2021, Du, Mengxue, Jariyavidyanont, Katalee, Kühnert, Ines, Boldt, Regine, Androsch, René

The concept of specific work of flow has been applied for the analysis of critical shearing conditions for the formation of crystal nuclei in poly (l-lactic acid) (PLLA). Systematic variation in both time and rate of shearing the melt in a parallel-plate rheometer revealed that these parameters are interconvertible regarding the shear-induced formation of crystal nuclei; that is, low shear rate can be compensated for by increasing the shear time and vice versa. This result supports the view that critical shearing conditions can be expressed by a single quantity, providing additional options for tailoring polymer processing routes when enhanced nuclei formation is desired/unwanted. Analysis of PLLA of different mass-average molar masses of 70, 90, 120, and 576 kDa confirmed improved shear-induced crystal nucleation for materials of higher molar mass, with critical specific works of flow, above which shear-induced nuclei formation occurs, of 550, 60, 25, and 5 kPa, respectively.

2020, Quattrosoldi, Silvia, Androsch, René, Janke, Andreas, Soccio, Michelina, Lotti, Nadia

The crystallization behavior of fully biobased poly(butylene isophthalate) (PBI) has been investigated using calorimetric and microscopic techniques. PBI is an extremely slow crystallizing polymer that leads, after melt-crystallization, to the formation of lamellar crystals and rather large spherulites, due to the low nuclei density. Based upon quantitative analysis of the crystal-nucleation behavior at low temperatures near the glass transition, using Tammann’s two-stage nuclei development method, a nucleation pathway for an acceleration of the crystallization process and for tailoring the semicrystalline morphology is provided. Low-temperature annealing close to the glass transition temperature (Tg) leads to the formation of crystal nuclei, which grow to crystals at higher temperatures, and yield a much finer spherulitic superstructure, as obtained after direct melt-crystallization. Similarly to other slowly crystallizing polymers like poly(ethylene terephthalate) or poly(l-lactic acid), low-temperature crystal-nuclei formation at a timescale of hours/days is still too slow to allow non-spherulitic crystallization. The interplay between glass relaxation and crystal nucleation at temperatures slightly below Tg is discussed.

2018, Yang, Bo, Wang, Rui, Ma, Hui-Ling, Li, Xiaolu, Brünig, Harald, Dong, Zhenfeng, Qi, Yue, Zhang, Xiuqin

Poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) blend as-spun fibers (50/50, wt.%) were prepared by melt spinning. Structure mediation under temperature and stress and properties of poly(l-lactic acid)/poly(d-lactic acid)(PLLA/PDLA) as-spun fibers were investigated by wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC). The results show that highly oriented stereocomplex (SC) crystals can be formed in PLLA/PDLA blend fibers drawn at 60 °C and annealed at 200 °C. However, at drawn temperature of 80 °C, only lower oriented SC crystals can be formed. For PLLA/PDLA blend fibers drawn twice at 60 °C (PLLA/PDLA-60-2), the crystallinity of SC crystals increases with annealing temperature in the range of 200 to 215 °C, while the degree of orientation decreases slightly. When the annealing temperature is 210 °C, the crystallinity and orientation of SC crystals in PLLA/PDLA-60-2 fibers reach 51% and −0.39, respectively. Moreover, PLLA/PDLA-60-2-210 fibers exhibit excellent heat-resistant property even at 200 °C. The results indicate that the oriented PLLA/PDLA blend fibers with high SC crystals content can be regulated in a short time.

2020, Spoerer, Yvonne, Androsch, René, Jehnichen, Dieter, Kuehnert, Ines

Polyamide 66 (PA 66) was injection-molded to obtain samples with a structure gradient between skin and core, as it was revealed by analysis of the semi-crystalline morphology using polarized-light optical microscopy (POM). Wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS) were employed to characterize thin sections with a thickness in the order of magnitude of 50 µm, allowing detection of crystals of different perfection, as a function of the distance from the surface. It was found that the transparent and non-spherulitic skin layer contains rather imperfect α-crystals while the perfection of α-crystals continuously increases with extending distance from the surface. Since variation of the molding conditions allows tailoring the skin-core morphology, the present study was performed to suggest a reliable route to map the presence of specific semi-crystalline morphologies in such samples