ABSTRACT
Plastic pollution poses a significant environmental challenge, necessitating the investigation of bioplastics with reduced end-of-life impact. This study systematically characterizes four promising bioplastics-polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), and polylactic acid (PLA). Through a comprehensive analysis of their chemical, thermal, and mechanical properties, we elucidate their structural intricacies, processing behaviors, and potential morphologies. Employing an environmentally friendly process utilizing supercritical carbon dioxide, we successfully produced porous materials with microcellular structures. PBAT, PBS, and PLA exhibit closed-cell morphologies, while PHBV presents open cells, reflecting their distinct overall properties. Notably, PBAT foam demonstrated an average porous area of 1030.86 µm2, PBS showed an average porous area of 673 µm2, PHBV displayed open pores with an average area of 116.6 µm2, and PLA exhibited an average porous area of 620 µm2. Despite the intricacies involved in correlating morphology with material properties, the observed variations in pore area sizes align with the findings from chemical, thermal, and mechanical characterization. This alignment enhances our understanding of the morphological characteristics of each sample. Therefore, here, we report an advancement and comprehensive research in bioplastics, offering deeper insights into their properties and potential morphologies with an easy sustainable foaming process. The alignment of the process with sustainability principles, coupled with the unique features of each polymer, positions them as environmentally conscious and versatile materials for a range of applications.
ABSTRACT
Hybrid hydrogels are hydrogels that exhibit heterogeneity in the network architecture by means of chemical composition and/or microstructure. The different types of interactions, together with structural heterogeneity, which can be created on different length scales, determine the mechanical properties of the final material to a large extent. In this work, the microstructure-mechanical property relationships for a hybrid hydrogel that contains both electrostatic and covalent interactions are investigated. The hybrid hydrogel is composed of a microphase-separated polyelectrolyte complex network (PEC) made of poly(4-styrenesulfonate) and poly(diallyldimethylammonium chloride) within a soft and elastic polyacrylamide hydrogel network. The system exhibits a granular structure, which is attributed to the liquid-liquid phase separation into complex coacervate droplets induced by the polymerization and the subsequent crowding effect of the polyacrylamide chains. The coacervate droplets are further hardened into PEC granules upon desalting the hydrogel. The structure formation is confirmed by a combination of electron microscopic imaging and molecular dynamics simulations. The interpenetration of both networks is shown to enhance the toughness of the resulting hydrogels due to the dissipative behavior of the PEC through the rupture of electrostatic interactions. Upon cyclic loading-unloading, the hydrogels show recovery of up to 80% of their original dissipative behavior in less than 300 s of rest with limited plasticity. The granular architecture and the tough and self-recoverable properties of the designed hybrid networks make them good candidates for applications, such as shape-memory materials, actuators, biological tissue mimics, and elastic substrates for soft sensors.
ABSTRACT
Electrically conductive polymer nanocomposites have been the subject of intense research due to their promising potential as piezoresistive biomedical sensors, leveraging their flexibility and biocompatibility. Although intrinsically conductive polymers such as polypyrrole (PPy) and polyaniline have emerged as lucrative candidates, they are extremely limited in their processability by conventional solution-based approaches. In this work, ultrathin nanostructured coatings of doped PPy are realized on polyurethane films of different architectures via oxidative chemical vapor deposition to develop stretchable and flexible resistance-based strain sensors. Holding the substrates perpendicular to the reactant flows facilitates diffusive transport and ensures excellent conformality of the interfacial integrated PPy coatings throughout the 3D porous electrospun fiber mats in a single step. This allows the mechanically robust (stretchability > 400%, with fatigue resistance up to 1000 cycles) nanocomposites to elicit a reversible change of electrical resistance when subjected to consecutive cycles of stretching and releasing. The repeatable performance of the strain sensor is linear due to dimensional changes of the conductive network in the low-strain regime (ε ≤ 50%), while the evolution of nano-cracks leads to an exponential increase, which is observed in the high-strain regime, recording a gauge factor as high as 46 at 202% elongational strain. The stretchable conductive polymer nanocomposites also show biocompatibility toward human dermal fibroblasts, thus providing a promising path for use as piezoresistive strain sensors and finding applications in biomedical applications such as wearable, skin-mountable flexible electronics.
ABSTRACT
A solvent-free route of initiated chemical vapor deposition (iCVD) was used to synthesize a bio-renewable poly(α-Methylene-γ-butyrolactone) (PMBL) polymer. α-MBL, also known as tulipalin A, is a bio-based monomer that can be a sustainable alternative to produce polymer coatings with interesting material properties. The produced polymers were deposited as thin films on three different types of substrates-polycarbonate (PC) sheets, microscopic glass, and silicon wafers-and characterized via an array of characterization techniques, including Fourier-transform infrared (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR), ultraviolet visible spectroscopy (UV-vis), differential scanning calorimetry (DSC), size-exclusion chromatography (SEC), and thermogravimetric analysis (TGA). Optically transparent thin films and coatings of PMBL were found to have high thermal stability up to 310 °C. The resulting PMBL films also displayed good optical characteristics, and a high glass transition temperature (Tg~164 °C), higher than the Tg of its structurally resembling fossil-based linear analogue-poly(methyl methacrylate). The effect of monomer partial pressure to monomer saturation vapor pressure (Pm/Psat) on the deposition rate was investigated in this study. Both the deposition rate and molar masses increased linearly with Pm/Psat following the normal iCVD mechanism and kinetics that have been reported in literature.