Citation: Xiao-xia Wang, Lin-ling Li, Lai Wei, Qi Xue, Dong-shan Zhou. Crystallization of Poly(L-lactide) Oligomer Confined in Alumina Nanopores[J]. Acta Polymerica Sinica, ;2019, 50(8): 841-849. doi: 10.11777/j.issn1000-3304.2019.19024 shu

Crystallization of Poly(L-lactide) Oligomer Confined in Alumina Nanopores

Xiao-xia Wang ^1,2 ,
Lin-ling Li ^2,, ,
Lai Wei ¹ ,
Qi Xue ² ,
Dong-shan Zhou ^1,2,,

1.
College of Physical Science and Technology, Xinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matter Physics, YiLi Normal University, Yining 835000
2.
School of Chemistry and Chemical Engineering, The State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023

Corresponding author: Lin-ling Li, llli@nju.edu.cn Dong-shan Zhou, dzhou@nju.edu.cn
Received Date: 29 January 2019
Revised Date: 2 March 2019
Available Online: 18 April 2019

The glass transition, crystallization, and melting behaviors of oligomer poly(L-lactide) (PLLA) confined in anodic aluminum oxide (AAO) nanopores were invesitgated by calorimetry. Compared with the bulk counterpart, PLLA located inside AAO nanopores showed frustrated crystallization during the cooling process, and the crystallization enthalpy gradually decreased with the reduction of pore size. In large nanopores, the crystallization peaks of PLLA nanorods were very close to that of bulk sample, which indicated the predomination of heterogeneous nucleation. Meanwhile, the nonisothermal crystallization results displayed that temperature dependence of nucleation rate of PLLA in nanopores was weaker than that in bulk state. As the diameter of nanopore was smaller than 28 nm, the crystallization peak disappeared. The glass state of PLLA nanorods exhibited double glass transition temperatures (T_gs), the higher T_g attributed to chains in the interfacial adsorbed layer adjacent to pore walls, and the lower T_g belonged to chains in the pore center. The two T_gs showed opposite pore size dependences—the lower one decreased with the reduction of pore size, while the higher one increased. During the heating process, PLLA confined in nanopores showed the pronounced cold crystallization phenomenon, which took place at higher temperatures and the peak was much broader than that of bulk state, which could be ascribed to the supressed nucleation rate, the poor nucleation activity, and the broad nucleation dispersion in PLLA nanorods. Apart form the influence of nucleation, hetergeneous chain mobilities in nanopores also played an important role. Due to the existence of adsorbed layer, surface induced nucleation was hindered. Interestingly, by the nonisothermal crystallization experiments, PLLA chains in the interfacial layer and pore center displayed independent cold crystallization behaviors, and the latter happened at the higher temperatures. Finally, the interfacial effect gradually dominated as the pore size decreased. PLLA crystals formed in small nanopores became unstable, obvious melting-recrystallization phenomena occurred, and the crystallinity and melting temperature of PLLA crystals were lower in smaller nanopores.
- Poly(L-lactide),
- Polymer crystallization,
- Anodic aluminum oxide template,
- Nano-confinement
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