Diffusion of cyclic versus linear poly(oxyethylene) oligomers in poly(methyl methacrylate) by ATR-FTIR spectroscopy

Diffusion of linear and cyclic poly(oxyethylene) (POE) oligomers in poly(methyl methacrylate) (PMMA) matrix was investigated in situ using attenuated total reflectance (ATR) infrared (IR) spectroscopy technique. The temperatures of studies were 60 oC, 85 oC and 110 oC. A film of PMMA was solution-cast onto an ATR zinc selenide crystal and POE was added to the surface. The IR peak at 1109 cm-1 characteristic to ether bond present in POE was used for quantitative analysis. Deconvolution of this peak from IR spectra allowed us to determine the absorbance of diffusing component as a function of interdiffusion time. The data were fit using appropriate mathematical models from where the interdiffusion constants were extracted and used in diffusion interpretation. By looking at different molecular weight of cyclic and linear POE oligomers diffusing into high molecular weight PMMA matrix, it was possible to analyze how penetrant topology and its molecular weight are influencing the diffusion process. The results indicated that cyclic POE moves faster than linear analogous one and an increase in penetrant molecular weight slows down the interdiffusion. The knowledge gained from this study gives us a deeper understanding of transport behavior of low-molecular-weight additives, such as oligomers into polymer matrices and, in particular the influence of topology on diffusion.Ph.D.Committee Chair: Haskell W. Beckham; Committee Co-Chair: David Bucknall; Committee Member: Andrew Lyon; Committee Member: Jiri Janata; Committee Member: Lawrence Bottomley; Committee Member: Mohan Srinivasara