Galeski Andrzej, Bartczak Zbigniew, Vozniak Alina, Pawlak Andrzej, Walkenhorst Rainer
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland.
Celanese GmbH Industriepark Höchst, Brüningstr. 50, Building G832, 65926 Frankfurt am Main, Germany.
Macromolecules. 2020 Jul 28;53(14):6063-6077. doi: 10.1021/acs.macromol.9b02154. Epub 2020 Jul 17.
The structure, morphology, and mechanical properties of two compression-molded grades of ultrahigh-molecular-weight polyethylene (UHMWPE) and, for comparison, one conventional linear polyethylene (HDPE) were studied. Compression molding resulted in some preferred orientation of lamellae in the compression direction in UHMWPE samples, while no preferred orientation in HDPE. The mean crystal thickness estimated from the size distribution agrees better with those obtained from small-angle X-ray scattering (SAXS) and mechanical yield data than the thickness determined from the melting peak temperature. Microscopic examination of microtomed and etched UHMWPE samples showed that the lamellae are in the form of platelets with the width and length in the range of 300-700 nm. The lamellae radiate from primary nuclei forming small embryonal spherulites; their radial growth ends at 0.3-0.7 μm from the center. There is no evidence of branching and secondary nucleation from those primary lamellae. Because the lamellae are radially ordered, there is no parallel stacking of lamellae. Samples were subjected to deformation by plane-strain compression at a constant true strain rate. In axial UHMWPE samples, where lamellae were preferentially oriented along the loading direction, the second yield was clearly observed. The second yield was found to be related to the deformation instability leading to kinking of lamellae oriented initially along the loading direction. Kinking was clearly shown by SAXS and microscopic observation of microtomed and etched samples. No cooperativity of kinking was observed because the lamellae are arranged in small spherulites and not parallel in stacks. The stress-strain curves were fitted with model curves assuming crystal plasticity and network elasticity in the amorphous component. The effective density of the molecular network within the amorphous phase depended on the molecular weight of UHMWPE.
研究了两种压缩成型级别的超高分子量聚乙烯(UHMWPE)以及一种常规线性聚乙烯(HDPE,用于对比)的结构、形态和力学性能。压缩成型导致UHMWPE样品中的片晶在压缩方向上出现一些择优取向,而HDPE中则没有择优取向。根据尺寸分布估算的平均晶体厚度与从小角X射线散射(SAXS)和力学屈服数据获得的结果相比,比从熔融峰温度确定的厚度更吻合。对切片和蚀刻后的UHMWPE样品进行显微镜检查表明,片晶呈片状,宽度和长度在300 - 700纳米范围内。片晶从初级核辐射而出,形成小的胚胎球晶;它们的径向生长在距中心0.3 - 0.7微米处结束。没有证据表明这些初级片晶会发生分支和二次成核。由于片晶是径向有序的,所以不存在片晶的平行堆叠。样品在恒定真应变速率下通过平面应变压缩进行变形。在轴向UHMWPE样品中,片晶优先沿加载方向取向,清晰地观察到了二次屈服。发现二次屈服与变形不稳定性有关,这种不稳定性导致最初沿加载方向取向的片晶发生扭结。SAXS以及对切片和蚀刻样品的显微镜观察清楚地显示了扭结现象。未观察到扭结的协同作用,因为片晶排列成小球晶,而不是平行堆叠。应力 - 应变曲线与假设晶体可塑性和非晶组分中的网络弹性的模型曲线进行了拟合。非晶相内分子网络的有效密度取决于UHMWPE的分子量。