In this report, we studied the formation mechanism of cagelike polymer microspheres fabricated conveniently and efficiently through a swelling-osmosis process of sulfonated polystyrene (SPS) microspheres in a ternary mixed solvent (water/ethanol/heptane). The scanning electron microscopy and transmission electron microscopy observations indicated that the morphology of the final cagelike SPS microspheres is mainly controlled by the composition of the mixed solvent and the swelling temperature. Considering the solubility parameters of related reagents and the low interface tension of heptane and the aqueous solution of ethanol (only 6.9 mN/m), we confirm that the porogen procedure starts from the swelling of SPS microspheres by heptane, followed by the osmosis process of water molecules into the swollen SPS microspheres forced by the strong hydrophilicity of -SO3H group. The water molecules permeated into SPS microspheres will aggregate into water pools, which form the pores after the microspheres are dried. These prepared cagelike SPS microspheres are further served as the scaffold for the in situ generated CdS nanoparticles under γ-ray radiation. The CdS/SPS composite microspheres show good fluorescence performance. This work shows that the cagelike SPS microspheres have a wide industrial application prospect due to their economical and efficient preparation and loading nanoparticles.
Weak polyelectrolyte multilayers (PEMs) prepared by the layer-by-layer technique have attracted a great deal of attention as smart responsive materials for biological and other applications in aqueous medium, but their dynamic behavior as a function of exposure to a wide temperature range is still not well understood. In this work, the thermally dependent swelling behavior of PEMs consisting of branched poly(ethylenimine) and poly(acrylic acid) is studied by temperature controlled in situ spectroscopic ellipsometry. Because of diffusion and interpenetration of polyelectrolytes during film deposition, the PEMs densify with increasing bilayer number, which further affects their water uptake behavior. Upon heating to temperatures below 60 °C, the worsened solvent quality of the PEM in water causes deswelling of the PEMs. However, once heated above this critical temperature, the hydrogen bonds within the PEMs are weakened, which allows for chain rearrangement within the film upon cooling, resulting in enhanced water uptake and increased film thickness. The current work provides fundamental insight into the unique dynamic behavior of weak polyelectrolyte multilayers in water at elevated temperatures.
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