The exact knowledge of hydrogel microstructure, mainly its pore topology, is a key issue in hydrogel engineering. For visualization of the swollen hydrogels, the cryogenic or high vacuum scanning electron microscopies (cryo-SEM or HVSEM) are frequently used while the possibility of artifact-biased images is frequently underestimated. The major cause of artifacts is the formation of ice crystals upon freezing of the hydrated gel. Some porous hydrogels can be visualized with SEM without the danger of artifacts because the growing crystals are accommodated within already existing primary pores of the gel. In some non-porous hydrogels the secondary pores will also not be formed due to rigid network structure of gels that counteracts the crystal nucleation and growth. We have tested the limits of true reproduction of the hydrogel morphology imposed by the swelling degree and mechanical strength of gels by investigating a series of methacrylate hydrogels made by crosslinking polymerization of glycerol monomethacrylate and 2-hydroxyethyl methacrylate including their interpenetrating networks. The hydrogel morphology was studied using cryo-SEM, HVSEM, environmental scanning electron microscopy (ESEM), laser scanning confocal microscopy (LSCM) and classical wide-field light microscopy (LM). The cryo-SEM and HVSEM yielded artifact-free micrographs for limited range of non-porous hydrogels and for macroporous gels. A true non-porous structure was observed free of artifacts only for hydrogels exhibiting relatively low swelling and high elastic modulus above 0.5 MPa, whereas for highly swollen and/or mechanically weak hydrogels the cryo-SEM/HVSEM experiments resulted in secondary porosity. In this contribution we present several cases of severe artifact formation in PHEMA and PGMA hydrogels during their visualization by cryo-SEM and HVSEM. We also put forward empirical correlation between hydrogel morphological and mechanical parameters and the occurrence and intensity of artifacts.
The study deals with improvement of poly(E-caprolactone) (PCL) parameters by in situ forming of poly(lactic acid) (PLA) fibrils. This structure is achieved by preparation of the melt-drawn microfibrillar composite (MFC) from the PCL/PLA 80/20 blend containing the organophilized montmorillonite (oMMT) added using various mixing protocols. Improved mechanical behavior corresponds to the micron-sized fibrils formation and reinforcement of both polymer components by oMMT, and to increased crystalline phase content in the fibrillar PLA phase. Effective melt drawing is only possible after the rheological parameters of the polymer components have been modified by oMMT where the clay addition method and content are of primary importance. From the results obtained, it follows that the role of oMMT in MFC is quite complex, numerous clay-induced effects may be contradictory and must be harmonized to achieve PCL-based biodegradable MFCs with improved parameters. V C 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016, 133, 43061.
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