ABSTRACT
This study presents for the first time results about the microplastic concentration and their origin in a stream of the Pampas region in Argentina, receiving wastewater of an intermediate city. The most appropriate procedure to analyze and quantify the microplastics in the studied system is the use of an oxidative digestion process using a 30% H2O2 solution to eliminate the organic matter in the samples. A high quantity of MPs, on the order of millions of microplastics per m3 of water, was estimated in the Langueyú stream. 56% of the microplastics correspond to fibers with diameters between 10 and 15 µm and lengths less than 500 µm, while 44% are fragments with sizes of tens of micrometers. Raman microspectroscopy was used to identify the type of fibers. The characteristics of the microplastic fibers released in a wash load test are comparable with those observed in the Langueyú stream, in particular, the average sizes and the distribution of the diameters of the MPFs are similar. The processes in the sewage treatment plant, prior to their discharge in the stream, would affect the color of the fibers and their length.
ABSTRACT
We report on a new methodology to track chain interdiffusion between polymer slabs based on Raman enhanced by plasmonic substrates. Diffusion is studied in a deuterated-polystyrene/polystyrene (dPS/PS) polymer pair, designed to provide a well-characterized diffusion behavior. The bilayer, 160 nm thick in total, is supported on a plasmonic substrate that provides local amplification of Raman signals in sample regions of close proximity to it. Gold-based substrates with structures of inverted pyramids, spherical nanoparticles and tipped pillars were investigated. Interdiffusion between dPS and PS is promoted upon annealing and followed in situ by dynamic spectral acquisition. A simple model that describes the coupling between the sampled region arising from the plasmonic effect and the diffusion process is employed to interpret spectral evolution data. It is shown that a highly regular topology and surface continuity are key features of the plasmonic substrate in order to provide reliable results. With pyramidal substrates, the most suitable substrates for this application, data are consistent with diffusion coefficients in the range 10-13-10-15 cm2 s-1 and dimensions of sampled regions below 40 nm. The strategy provides a reliable labeling-free technique to investigate polymer interdiffusion on the nanoscale.
ABSTRACT
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.
ABSTRACT
Raman spectroscopy is used to elucidate fine details of the rather complex microstructure of ethylene-propylene copolymers (EPCs). This paper is focused on a series of commercial EPCs (Versify by Dow) with well-characterized ethylene content. Particular emphasis is given on the analysis of crystal type and content and their relation with EPC chain microstructure. Information provided by Raman is compared with that obtained by differential scanning calorimetry (DSC), a well-established technique widely used in the polymer field. Temperature-resolved Raman experiments are also carried out to interpret more precisely the complex melting patterns observed in the DSC traces. These experiments reveal with more detail the crystal chemical composition and melting temperature ranges of EPC samples, key features to design processing conditions that guarantee optimum lifetime and recyclability of overmolded parts.
ABSTRACT
The data obtained in confocal Raman microscopy (CRM) depth profiling experiments with dry optics are subjected to significant distortions, including an artificial compression of the depth scale, due to the combined influence of diffraction, refraction, and instrumental effects that operate on the measurement. This work explores the use of (1) regularized deconvolution and (2) the application of simple rescaling of the depth scale as methodologies to obtain an improved, more precise, confocal response. The deconvolution scheme is based on a simple predictive model for depth resolution and the use of regularization techniques to minimize the dramatic oscillations in the recovered response typical of problem inversion. That scheme is first evaluated using computer simulations on situations that reproduce smooth and sharp sample transitions between two materials and finally it is applied to correct genuine experimental data, obtained in this case from a sharp transition (planar interface) between two polymeric materials. It is shown that the methodology recovers very well most of the lost profile features in all the analyzed situations. The use of simple rescaling appears to be only useful for correcting smooth transitions, particularly those extended over distances larger than those spanned by the operative depth resolution, which limits the strategy to the study of profiles near the sample surface. However, through computer simulations, it is shown that the use of water immersion objectives may help to reduce optical distortions and to expand the application window of this simple methodology, which could be useful, for instance, to safely monitor Fickean sorption/desorption of penetrants in polymer films/coatings in a nearly noninvasive way.
ABSTRACT
We describe fluorescence resonance energy transfer (FRET) experiments carried out to examine the effect of ethylene glycol and propylene glycol on the early stages of polymer diffusion in poly(butyl acrylate-co-methyl methacrylate) latex films. In our approach, we temporarily arrest the drying process of a wet latex film by sealing the film in a previously cooled airtight sample chamber. This arrests propagation of the drying front and suppresses polymer diffusion during the measurements. We then measure donor fluorescence decays from 0.5 mm diameter spots at various locations on the film. From our analysis, we obtain information about the earliest stages of polymer diffusion as the film is still drying. We also investigate the effect of these glycols on polymer diffusion at longer aging times on predried latex films. Ethylene glycol and propylene glycol retard polymer diffusion at early times immediately after the passing of the drying front but enhance the rate of polymer diffusion at later aging times. This behavior is described quantitatively in terms of free-volume theory and the partitioning of the glycols between the aqueous and polymer phases in the film.
ABSTRACT
It has been well documented that the use of dry optics in depth profiling by confocal Raman microspectroscopy significantly distorts the laser focal volume, thus negatively affecting the spatial resolution of the measurements. In that case, the resulting in-depth confocal profile is an outcome of several contributions: the broadening of the laser spot due to instrumental factors and diffraction, the spreading of the illuminated region due to refraction of the laser beam at the sample surface, and the influence of the confocal aperture in the collection path of the laser beam. Everall and Batchelder et al. developed simple models that describe the effect of the last two factors, i.e., laser refraction and the diameter of the pinhole aperture, on the confocal profile. In this work, we compare these theoretical predictions with experimental data obtained on a series of well-defined planar interfaces, generated by contact between thin polyethylene (PE) films (35, 53, 75, and 105 microm thickness) and a much thicker poly(methyl methacrylate) (PMMA) piece. We included two refinements in the above-mentioned models: the broadening of the laser spot due to instrumental factors and diffraction and a correction for the overestimation in the decay rate of collection efficiency predicted by Batchelder et al. These refinements were included through a semiempirical approach, consisting of independently measuring the Raman step-response in the absence of refraction by using a silicon wafer and the actual intensity decay of a thick and transparent polymer film. With these improvements, the model reliably reproduces fine features of the confocal profiles for both PE films and PMMA substrates. The results of this work show that these simple models can not only be used to assist data interpretation, but can also be used to quantitatively predict in-depth confocal profiles in experiments carried out with dry optics.
ABSTRACT
Liquid-glassy polymer diffusion is an important topic in polymer physics, with several mechanistic aspects that still remain unclear. Here we describe the use of confocal Raman microspectroscopy (CRM) to study directly several features of interphase evolution in a system of this type. The interphase studied was generated by contact between liquid polystyrene (PS) and glassy polyphenylene oxide (PPO). Interphase evolution on thin films made from these polymers was followed by depth profiling in combination with immersion optics. We also applied regularized deconvolution to improve the spatial resolution of the measurements. With the help of these techniques, we examined interphase PPO concentration profiles and kinetics of interphase evolution in the range 120-180 degrees C, well below the glass transition temperature of the PPO-based films (185 degrees C). Overall, the experiment captures the most important features needed to discern the mechanistic factors that control this process. In this sense, confocal Raman microspectroscopy emerges as one of the best experimental techniques for the study of diffusion kinetics in this type of system.
