Effect of crystallization of the polyhedral oligomeric silsesquioxane block on self-assembly in hybrid organic-inorganic block copolymers with salt
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This study primarily focuses on examining the impact that geometric structure has on thermal conductivity of multi-phase constructs in different 3D-printed poly(lactic acid), PLA, samples. The investigated structures are inspired by morphologies formed by diblock copolymers: lamellae, hexagonally packed cylinders, and gyroid. This research also investigates how volume percentage and material combination influence the thermal conductivity of these structures. Further, the samples can be tailored to simulate various thermal management structures observed in practical applications, such as thermal interface materials in electronic devices. Thermal conductivity ratio is controlled using air, the least conductive material at 0.026 W/(m K), PLA at 0.136 W/(m K), and thermal paste at 5.11 W/(m K). Different models were tested against thermal conductivity measurements in order to capture the effect of material type (PLA-Air versus PLA-Thermal Paste), volume percentage, structure, and orientation. Simple, effective medium models were good predictions of thermal conductivity in lamellar structures, but it was necessary to develop models for conduction through cylindrical and gyroid structures. Finally, all results were normalized to find a universal model that is independent of structure and material. This approach provides a simple method to predict how to reduce or enhance transport properties and heat management capabilities of 3D printed objects.
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Poly(3-hydroxyhexanoate) (P3HHx)-based poly(3- hydroxyalkanoate)s (PHAs) are biologically produced, commercially implemented PHAs, but little is known in the open literature about the structure and property characterizations of discrete, authentic homopolymer P3HHx, and its copolymers with poly(3- hydroxybutyrate) (P3HB). Here, we introduce a chemocatalytic route to stereoregular (both isotactic and syndiotactic) P3HHx and PHA copolymers with P3HB, including statistical copolymer P3HBHx with various levels of 3HHx incorporation and discrete hard−soft−hard triblock copolymer P3HB-b-P3HHx-b-P3HB, and present extensive characterizations of their structures, thermal properties, and mechanical performance. The synthesis is efficiently achieved by one-pot polymerization of eight-membered di(n-propyl) and dimethyl (for copolymerization) diolides catalyzed by chiral molecular catalysts. Notably, P3HBHx can be rapidly produced in quantitative yield and exhibits high molar mass (M n up to 551 kg/mol) as well as both high modulus (up to 1.39 GPa) and ductility (up to 445%), while P3HB-b-P3HHx-b-P3HB further extends application temperature windows by possessing a unique combination of low T g (−18 °C) and high T m (154 °C) values. These findings highlight the stereomicrostructural and architectural versatility of chemocatalytic routes to PHAs, which, in turn, can be utilized to largely tune the PHA thermal properties and mechanical performance.
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