Cras Guillaume Le, Hespel Louise, Guinault Alain, Sollogoub Cyrille, Alexandre Stéphane, Marais Stéphane, Follain Nadège
Univ Rouen Normandie, INSA Rouen Normandie, CNRS, Normandie Univ, PBS UMR 6270, Rouen F-76000, France.
PIMM, Arts et Métiers ParisTech/CNRS/CNAM, Paris 75013, France.
ACS Appl Mater Interfaces. 2024 Aug 21;16(33):43961-43978. doi: 10.1021/acsami.4c07839. Epub 2024 Aug 12.
Bio-based multilayer films were prepared by using the innovative nanolayer coextrusion process to produce films with a number of alternating layers varying from 3 to 2049. For the first time, a semicrystalline polymer was confined by another semicrystalline polymer by nanolayering in order to develop high barrier polyamide (PA11)/polylactic acid (PLA) films without compromising thermal stability and mechanical behavior. This process allows the preparation of nanostratified films with thin layers (down to nanometric thicknesses) in which a confinement effect can be induced. The stratified structure has been investigated, and the layer thicknesses have been measured. Barrier properties were successfully correlated to the microstructure, as well as the thermal behavior, and mechanical properties. The layer continuity was fully achieved for most of the films, but some layer breakups have been observed on the film with the thinnest PLA layer (2049-layers film). Coextruding PLA with PA11 has induced an increase in PLA crystallinity (from 4 to 16%) along with an increase in thermal stability of the multilayer films without impacting PA11 properties. Gas barrier properties were driven by the PLA confined layers due to the microstructural rearrangement by increasing crystallinity, whereas water barrier properties were governed by the PA11 confining layers due to its lower water affinity. As a consequence, a decrease of water permeability (up to 11 times less permeable for the 6M film) but an increase of gas barrier properties (barrier improvement factor (BIF) of 66% for the 0M film for N and BIF of 36% for the 6M film for CO for instance) were evidenced as the layer number was increased. This study paves the way for the development of ecofriendly materials with outstanding barrier performances and highlights the importance of nonmiscible polymers adhesion at melt state and additives presence.
通过使用创新的纳米层共挤出工艺制备了生物基多层膜,以生产具有3至2049个交替层的薄膜。首次通过纳米层压将一种半结晶聚合物限制在另一种半结晶聚合物中,以开发高阻隔聚酰胺(PA11)/聚乳酸(PLA)薄膜,同时不影响热稳定性和机械性能。该工艺允许制备具有薄层(低至纳米厚度)的纳米分层薄膜,其中可以诱导限制效应。研究了分层结构,并测量了层厚度。阻隔性能与微观结构、热行为和机械性能成功相关。大多数薄膜实现了层的完全连续性,但在PLA层最薄的薄膜(2049层薄膜)上观察到了一些层破裂。将PLA与PA11共挤出导致PLA结晶度增加(从4%增加到16%),同时多层膜的热稳定性增加,而不影响PA11的性能。由于结晶度增加导致微观结构重排,气体阻隔性能由PLA受限层驱动,而水阻隔性能由PA11限制层控制,因为其水亲和力较低。因此,随着层数增加,水渗透率降低(例如,6M薄膜的渗透率降低了11倍),但气体阻隔性能提高(例如,0M薄膜对N的阻隔改善因子(BIF)为66%,6M薄膜对CO的BIF为36%)。这项研究为开发具有优异阻隔性能的环保材料铺平了道路,并突出了非混溶聚合物在熔融状态下的粘附和添加剂存在的重要性。