RESUMO
Incorporating dynamic covalent bonds into block copolymers provides useful molecular level information during mechanical testing, but it is currently unknown how the incorporation of these units affects the resultant polymer morphology. High-molecular-weight polyisobutylene-b-polystyrene block copolymers containing an anthracene/maleimide dynamic covalent bond are synthesized through a combination of postpolymerization modification, reversible addition-fragmentation chain-transfer polymerization, and Diels-Alder coupling. The bulk morphologies with and without dynamic covalent bond are characterized by atomic force microscopy and small-angle X-ray scattering, which reveal a strong dependence on annealing time and casting solvent. Morphology is largely unaffected by the inclusion of the mechanophore. The high-molecular-weight polymers synthesized allow interrogation of a large range of polymer domain sizes.
RESUMO
In this investigation, composite poly(lactic acid) (PLA) systems of hollow glass microspheres (MS) and carbonyl iron particles (CIP) were processed and characterized to investigate the effects of using conductive and insulating particles as additives in a polymer system. PLA-MS and PLA-CIP were set at the two levels of 3.94 and 7.77 vol.% for each particle type to study the effects of the particle material type and loading on neat PLA's thermal properties. It was observed during the twin-screw extrusion that the addition of CIP greatly decreased the viscosity of the PLA melt during processing. Correlations determined using thermogravimetric analysis, differential scanning calorimetry, thermal conductivity, and shear rheology provided insights into how thermal stability was affected. The incorporation of MS and CIP altered thermal properties such as the glass transition temperature (Tg), melting temperature (Tm), and cold crystallization temperature (Tcc). The metal CIP-filled systems had large increases in their thermal conductivity values and viscoelastic transitions compared to those with PLA that were correlated with the observed overheating during extrusion.
RESUMO
Polylactic acid (PLA) and poly(ethylene terephthalate glycol) (PETG) are popular thermoplastics used in additive manufacturing applications. The mechanical properties of PLA and PETG can be significantly improved by introducing fillers, such as glass and iron nanoparticles (NPs), into the polymer matrix. Molecular dynamics (MD) simulations with the reactive INTERFACE force field were used to predict the mechanical responses of neat PLA/PETG and PLA-glass/iron and PETG-glass/iron nanocomposites with relatively high loadings of glass/iron NPs. We found that the iron and glass NPs significantly increased the elastic moduli of the PLA matrix, while the PETG matrix exhibited modest increases in elastic moduli. This difference in reinforcement ability may be due to the slightly greater attraction between the glass/iron NP and PLA matrix. The NASA Multiscale Analysis Tool was used to predict the mechanical response across a range of volume percent glass/iron filler by using only the neat and highly loaded MD predictions as input. This provides a faster and more efficient approach than creating multiple MD models per volume percent per polymer/filler combination. To validate the micromechanics predictions, experimental samples incorporating hollow glass microspheres (MS) and carbonyl iron particles (CIP) into PLA/PETG were developed and tested for elastic modulus. The CIP produced a larger reinforcement in elastic modulus than the MS, with similar increases in elastic modulus between PLA/CIP and PETG/CIP at 7.77 vol % CIP. The micromechanics-based mechanical predictions compare excellently with the experimental values, validating the integrated micromechanical/MD simulation-based approach.