Influence of Epoxidized Cardanol Functionality and Reactivity on Network Formation and Properties.
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ABSTRACT:
SUBMITTER: Kinaci E
PROVIDER: S-EPMC7563135 | biostudies-literature | 2020 Aug
REPOSITORIES: biostudies-literature
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Project description:Cardanol is a natural alkylphenolic compound derived from Cashew NutShell Liquid (CNSL), a non-food annually renewable raw material extracted from cashew nutshells. In the quest for sustainable materials, the curing of biobased monomers and prepolymers with environmentally friendly processes attracts increasing interest. Photopolymerization is considered to be a green technology owing to low energy requirements, room temperature operation with high reaction rates, and absence of solvents. In this work, we study the photocuring of a commercially available epoxidized cardanol, and explore its use in combination with microfibrillated cellulose (MFC) for the fabrication of fully biobased composites. Wet MFC mats were prepared by filtration, and then impregnated with the resin. The impregnated mats were then irradiated with ultraviolet (UV) light. Fourier Transform InfraRed (FT-IR) spectroscopy was used to investigate the photocuring of the epoxidized cardanol, and of the composites. The thermomechanical properties of the composites were assessed by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. We confirmed that fully cured composites could be obtained, although a high photoinitiator concentration was needed, possibly due to a side reaction of the photoinitiator with MFC.
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Project description:Ecologists are increasingly interested in plant-pollinator networks that synthesize in a single object the species and the interactions linking them within their ecological context. Numerous indices have been developed to describe the structural properties and resilience of these networks, but currently, these indices are calculated for a network resolved to the species level, thus preventing the full exploitation of numerous datasets with a lower taxonomic resolution. Here, we used datasets from the literature to study whether taxonomic resolution has an impact on the properties of plant-pollinator networks.For a set of 41 plant-pollinator networks from the literature, we calculated nine network index values at three different taxonomic resolutions: species, genus, and family. We used nine common indices assessing the structural properties or resilience of networks: nestedness (estimated using the nestedness index based on overlap and decreasing fill [NODF], weighted NODF, discrepancy [BR], and spectral radius [SR]), connectance, modularity, robustness to species loss, motifs frequencies, and normalized degree.We observed that modifying the taxonomic resolution of these networks significantly changes the absolute values of the indices that describe their properties, except for the spectral radius and robustness. After the standardization of indices measuring nestedness with the Z-score, three indices-NODF, BR, and SR for binary matrices-are not significantly different at different taxonomic resolutions. Finally, the relative values of all indices are strongly conserved at different taxonomic resolutions.We conclude that it is possible to meaningfully estimate the properties of plant-pollinator interaction networks with a taxonomic resolution lower than the species level. We would advise using either the SR or robustness on untransformed data, or the NODF, discrepancy, or SR (for weighted networks only) on Z-scores. Additionally, connectance and modularity can be compared between low taxonomic resolution networks using the rank instead of the absolute values.
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Project description:Two major obstacles to utilizing polyhydroxybutyrate (PHB)-a biodegradable and biocompatible polymer-in commercial applications are its low tensile yield strength (<10 MPa) and elongation at break (~5%). In this work, we investigated the modification of the mechanical properties of PHB through the use of a variety of bio-derived additives. Poly(lactic acid) (PLA) and sugarcane-sourced cellulose nanocrystals (CNCs) were proposed as mechanical reinforcing elements, and epoxidized canola oil (eCO) was utilized as a green plasticizer. Zinc acetate was added to PHB and PLA blends in order to improve blending. Composites were mixed in a micro-extruder, and the resulting filaments were molded into 2-mm sheets utilizing a hot-press prior to characterization. The inclusion of the various additives was found to influence the crystallization process of PHB without affecting thermal stability. In general, the addition of PLA and, to a lesser degree, CNCs, resulted in an increase in the Young's modulus of the material, while the addition of eCO improved the strain at break. Overall, samples containing eCO and PLA (at concentrations of 10 wt %, and 25 wt %, respectively) demonstrated the best mechanical properties in terms of Young's modulus, tensile strength and strain at break.
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Project description:The quenching ability of modified and unmodified cottonseed oils was investigated using AISI 1070 steel. In the event of the quenching, the steel samples immersed in each of five distinct quench media, namely epoxidized cottonseed oil (EC), epoxidized-transesterified cottonseed oil (ETC), transesterified cottonseed oil (TC) and fresh cottonseed oil (FC). Tests and analysis conducted determined mechanical properties and microstructures of the quenched samples. The data obtained showed that ETC outperformed other quench media with hardness value of the quenched sample; 407 HVN (hardness value from the FC-quenched sample) increased to 746 HVN indicating an 83.29% improvement. Notably, in the microstructure of ETC-quenched sample, a unique homogeneous microstructure containing a mixture of lath and plate martensite observed with largest martensite per cent of 95.
