Various oxirane monomers including alkyl ether or allyl-substituted ones such as 1-butene oxide, 1-hexene oxide, 1-octene oxide, butyl glycidyl ether, allyl glycidyl ether, and 2-ethylhexyl glycidyl ether were anionically copolymerized with CO 2 into polycarbonates using onium salts as initiator in the presence of triethylborane. All copolymerizations exhibited a “living” character, and the monomer consumption was monitored by in situ Fourier-transform infrared spectroscopy. The various polycarbonate samples obtained were characterized by 1 H NMR, GPC, and differential scanning calorimetry. In a second step, all-polycarbonate triblock copolymers demonstrating elastomeric behavior were obtained in one pot by sequential copolymerization of CO 2 with two different epoxides, using a difunctional initiator. 1-Octene oxide was first copolymerized with CO 2 to form the central soft poly(octene carbonate) block which was flanked by two external rigid poly(cyclohexene carbonate) blocks obtained through subsequent copolymerization of cyclohexene oxide with CO 2 . Upon varying the ratio of 1-octene oxide to cyclohexene oxide and their respective ratios to the initiator, three all-polycarbonate triblock samples were prepared with molar masses of about 350 kg/mol and 22, 26, and 29 mol % hard block content, respectively. The resulting triblock copolymers were analyzed using 1 H NMR, GPC, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy. All three samples demonstrated typical elastomeric behavior characterized by a high elongation at break and ultimate tensile strength in the same range as those of other natural and synthetic rubbers, in particular those used in applications such as tissue engineering.
Fungal mycelium is an emerging bio-based material. Here, mycelium films are produced from liquid shaken cultures that have a Young's modulus of 0.47 GPa, an ultimate tensile strength of 5.0 MPa and a strain at failure of 1.5%. Treating the mycelial films with 0-32% glycerol impacts the material properties. The largest effect is observed after treatment with 32% glycerol decreasing the Young's modulus and the ultimate tensile strength to 0.003 GPa and 1.8 MPa, respectively, whereas strain at failure increases to 29.6%. Moreover, glycerol treatment makes the surface of mycelium films hydrophilic and the hyphal matrix absorbing less water. Results show that mycelium films treated with 8% and 16-32% glycerol classify as polymer-and elastomer-like materials, respectively, while non-treated films and films treated with 1-4% glycerol classify as natural material. Thus, mycelium materials can cover a diversity of material families.
Reprocessing of reinforced composites is generally accompanied by loss of value and performance, as normally the reinforcing phase is damaged, or the matrix is lost in the process. In the search for more sustainable recyclable composite materials, we identify blends based on poly( l -lactide) (PLA) and thermotropic liquid crystalline polymers (LCP) as highly promising self-reinforced thermoplastic composites that can be recycled several times without loss in mechanical properties. For example, irrespective of the thermal history of the blend, injection molded bars of PLA containing 30 wt % LCP exhibit a tensile modulus of 6.4 GPa and tensile strength around 110 MPa, as long as the PLA matrix has a molecular weight of 170 kg mol –1 or higher. However, after several mechanical reprocessing steps, with the gradual decrease in the molecular weight of the PLA matrix, deterioration of the mechanical performance is observed. The origin of this behavior is found in the increasing LCP to PLA viscosity ratio: at a viscosity ratio below unity, the dispersed LCP droplets are effectively deformed into the desired fibrillar morphology during injection molding. However, deformation of LCP droplets becomes increasingly challenging when the viscosity ratio exceeds unity (i.e., when the PLA matrix viscosity decreases during consecutive reprocessing), eventually resulting in a nodular morphology, a poor molecular orientation of the LCP phase, and deterioration of the mechanical performance. This molecular weight dependency effectively places a limit on the maximum number of mechanical reprocessing steps before chemical upgrading of the PLA phase is required. Therefore, a feasible route to maintain or enhance the mechanical properties of the blend, independent of the number of reprocessing cycles, is proposed.
Thermoplastic composites based on thermotropic liquid crystalline polymer (LCP) materials are interesting candidates for reinforced composite application due to their promising mechanical performance and potential for recyclability. In combination with a societal push toward the more sustainable use of materials, these properties warrant new interest in this class of composites. Though numerous studies have been performed in the past, a coherent set of design rules for LCP design for the generation of injection-molded reinforced thermoplastic composites is not yet available, likely due to the complex interplay between LCP and matrix components. In this study, we report on the processing of poly(l-lactide) with two different LCPs, at relatively low processing temperatures. The study focuses on critical parameters for the morphological development and mechanical performance of LCP-reinforced composites. The influence of blend composition and the processing conditions, on the mechanical response of the composites, is investigated using rheology, wide-angle X-ray diffraction, mechanical analysis, and microscopy techniques. The study conclusively demonstrates that both the matrix viscosity and viscosity ratio between the dispersed and matrix phase, determine the deformation and breakup of the dispersed LCP droplets during extrusion. In addition, the thermal dependence of the viscosity ratio appears to be a critical parameter for the composite performance after injection molding. For example, during injection molding, stretching and molecular orientation of the LCP phase into highly oriented fibrils are prevented when the viscosity ratio increases rapidly upon cooling. In contrast, melt drawing proves to be a more effective processing route as the extensional flow field stabilizes elongated droplets, independent of the viscosity ratio. Overall, these findings provide valuable insights in the morphological development of LCP-reinforced blends, highlighting the importance of the development of viscoelastic properties as a function of temperature, and provide guidelines for the design of new LCP polymers and their thermoplastic composites.
We report on the role of temperature and shear on the melt behavior of iPP in the presence of the organic compound N1,N1′-(propane-1,3-diyl)bis(N2-hexyloxalamide) (OXA3,6). It is demonstrated that OXA3,6 facilitates a viscosity suppression when it resides in the molten state. The viscosity suppression is attributed to the interaction of iPP chains/subchains with molten OXA3,6 nanoclusters. The exact molecular mechanism has not been identified; nevertheless, a tentative explanation is proposed. The observed viscosity suppression appears similar to that encountered in polymer melts filled with solid nanoparticles, with the difference that the OXA3,6 compound reported in this study facilitates the viscosity suppression in the molten state. Upon cooling, as crystal growth of OXA3,6 progresses, the decrease in viscosity is suppressed. Retrospectively, segmental absorption of iPP chains on the surface of micrometer-sized OXA3,6 crystallites favors the formation of dangling arms, yielding OXA3,6 crystallites decorated with partially absorbed iPP chains. In other words, the resulting OXA3,6 particle morphology resembles that of a hairy particle or a starlike polymer chain. Such hairy particles effectively facilitate a viscosity enhancement, similar to branched polymer chains. This hypothesis and its implications for the shear behavior of iPP are discussed and supported using plate–plate rheometry and slit-flow experiments combined with small-angle X-ray scattering analysis.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.