Citation: Huan Ge, Fa-jun Zhang, Hai-ying Huang, Tian-bai He. Studies on the Crystallization Orientation in Micromolded PCL-b-PLLA Thin Films[J]. Acta Polymerica Sinica, ;2019, 50(1): 82-90. doi: 10.11777/j.issn1000-3304.2018.18137 shu

Studies on the Crystallization Orientation in Micromolded PCL-b-PLLA Thin Films

Huan Ge ^1,2 ,
Fa-jun Zhang ³ ,
Hai-ying Huang ^1,2,, ,
Tian-bai He ^1,2,,

1.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022
2.
University of Chinese Academy of Sciences, Beijing 100049
3.
Institut für Angewandte Physik, Universität Tübingen, Auf der Morgenstelle 10, 72076 Tübingen, Germany

Corresponding author: Hai-ying Huang, hyhuang@ciac.ac.cn Tian-bai He, tbhe@ciac.ac.cn
Received Date: 5 June 2018
Revised Date: 23 July 2018
Available Online: 28 August 2018

In this work, we have studied the crystallization orientation behavior of poly(ɛ-caprolactone)-b-poly(l-lactide) (PCL-b-PLLA) under physically confined environment provided via a soft nanoimprinting lithography (NIL) process. The confined thin films were annealed and crystallized following two different routes, and the resulting morphology and crystal orientation were systematically investigated by atomic force microscopy (AFM) and grazing-incidence X-ray diffraction (GIXRD). Based on the large difference of the crystallization temperatures of PCL and PLLA, both one-step (T − T_c,PCL) and two-step crystallization (T − T_c,PLLA − T_c,PCL) processes were used. It was found that PCL crystals were successfully confined in the micromolded domains after one-step crystallization. Interestingly, the fast growth direction of PCL crystals (b-axis) was either along the normal or the parallel direction of the trench, depending on the flow mechanisms during the nanoimprinting process. In the melt nanoimprinting process, polymer melt was squeezed into the trench and forced into the normal direction by the shearing effect and the expanding of the soft mold. By contrast, in room temperature (RT) imprinting process, upon annealing, polymer melt went into the trench by the capillary force and the flow direction of polymer melt was inclined to along the trench. For two-step crystallization process, both PLLA and PCL crystal were confined in the trench. However, due to the high crystallization temperature of PLLA, in the first step of PLLA crystallization, no preferential growth orientation was observed. These results indicated that, without imprinting induced shear flow (which relaxed quickly at PLLA crystallization temperature), the physical confinement of the soft mold was not strong enough to guide the crystal growth direction. Subsequent second step of PCL crystallization was enhanced by the existing PLLA crystal, resulting randomly distributed crystal orientation.
- Block copolymer,
- Nanoimprinting,
- Crystal orientation,
- Melt flow
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