Polymer adsorption at solid interfaces plays an important role in the dynamics of nanoscale polymer films.We investigated the influence of the interfacial chain adsorption on the glass transition temperature(Tg)and de...Polymer adsorption at solid interfaces plays an important role in the dynamics of nanoscale polymer films.We investigated the influence of the interfacial chain adsorption on the glass transition temperature(Tg)and dewetting of polystyrene(PS)thin films on a graphene substrate that has strong interaction with PS.We found that the Tgs of PS films show a non-monotonic trend with increasing amount of polymer adsorption at the interface—first increasing and then decreasing,and this change in Tg is accompanied by a wetting-dewetting transition of the PS films.Film morphological analysis showed that the PS films dewet from the interfacially adsorbed layers rather than from the substrate,i.e.,autophobic dewetting,indicating the presence of an unfavorable interaction between the adsorbed and free PS chains.We ascribed the repulsive interaction to the formation of a dense adsorbed layer on graphene due to the π-π interaction between PS and graphene,which prevents the nonadsorbed PS chain from penetrating into the adsorbed layer.This may lead to drops in Tg at high adsorption extent.展开更多
We have investigated the crystallization and morphological behaviors of poly（ε-caprolactone）-b-poly（L-lactide） （PCL-b-PLLA） in its autophobic dewetted ultrathin films （-11 nm） using atomic force microscopy （...We have investigated the crystallization and morphological behaviors of poly（ε-caprolactone）-b-poly（L-lactide） （PCL-b-PLLA） in its autophobic dewetted ultrathin films （-11 nm） using atomic force microscopy （AFM） and transmission electron microscopy （TEM）. The autophobic dewetting process creates a well defined film geometry containing an extremely thin wetting layer （-4.5 nm） with densely distributed micrometer droplets atop, which re- stricts the primary nucleation process to occurring only in the droplets. In addition to the normally encountered flat-on lamellae, the growth of edge-on lamellae in such a thin wetting layer has been observed on both of two crys- tallization paths. In thermal crystallization, flat-on lamellae are favored at small supercoolings while edge-on la- mellae appear at very large supercoolings both in the droplets and the wetting layer. For cold crystallization, the edge-on lamellae can form easily in the droplets and grow into the wetting layer even at very small supercoolings. These observations are explained on the basis that the nucleation and lamellar orientation are strongly affected by the film geometry, the crystallization paths, and the applied supercoolings.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22122306,22303084 and 52373025)。
文摘Polymer adsorption at solid interfaces plays an important role in the dynamics of nanoscale polymer films.We investigated the influence of the interfacial chain adsorption on the glass transition temperature(Tg)and dewetting of polystyrene(PS)thin films on a graphene substrate that has strong interaction with PS.We found that the Tgs of PS films show a non-monotonic trend with increasing amount of polymer adsorption at the interface—first increasing and then decreasing,and this change in Tg is accompanied by a wetting-dewetting transition of the PS films.Film morphological analysis showed that the PS films dewet from the interfacially adsorbed layers rather than from the substrate,i.e.,autophobic dewetting,indicating the presence of an unfavorable interaction between the adsorbed and free PS chains.We ascribed the repulsive interaction to the formation of a dense adsorbed layer on graphene due to the π-π interaction between PS and graphene,which prevents the nonadsorbed PS chain from penetrating into the adsorbed layer.This may lead to drops in Tg at high adsorption extent.
文摘We have investigated the crystallization and morphological behaviors of poly（ε-caprolactone）-b-poly（L-lactide） （PCL-b-PLLA） in its autophobic dewetted ultrathin films （-11 nm） using atomic force microscopy （AFM） and transmission electron microscopy （TEM）. The autophobic dewetting process creates a well defined film geometry containing an extremely thin wetting layer （-4.5 nm） with densely distributed micrometer droplets atop, which re- stricts the primary nucleation process to occurring only in the droplets. In addition to the normally encountered flat-on lamellae, the growth of edge-on lamellae in such a thin wetting layer has been observed on both of two crys- tallization paths. In thermal crystallization, flat-on lamellae are favored at small supercoolings while edge-on la- mellae appear at very large supercoolings both in the droplets and the wetting layer. For cold crystallization, the edge-on lamellae can form easily in the droplets and grow into the wetting layer even at very small supercoolings. These observations are explained on the basis that the nucleation and lamellar orientation are strongly affected by the film geometry, the crystallization paths, and the applied supercoolings.
