Comment on Observation of mutual diffusion of macromolecules in PS/PMMA binary films by confocal Raman microscopy'' by C. Hu, X. Chen, J. Chen, W. Zhang and M. Q. Zhang, Soft Matter, 2012, 8, 4780

A paper by Hu et al. (Soft Matter, 2012, 8, 4780) reports on the use of confocal Raman microscopy to resolve mutual diffusion between polystyrene (PS) and poly(methyl methacrylate) (PMMA). In-depth optical sectioning is employed to measure the diffusive broadening of the originally planar PS-PMMA interface, from which tracer and mutual diffusion coefficients and values for the PS-PMMA thermodynamic interaction parameter are extracted. Here, a reinterpretation of Hu's data that leads to a completely different scenario is presented, as apparent diffusive broadening can be mostly attributed to optical distortions inherent to the probe methodology. It also explains the lack of consistency of kinetic and thermodynamic parameters obtained by the authors from their diffusion analysis in comparison with earlier published data on this system. Overall, it highlights the importance of carrying out appropriate data analysis when confocal Raman microscopy is applied in dry depth-profiling investigations.