Wan Hai, Wang Yanping, Jin Wenbin, Huang Shuohan, Wang Yimin, He Yong, Wei Peng, Chen Yuwei, Xia Yumin
State Key Laboratory for Modification of Chemical Fibers and Polymer Material, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China.
Key Laboratory of High Performance Fibers & Products, Engineering Research Center of Technical Textiles, College of Science, Donghua University, Ministry of Education, Shanghai 201620, China.
Polymers (Basel). 2023 Apr 23;15(9):2001. doi: 10.3390/polym15092001.
According to the demand for high-performance fibers for high-latitude ocean exploration and development, this paper selects representative products of high-performance liquid crystal fibers: thermotropic liquid crystal polymer fibers (TLCP) and poly p-phenylene terephthalamide (PPTA) fibers. Through a series of freeze-thaw (F-T) experiments for simulating a real, cold marine environment, we then measure the retention of mechanical properties of these two kinds of fibers. Before that, due to the difference in their chemical structures, we tested their Yang-Laplace contact angle (YLCA) and water absorption; the results suggested that PPTA fibers would absorb more moisture. Surprisingly, then, compared with thermotropic liquid crystal polymer (TLCP) fibers, the retention of the mechanical properties of poly p-phenylene terephthalamide (PPTA) fibers decreased by around 25% after the F-T experiments. The Fourier-transformed infrared (FT-IR) analysis, the attenuated total reflection (ATR) accessory analysis and the degree of crystal orientation measured by two-dimensional wide-angle X-ray diffraction (2D-WAXD) confirm that no changes in the chemical and the orientation structure of the crystal region of the fibers occurred after they underwent the F-T cycles. However, as observed by scanning electron microscopy (SEM), there are microcracks of various extents on the surface of the PPTA fibers, but they do not appear on the surface of TLCP fibers. It is obvious that these microcracks will lead to the loss of mechanical properties; we infer that the moisture absorbed by the PPTA fibers freezes below the freezing point, and the volume expansion of the ice causes the collapse of the microfibrillar structure. The two sorts of fibers subjected to the F-T experiments are immersed in a sodium chloride solution, and the amount of water infiltrated into the PPTA microfibrillar structure is evaluated according to the content of sodium ions in the fiber surface and subsurface layers through X-ray spectroscopy (EDS) elemental analysis. From the above analysis, we found that TLCP fibers can more effectively meet the operating standards of the severe and cold marine environment.
根据高纬度海洋勘探开发对高性能纤维的需求,本文选取了高性能液晶纤维的代表性产品:热致液晶聚合物纤维(TLCP)和聚对苯二甲酰对苯二胺(PPTA)纤维。通过一系列模拟真实寒冷海洋环境的冻融(F-T)实验,我们测量了这两种纤维的力学性能保持率。在此之前,由于它们化学结构的差异,我们测试了它们的杨-拉普拉斯接触角(YLCA)和吸水性;结果表明PPTA纤维会吸收更多水分。然而,令人惊讶的是,与热致液晶聚合物(TLCP)纤维相比,聚对苯二甲酰对苯二胺(PPTA)纤维在冻融实验后的力学性能保持率下降了约25%。傅里叶变换红外(FT-IR)分析、衰减全反射(ATR)附件分析以及通过二维广角X射线衍射(2D-WAXD)测量的晶体取向度证实,纤维在经历冻融循环后,其晶体区域的化学结构和取向结构没有发生变化。然而,通过扫描电子显微镜(SEM)观察发现,PPTA纤维表面存在不同程度的微裂纹,而TLCP纤维表面未出现微裂纹。显然,这些微裂纹会导致力学性能的损失;我们推断PPTA纤维吸收的水分在冰点以下冻结,冰的体积膨胀导致微纤结构的坍塌。将经过冻融实验的两种纤维浸入氯化钠溶液中,通过X射线光谱(EDS)元素分析,根据纤维表面和次表面层中钠离子的含量来评估渗入PPTA微纤结构中的水量。从上述分析中,我们发现TLCP纤维能够更有效地满足严寒海洋环境的作业标准。