NANOPARTICLE DYNAMICS IN POLYMER NANOCOMPOSITES USING TIME-OF-FLIGHT SECONDARY ION MASS SPECTROMETRY
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Chemistry
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nanocomposites
tof-sims
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Abstract
Nanocomposites are vital for their ability to enhance material properties such as mechanical strength, thermal stability, and barrier performance through the controlled integration of nanoparticles into polymer matrices. Understanding nanoparticle (NP) diffusion is crucial for tuning the dispersion, processing conditions, and in result the composite performance. This dissertation significantly advances the understanding of nanoparticle dynamics in polymer nanocomposites (PNCs) through the innovative use of time-of-flight secondary ion mass spectrometry (ToF-SIMS), focusing on the diffusion behaviors of NPs. To rigorously analyze NP diffusion, a robust methodology has been established for employing ToF-SIMS. This technique not only allows for precise measurement of NP and polymer diffusion but also expands the boundaries of possible diffusion measurements across extensive length scales and within a broader array of materials. By establishing ToF-SIMS as a reliable method for measuring nanoparticle and polymer diffusion with materials such as poly(2-vinyl pyridine), silica nanoparticles, and deuterated polystyrene, this work extends the scope of diffusion studies in PNCs.The investigation explores NP diffusion within attractive polymer melts, adapting theoretical insights to discern two distinct diffusion modes—core-shell and vehicular—evident in the experimental data. The presence of a bound polymer layer in attractive PNCs causes NPs to deviate significantly from classical Stokes-Einstein behavior, with the degree of deviation correlated to the monomeric desorption times (τdes) of the bound polymer. We find experimentally that the τdes¬¬ of Al2O3 significantly shorter (~ 50 s) compared to SiO2 (τdes > 6000 s) at 180°C, and that this desorption time is independent of NP diameter.
Moreover, the dissertation addresses the practical application of NPs in crowded environments, which introduces complex behaviors. Applying ToF-SIMS, this study successfully differentiates smaller Al2O3 NPs from a PNC with larger SiO2 NPs and quantifies the Al2O3 NP diffusion in crowded PNCs. NP loading and interparticle distance are shown to critically influence NP diffusion and subsequently modulate the local polymer dynamics, affecting both the monomeric desorption times and overall NP diffusion mode.
This foundational work significantly enhances the understanding of polymer-bound layers and complex NP diffusion mechanisms, setting the stage for future advancements in PNCs. These insights are poised to improve the processability of PNCs and expand their applications in dynamic environments, from self-healing materials to targeted drug delivery systems.