Enhancing Mechanical Performance of High-Density Polyethylene at Different Environmental Conditions with Outstanding Foamability through In-Situ Rubber Nanofibrillation: Exploring the Impact of Interface Modification.

In this study, we utilized in situ nanofibrillation of thermoplastic polyester ether elastomer (TPEE) within a high-density polyethylene (HDPE) matrix to enhance the rheological properties, foamability, and mechanical characteristics of the HDPE nanocomposite at both room and subzero temperatures. Due to the inherent polarity differences between these two components, TPEE is thermodynamically incompatible with the nonpolar HDPE. To address this compatibility issue, we employed a compatibilizer, styrene/ethylene-butylene/styrene copolymer-grafted maleic anhydride (SEBS-g-MA), to reduce the interfacial tension between the two blend components. In the initial step, we prepared a 10% masterbatch of HDPE/TPEE with and without the compatibilizer using a twin-screw extruder. Subsequently, we processed the 10% masterbatch further through spun bonding to create fiber-in-fiber composites. Scanning electron microscopy (SEM) analysis revealed a significant reduction in the spherical size of HDPE/TPEE particles following the inclusion of SEBS-g-MA, as well as a much smaller TPEE nanofiber size (approximately 60-70 nm for 5% TPEE). Moreover, extensional rheological testing revealed a notable enhancement in extensional rheological properties, with strain-hardening behavior being more pronounced in the compatibilized nanofibrillar composites compared to the noncompatibilized ones. SEM images of the foam structures depicted substantial improvement in the foamability of HDPE in terms of the cell size and density following the nanofibrillation process and the use of the compatibilizer. Ultimately, the in situ rubber fibrillation and enhancement of HDPE and TPEE interface using a compatibilizer led to increasing the HDPE ductility at room and subzero temperatures while maintaining its stiffness.

Molecular dynamics simulation of the 3-15alkyphenol compatibilizer in highly toughened and robust polyamide 10,12/MWCNT composites.

Highly toughened and stiff polyamide 10,12 (PA10,12) composites present a promising alternative to metal products for high-impact environments. However, it is challenging to toughen PA10,12 composites without compromising their robustness. Herein, we report a facile and scalable route to simultaneously develop reinforced and toughened PA10,12 composites via compounding PA10,12, carbon nanotubes (CNTs) and 3-15alkyphenol (PDP). The PDP acted as a compatibilizer to well-disperse MWCNTs since they tended to be adsorbed onto the CNT surface, which was revealed by molecular dynamics simulation. According to the simulation statistics, the vertical PDP conformations (to the CNT surface) were predominant in the ternary composites with ∼78.7% probability. Moreover, the hydrogen bonds (H-bonds) between the PDP and the PA matrix were confirmed using FTIR. A crystallization kinetics study also revealed that the crystallization temperature increased from 166.7 °C for the neat PA10,12 to 168.7 °C for the ternary PA/PDP/CNT composites containing 1.5 wt% CNTs, while the crystallization half-time increased from 0.58 s for the neat PA10,12 to 1.2 s for the ternary composites. It was also found that the notched impact strength of the ternary composites reached 75.2 kJ m-2, which was 970% higher than that of the neat PA10,12 without compromising their tensile strength of 50.5 MPa much. This work provides a new insight into PDP as a compatibilizer to develop simultaneously stiff and toughened nylon composites.

Entirely environment-friendly polylactide composites with outstanding heat resistance and superior mechanical performance fabricated by spunbond technology: Exploring the role of nanofibrillated stereocomplex polylactide crystals.

