ABSTRACT
This paper describes a detailed understanding of how nanofillers function as radiation barriers within the polymer matrix, and how their effectiveness is impacted by factors such as composition, size, loading, surface chemistry, and dispersion. We designed a comprehensive investigation of heavy ion irradiation resistance in epoxy matrix composites loaded with surface-modified ceria nanofillers, utilizing tandem computational and experimental methods to elucidate radiolytic damage processes and relate them to chemical and structural changes observed through thermal analysis, vibrational spectroscopy, and electron microscopy. A detailed mechanistic examination supported by FTIR spectroscopy data identified the bisphenol A moiety as a primary target for degradation reactions. Results of computational modeling by the Stopping Range of Ions in Matter (SRIM) Monte Carlo simulation were in good agreement with damage analysis from surface and cross-sectional SEM imaging. All metrics indicated that ceria nanofillers reduce the damage area in polymer nanocomposites, and that nanofiller loading and homogeneity of dispersion are key to effective damage prevention. The results of this study represent a significant pathway for engineered irradiation tolerance in a diverse array of polymer nanocomposite materials. Numerous areas of materials science can benefit from utilizing this facile and effective method to extend the reliability of polymer materials.
ABSTRACT
Microwave absorbing materials, particularly ones that can achieve high electromagnetic interference (EMI) absorption while minimizing weight and thickness are in high demand for many applications. Herein we present an approach that relies on the introduction of periodically placed air-filled pores into polymer composites in order to reduce material requirements and maximize microwave absorption. In this study, graphene nano platelet (xGNP)/poly-lactic acid (PLA) composites with different aspect ratio fillers were characterized and their complex electromagnetic properties were extracted. Using these materials, we fabricated non-perfect electrical conductor (PEC) backed, porous composites and explored the effect of filler aspect ratio and pore geometry on EMI shielding properties. Furthermore, we developed and experimentally verified a computational model that allows for rigorous, high-throughput optimization of absorbers with periodic porous geometries. Finally, we extend the modeling approach to explore the effect of pore addition on PEC-backed composites. Our composite structures demonstrated decreased fractions of reflected power and increased fractions of absorbed power over the majority of the X Band due to the addition of periodically arranged cylindrical pores. Furthermore, we showed that for xGNP/PLA composite material, reflection loss can be increased by as much as 13 dB through the addition of spherical pores. The ability to adjust shielding properties through the fabrication of polymer composites with periodically arranged pores opens new strategies for the modeling and development of new microwave absorption materials.
ABSTRACT
We synthesized a series of purely organic phosphors, bromobenzaldehyde derivatives, with varying conjugation length to investigate the effects of conjugation length on their phosphorescence emission properties. As the conjugation length increases phosphorescence efficiency decreases with a redshift in the emission color at 77 K. Our computational results imply that this correlation is related to the intersystem crossing rate and that the rate is determined by spin-orbit coupling strength rather than by simply the energy difference between the lowest lying singlet and triplet states. TD-DFT calculations show that the S1 â T1 transition occurs more dominantly than the S1 â T2 transition for all cases. Moreover, singlet excited states are localized on the aldehyde functional group, regardless of the conjugation length, while triplet excited states are evenly distributed over the conjugated backbone. Consequently, as the conjugation length increases, the larger spatial separation between singlet and triplet states diminishes the spin-orbit coupling efficiency, resulting in reduced phosphorescence.
