Significantly Enhanced Crystallization of Poly(ethylene succinate-co-1,2-propylene succinate) by Cellulose Nanocrystals as an Efficient Nucleating Agent

Poly(ethylene succinate-co-1,2-propylene succinate) (PEPS) is a novel aliphatic biodegradable polyester with good mechanical properties. Due to the presence of methyl as a side group, the crystallization rate of PEPS is remarkably slower than that of the poly(ethylene succinate) homopolymer. To promote the potential application of PEPS, the effect of cellulose nanocrystals (CNC) on the crystallization behavior, crystalline morphology, and crystal structure of PEPS was investigated in this research with the aim of increasing the crystallization rate. CNC enhanced both the melt crystallization behavior of PEPS during the cooling process and the overall crystallization rate during the isothermal crystallization process. The crystallization rate of PEPS became faster with an increase in CNC content. The crystalline morphology study directly confirmed the heterogeneous nucleating agent role of CNC. The crystal structure of PEPS remained unchanged in the composites. On the basis of the interfacial energy, the nucleation mechanism of PEPS in the composites was further discussed by taking into consideration the induction of CNC.

Photoconductivity of Intrinsic Semiconductor Phthalocyanine-Based Covalent Organic Polymer with Benzimidazole Linkage

Novel phthalocyanine-based benzimidazole linked conjugated covalent organic polymer (NiPc-COP1) have been synthesized with multiple randomly ordered crystalline morphology. This unique alignment leads to significantly enhanced panchromatic light-absorption capability, thus high photoconductivity with high photoresponce speed.

Investigation of the Ordered Structure in Partially Melted Isotactic Polypropylene

The ordered structure of partially melted isotactic polypropylene (iPP) was investigated using polarized optical microscopy (POM) and small-/wide-angle X-ray scattering (SAXS/WAXS) measurements. The crystalline morphology was first examined by means of pulling a glass fiber through the iPP melt, which was generated by partially melting a preformed spherulite. The results from the POM experiments indicated that, even at a minimal pulling rate, the surviving ordered structure could also relocate along the direction of fiber pulling and grow into cylindrites eventually. In addition, during the quiescent crystallization from the partially melted sample, which had the same thermal history of fiber-pulling experiments, the obvious memory effect of melt was also observed from the results of X-ray experiments. Moreover, the SAXS profile derived from the partially melted iPP at 170 °C was fitted by the theory of scattering amplitude with the cylindrical form factor. The fit result implied that the surviving ordered structure is of cylindrical nanocrystals with a diameter D ≈ 30 ± 3 nm and height h ≈ 45 ± 3 nm, which can significantly influence the crystallization morphology and kinetics during the subsequent crystallization process.

Manipulating Crystallization for Simultaneous Improvement of Impact Strength and Heat Resistance of Plasticized Poly(l-lactic acid) and Poly(butylene succinate) Blends

Crystalline morphology and phase structure play a decisive role in determining the properties of polymer blends. In this research, biodegradable blends of poly(l-lactic acid) (PLLA) and poly(butylene succinate) (PBS) have been prepared by melt-extrusion and molded into specimens with rapid cooling. The crystalline morphology (e.g., crystallinity, crystal type and perfection) is manipulated by annealing the molded products from solid-state within a short time. This work emphasizes on the effects of annealing conditions on crystallization and properties of the blends, especially impact toughness and thermal stability. Phase-separation morphology with PBS dispersed particles smaller than 1 μm is created in the blends. The blend properties are successfully dictated by controlling the crystalline morphology. Increasing crystallinity alone does not ensure the enhancement of impact toughness. A great improvement of impact strength and heat resistance is achieved when the PLLA/PBS (80/20) blends are plasticized with 5% medium molecular-weight poly(ethylene glycol), and simultaneously heat-treated at a temperature close to the cold-crystallization of PLLA. The plasticized blend annealed at 92 °C for only 10 min exhibits ten-fold impact strength over the starting PLLA and slightly higher heat distortion temperature. The microscopic study demonstrates the fracture mechanism changes from crazing to shear yielding in this annealed sample.

Size control of shape switchable micronetworks by fast two-step microfluidic templating

Shape-memory polymer micronetworks (MN) are micrometer-sized objects that can switch their outer shape upon external command. This study aims to scale MN sizes to the low micrometer range at very narrow size distributions. In a two-step microfluidic strategy, the specific design of coaxial class capillary devices allowed stabilizing the thread of the dispersed phase to efficiently produce precursor particles in the tip-streaming regime at rates up to ~ 170 kHz and final sizes down to 4 µm. In a subsequent melt-based microfluidic photocrosslinking of the methacrylate-functionalized oligo(ɛ-caprolactone) precursor material, MN could be produced without particle aggregation. A comprehensive analysis of MN properties illustrated successful crosslinking, semi-crystalline morphology, and a shape-switching functionality for all investigated MN sizes (4, 6, 9, 12, 22 µm). Such functional micronetworks tailored to and below the dimension of cells can enable future applications in technology and medicine like controlling cell interaction. Graphic abstract

The Extent of Interlayer Bond Strength during Fused Filament Fabrication of Nylon Copolymers: An Interplay between Thermal History and Crystalline Morphology

One of the main drawbacks of Fused Filament Fabrication is the often-inadequate mechanical performance of printed parts due to a lack of sufficient interlayer bonding between successively deposited layers. The phenomenon of interlayer bonding becomes especially complex for semi-crystalline polymers, as, besides the extremely non-isothermal temperature history experienced by the extruded layers, the ongoing crystallization process will greatly complicate its analysis. This work attempts to elucidate a possible relation between the degree of crystallinity attained during printing by mimicking the experienced thermal history with Fast Scanning Chip Calorimetry, the extent of interlayer bonding by performing trouser tear fracture tests on printed specimens, and the resulting crystalline morphology at the weld interface through visualization with polarized light microscopy. Different printing conditions are defined, which all vary in terms of processing parameters or feedstock molecular weight. The concept of an equivalent isothermal weld time is utilized to validate whether an amorphous healing theory is capable of explaining the observed trends in weld strength. Interlayer bond strength was found to be positively impacted by an increased liquefier temperature and reduced feedstock molecular weight as predicted by the weld time. An increase in liquefier temperature of 40 °C brings about a tear energy value that is three to four times higher. The print speed was found to have a negligible effect. An elevated build plate temperature will lead to an increased degree of crystallinity, generally resulting in about a 1.5 times larger crystalline fraction compared to when printing occurs at a lower build plate temperature, as well as larger spherulites attained during printing, as it allows crystallization to occur at higher temperatures. Due to slower crystal growth, a lower tie chain density in the amorphous interlamellar regions is believed to be created, which will negatively impact interlayer bond strength.