This study aims at investigating the manufacturing and characterization of all-polylactide composites prepared by melt spunbond spinning technology. To do so, a series of asymmetric stereocomplex polylactide (SC-PLA) blends (PLLA 95 wt%/PDLA 5 wt%) was melt spun. To examine the impact of molecular structure of PDLA, the blends of linear PLLA, and low and high molecular weight as well as branched PDLAs, were subjected to a single step spunbond process. DSC thermograms of the samples showed two melting temperatures at around 170 °C and 210 °C, which were attributed to the melting of homo and stereocomplex crystals, respectively. The samples were spun at 190 °C, between the homo and stereocomplex crystals' melting temperatures, and at 230 °C, above the stereocomplex crystals' melting temperature. Morphology images showed the formation of fibers in the range of 40-50 µm. Shear rheological measurements revealed that the spun SC-PLA samples had a substantially higher viscosity and storage modulus in the low frequency region, and higher shear thinning behavior, compared to the non-spun samples. Extensional rheology measurements also showed that the spun samples demonstrated strain hardening behavior. Substantial enhancement of rheological properties was noted for the samples containing the branched and high molecular weight PDLA spun at 230 °C. After etching, the spun samples at 190 °C exhibited small spherical crystals with diameters in the range of 80-90 nm, whereas comparatively thin fibers in the size range of 60-70 nm were observed for the samples spun at 230 °C. Remarkable enhancements up to 100% and 60% was noted for the tensile modulus and strength, respectively, of the spun SC-PLA samples. The spun fibers also demonstrated a considerable reduction in boiling water and hot air shrinkage. The distinctive role of nanofibrillated stereocomplex crystals as a rheology modifier and a crystallization nucleating agent makes PLA more sustainable and paves the way for the fabricated all-PLA composites in applications requiring high heat resistance and superior mechanical performance. The present study unequivocally indicates a huge potential for the sustainable entirely all-PLA products manufactured by fiber in fiber and, indeed, unfolds unknown opportunities for PLA-based merchandises in future.

Novel and simple design of nanostructured, super-insulative and flexible hybrid silica aerogel with a new macromolecular polyether-based precursor.

This study reports a new strategy to fabricate a thermally super-insulative and flexible hybrid silica aerogel. A new generation of polymeric precursors was first synthesized for hybrid organic/inorganic silica aerogels from an epoxide ring containing a silica precursor. Ring opening polymerization (ROP) was used so as to insert flexible ether groups into the main chain. It has been demonstrated that the particulate structure of the polyether-based silica aerogel could be changed to a novel non-particulate and continuous one, by meticulous control of the thermodynamics, namely, through variations of the molecular weight of the polymeric precursor, the amount of the non-solvent, and the temperature. The study presents a new strategy to manufacture a polyether-based hybrid silica aerogel, which is fast and scalable, and also eliminates the aging process while accelerating the gelation time. This new strategy reduces the wet gel preparation time, including gelation, aging and solvent exchange, from several days to just a few seconds. However, this structure suffers from a low void fraction and wide pore size distribution. These drawbacks are then removed by chemically incorporating pre-polymerized vinyl trimethoxysilane chains. The resultant aerogels exhibit thermal superinsulation (λ = 15.9 mW·m-1·K-1) while providing good mechanical properties and flexibility. The polyether-based aerogels also demonstrated good performance as adsorbent material to remove organic solvents from water.

Robust, ultra-insulative and transparent polyethylene-based hybrid silica aerogel with a novel non-particulate structure.

Aerogels derived from pre-polymerized vinyl trimethoxy silane (VTMS) precursor with nano-size particles are known to exhibit outstanding mechanical and insulation properties. However, the density reduction has been limited by the poor connectivity. This paper presents an innovative technology to generate a new class of VTMS-based hybrid silica aerogels that possess outstanding non-particulate, reticulated structure and superior properties. This technology relies on spinodal decomposition instead of conventionally exploited binodal decomposition, which leads to a particulate structure. This new aerogel technology has significantly increased the void fraction of the pre-polymerized VTMS-based aerogel, which could not be achieved previously using binodal decomposition. The increased void fraction in the form of nano-pores with an average pore size of 21.75 nm nullifies the gas thermal conductivity effectively. Another consequence of the non-particulate structure is decreased processing time by removing the aging step. These improvements are due to the non-particulate structure's increased connectivity produced by spinodal decomposition. This novel structure was then compared to a particulate counterpart aerogel of the same material derived from the conventional binodal decomposition of the pre-polymerized VTMS precursor. To further decrease the processing cost, a lower molecular-weight polymeric precursor was synthesized under milder polymerization conditions. The effects of the polymeric precursor's molecular weight on the mechanical and thermal properties of the aerogel created via spinodal decomposition were also investigated.