When the size of the material is smaller than the size of the molecular chain,new nanostructures can be formed by crystallizing polymers in nanoporous alumina.However,the effect of pore wall and geometric constraints ...When the size of the material is smaller than the size of the molecular chain,new nanostructures can be formed by crystallizing polymers in nanoporous alumina.However,the effect of pore wall and geometric constraints on polymer nanostructures remains unclear.In this study,we demonstrate three new restricted nanostructures{upright-,flat-and tilting-ring}in polybutylene terephthalate(PBT)nanorods prepared from nanoporous alumina.The dual effects of geometrical constraints and interfacial interactions on the formation of PBT nanostructures were investigated for the first time by using X-ray diffraction and Cerius^(2) modeling packages.Under weak constraints,the interaction between pore wall and the PBT rings is dominant and the ring plane tends to be parallel to the pore wall and radiate outward to grow the upright-ring crystals.Surprisingly,in strong 2D confinement,a structural formation reversal occurs and geometrical constraints overpower the effect of pore wall.Rings tend to pile up vertically or obliquely along the long axis of the rod,so the flat-and tilting-ring crystals are predominate in the constrained system.In principle,our study of the nanostructure formation based on the geometrical constraints and the pore wall interfacial effects could provide a new route to manipulate the chain assembly at the nanoscale,further improving the performance of polymer nanomaterial.展开更多
基金financially supported by Natural Science Foundation of Shenzhen University(Nos.827-000150 and 860-000002110375).
文摘When the size of the material is smaller than the size of the molecular chain,new nanostructures can be formed by crystallizing polymers in nanoporous alumina.However,the effect of pore wall and geometric constraints on polymer nanostructures remains unclear.In this study,we demonstrate three new restricted nanostructures{upright-,flat-and tilting-ring}in polybutylene terephthalate(PBT)nanorods prepared from nanoporous alumina.The dual effects of geometrical constraints and interfacial interactions on the formation of PBT nanostructures were investigated for the first time by using X-ray diffraction and Cerius^(2) modeling packages.Under weak constraints,the interaction between pore wall and the PBT rings is dominant and the ring plane tends to be parallel to the pore wall and radiate outward to grow the upright-ring crystals.Surprisingly,in strong 2D confinement,a structural formation reversal occurs and geometrical constraints overpower the effect of pore wall.Rings tend to pile up vertically or obliquely along the long axis of the rod,so the flat-and tilting-ring crystals are predominate in the constrained system.In principle,our study of the nanostructure formation based on the geometrical constraints and the pore wall interfacial effects could provide a new route to manipulate the chain assembly at the nanoscale,further improving the performance of polymer nanomaterial.
