between Segmental Relaxation of Polystyrene Films and Stick–Slip Behavior during Dynamic Wetting of Liquid Droplets on Their Surfaces

A novel method was previously reported for detecting the glass transition of thin polystyrene (PS) films by correlating the relationships between the temperature-dependent viscoelasticity of the PS films and stick-slip behavior on their surfaces during dynamic wetting of liquid droplets. In the present study, the frequency dependence of the stick-slip behavior is investigated. The results show that the stick-slip behavior of liquid dynamic wetting on PS films is dependent on the contact line velocity, which is related to the deformation frequency of the PS surface during the moving liquid front. The stick-slip behavior was revealed to be determined by a dimensionless parameter (ξ), which is the ratio of the PS segmental relaxation time (τα) and the characteristic time (τc) for PS surface deformation near the droplet contact line. When ξ is close to 1 (τα ≈ τc), the Δθ (jumping angle), a scale of the stick-slip behavior, reaches a maximum. This correlation between Δθ and ξ demonstrates that the stick-slip behavior is related to the energy dissipation caused by the PS α-relaxation process, and the peak temperature (or frequency) in Δθ corresponds to the α-relaxation temperature (time) of the polymer. These results strongly demonstrate that the utilization of the stick-slip behavior is a creditable method, similar to dynamic viscoelastic measurement, for probing the glass transition and segmental relaxation of thin polymer films.

Progresses in the glass transition and molecular dynamics of thin polymer film

With the advances in nanotechnology, the glass transition and chain relaxation behavior for polymer molecules in a confined geometry have been attracted great attentions. Due to the nano-scale effects, the molecular dynamics of polymer thin film deviates from that in the bulk, and are a function of the dimension of films (i.e. thickness). The studies of the molecular dynamic in polymer thin film are of significant importance both in term of optimizing the physical properties of polymer nanomaterials and also in the developing our understanding of the nature of glass transition for amorphous materials. In this paper, some important results in the field of the dynamics of thin polymer film are reviewed. We summarized the physical mechanisms responsible for the deviation of chain dynamic from that in bulk, and discussed the distribution of chain mobility in polymer thin film, as well, some theoretical models describing the glass transition of thin polymer film was introduced. In the end, the problems in this field and prospects in the further studies were also discussed.