The introduction of molecularly woven three-dimensional (3D) covalent organic framework (COF) crystals into polymers of varying types invokes different forms of contact between filler and polymer. Whereas the combination of woven COFs with amorphous and brittle polymethyl methacrylate results in surface interactions, the use of the liquid-crystalline polymer polyimide induces the formation of polymer-COF junctions. These junctions are generated by the threading of polymer chains through the pores of the nanocrystals, thus allowing for spatial arrangement of polymer strands. This offers a programmable pathway for unthreading polymer strands under stress and leads to the in situ formation of high-aspect-ratio nanofibrils, which dissipate energy during the fracture. Polymer-COF junctions also strengthen the filler-matrix interfaces and lower the percolation thresholds of the composites, enhancing strength, ductility, and toughness of the composites by adding small amounts (~1 weight %) of woven COF nanocrystals. The ability of the polymer strands to closely interact with the woven framework is highlighted as the main parameter to forming these junctions, thus affecting polymer chain penetration and conformation.

The introduction of molecularly woven three-dimensional (3D) covalent organic framework (COF) crystals into polymers of varying types invokes different forms of contact between filler and polymer. Whereas the combination of woven COFs with amorphous and brittle polymethyl methacrylate results in surface interactions, the use of the liquid-crystalline polymer polyimide induces the formation of polymer-COF junctions. These junctions are generated by the threading of polymer chains through the pores of the nanocrystals, thus allowing for spatial arrangement of polymer strands. This offers a programmable pathway for unthreading polymer strands under stress and leads to the in situ formation of high-aspect-ratio nanofibrils, which dissipate energy during the fracture. Polymer-COF junctions also strengthen the filler-matrix interfaces and lower the percolation thresholds of the composites, enhancing strength, ductility, and toughness of the composites by adding small amounts (~1 weight %) of woven COF nanocrystals. The ability of the polymer strands to closely interact with the woven framework is highlighted as the main parameter to forming these junctions, thus affecting polymer chain penetration and conformation.

Nanoconfinements are utilized to program how polymers entangle and disentangle as chain clusters to engineer pseudo bonds with tunable strength, multivalency, and directionality. When amorphous polymers are grafted to nanoparticles that are one magnitude larger in size than individual polymers, programming grafted chain conformations can "synthesize" high-performance nanocomposites with moduli of ≈25GPa and a circular lifecycle without forming and/or breaking chemical bonds. These nanocomposites dissipate external stresses by disentangling and stretching grafted polymers up to ≈98% of their contour length, analogous to that of folded proteins; use both polymers and nanoparticles for load bearing; and exhibit a non-linear dependence on composition throughout the microscopic, nanoscopic, and single-particle levels.

Biogenic materials like beeswax have potential for sustainable manufacturing by reducing environmental impact. This study introduces “Beeswax Luminaires”, a sustainable lighting solution made from natural beeswax and water via ice-casting. The objectives are to characterize beeswax properties, optimize luminaire design for mechanical strength and light diffusion, and develop scalable robotic fabrication. Results indicate that beeswax maintains rigidity up to 50 °C and possesses suitable translucency for lighting. Parametric modeling produced corrugations enhancing flexural rigidity and light diffusion uniformity. Robotic fabrication precisely controlled coating thickness and quality, reducing product defects. Life-cycle assessment showed the production was energy-efficient, consuming less energy than traditional methods. These findings support Beeswax Luminaires as an eco-friendly lighting option, combining sustainability, optimized design and efficient manufacturing. • Beeswax is used to make sustainable luminaires. • Comprehensive material characterization is conducted to optimize design and fabrication. • Optimized designs are made with parametric modeling and robotic fabrication. • Corrugation is used to allow for higher strength, fewer defects and improved light diffusion.

Keywords: polymeric materials, composites, multifunctional, structure-properties correlations, nanostructures

We utilize nanoconfinements to program how polymers entangle and disentangle as chain clusters to engineer pseudo bonds with tunable strength, multivalency, and directionality. When amorphous polymers are grafted to nanoparticles that are one magnitude larger in size than individual polymer, programming grafted chain conformations can “synthesize” high performance nanocomposites with moduli of ~25GPa and a circular lifecycle without forming and/or breaking chemical bonds. These nanocomposites dissipate external stresses by disentangling and stretching grafted polymers up to ~98% of their contour length, analogous to that of folded proteins; use both polymers and nanoparticles for load bearing; and exhibit a non-linear dependence on composition throughout the microscopic, nanoscopic and single particle levels.