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Project description:In an attempt to prepare sustainable epoxy thermosets, this study introduces for the first time the idea to use antagonist structures (aromatic/aliphatic) or functionalities (acid/amine) as hardeners to produce reprocessable resins based on epoxidized camelina oil (ECMO). Two kinds of mixtures were tested: one combines aromatic/aliphatic dicarboxylic acids: 2,2'-dithiodibenzoic acid (DTBA) and 3,3'-dithiodipropionic acid (DTDA); another is the combination of two aromatic structures with acid/amine functionality: DTBA and 4-aminophenyl disulfide (4-AFD). DSC and FT-IR analyses were used as methods to analyze the curing reaction of ECMO with the hardeners. It was found that the thermosets obtained with the dual crosslinked mechanism needed reduced curing temperatures and reprocessing protocols compared to the individual crosslinked thermosets. Thanks to the contribution of disulfide bonds in the network topology, the obtained thermosets showed recycling ability. The final thermomechanical properties of the virgin and mechanical reprocessed materials were analyzed by DMA and TGA. The obtained thermosets range from elastomeric to rigid materials. As an example, the ECMO/DTBA704-AFD30 virgin or reprocessed thermosets have tan δ values reaching 82-83 °C. The study also investigates the chemical recycling and the solvent resistance of these vitrimer-like materials.
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Project description:Biological materials combine stress relaxation and self-healing with non-linear stress-strain responses. These characteristic features are a direct result of hierarchical self-assembly, which often results in fiber-like architectures. Even though structural knowledge is rapidly increasing, it has remained a challenge to establish relationships between microscopic and macroscopic structure and function. Here, we focus on understanding how network topology determines the viscoelastic properties, i.e., stress relaxation, of biomimetic hydrogels. We have dynamically crosslinked two different synthetic polymers with one and the same crosslink. The first polymer, a polyisocyanopeptide (PIC), self-assembles into semi-flexible, fiber-like bundles, and thus displays stress-stiffening, similar to many biopolymer networks. The second polymer, 4-arm poly(ethylene glycol) (starPEG), serves as a reference network with well-characterized structural and viscoelastic properties. Using one and the same coiled coil crosslink allows us to decouple the effects of crosslink kinetics and network topology on the stress relaxation behavior of the resulting hydrogel networks. We show that the fiber-containing PIC network displays a relaxation time approximately two orders of magnitude slower than the starPEG network. This reveals that crosslink kinetics is not the only determinant for stress relaxation. Instead, we propose that the different network topologies determine the ability of elastically active network chains to relax stress. In the starPEG network, each elastically active chain contains exactly one crosslink. In the absence of entanglements, crosslink dissociation thus relaxes the entire chain. In contrast, each polymer is crosslinked to the fiber bundle in multiple positions in the PIC hydrogel. The dissociation of a single crosslink is thus not sufficient for chain relaxation. This suggests that tuning the number of crosslinks per elastically active chain in combination with crosslink kinetics is a powerful design principle for tuning stress relaxation in polymeric materials. The presence of a higher number of crosslinks per elastically active chain thus yields materials with a slow macroscopic relaxation time but fast dynamics at the microscopic level. Using this principle for the design of synthetic cell culture matrices will yield materials with excellent long-term stability combined with the ability to locally reorganize, thus facilitating cell motility, spreading, and growth.
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Project description:Glycidyl methacrylate (GMA) and a mixture of alkyl methacrylates (average chain length of 13 carbons; termed C13MA; derived from vegetable oils) were copolymerized by nitroxide-mediated polymerization to form epoxidized statistical and block copolymers with similar compositions (F GMA ∼0.8), which were further cross-linked by a bio-based diamine. Hybrid plate-like nanoparticles containing organophosphorus-titanium-silicon (PTS) with an average size of ∼130 nm and high decomposition temperature (485 °C) were synthesized via a hydrothermal reaction to serve as additives to simultaneously enhance the thermal and mechanical properties of the blend. Nanocomposites filled with PTS were prepared at different filler-loading levels (0.5, 2, 4 wt %). Transmission electron microscopy (TEM) of the cured block copolymer displayed reaction-induced macrophase-separated domains. TEM also showed an effective dispersion of PTS hybrids in the matrix without intense agglomeration. Thermogravimetric analysis at different heating rates revealed the activation energy of poly (GMA-stat-C13MA) at maximum decomposition increased from 143.5 to 327.2 kJ mol-1 with 4 wt % PTS. Decomposition temperature and char residue improved 12 °C and ∼7 wt %, respectively, and T g increased 12 °C by adding 4 wt % PTS. Targeting various PTS concentrations enabled tuning of the tensile modulus (up to 75%), tensile strength (up to 46%), and storage modulus in both glassy state (up to 59%) and rubbery plateau regions (up to 88%). Oscillatory frequency sweeps indicated that PTS makes the storage modulus frequency dependent, suggesting that the inclusion of the nanoparticles alters the relaxation of the surrounding matrix polymer.
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