Unveiling the Inner Structure of Micrometric Hollow Polymeric Fibers Using Synchrotron X-Ray Nanotomography.

In this study, a novel application of synchrotron X-ray nanotomography based on high-resolution full-field transmission X-ray microscopy for characterizing the structure and morphology of micrometric hollow polymeric fibers is presented. By employing postimage analysis using an open-source software such as Tomviz and ImageJ, various key parameters in fiber morphology, including diameter, wall thickness, wall thickness distribution, pore size, porosity, and surface roughness, were assessed. Electrospun polycaprolactone fibers with micrometric diameters and submicrometric features with induced porosity via gas dissolution foaming were used to this aim. The acquired synchrotron X-ray nanotomography data were analyzed using two approaches: 3D tomographic reconstruction and 2D radiographic projection-based analysis. The results of the combination of both approaches demonstrate unique capabilities of this technique, not achievable by other available techniques, allowing for a full characterization of the internal and external morphology and structure of the fibers as well as to obtain valuable qualitative insights into the overall fiber structure.

Encapsulation of Copper Nanoparticles in Electrospun Nanofibers for Sustainable Removal of Pesticides.

The excellent catalytic properties of copper nanoparticles (CuNPs) for the degradation of the highly toxic and recalcitrant chlorpyrifos pesticide are widely known. However, CuNPs generally present low stability caused by their high sensitivity to oxidation, which leads to a change of the catalytic response over time. In the current work, the immobilization of CuNPs into a polycaprolactone (PCL) matrix via electrospinning was demonstrated to be a very effective method to retard air and solvent oxidation and to ensure constant catalytic activity in the long term. CuNPs were successfully anchored into PCL electrospun fibers in the form of Cu2O at different concentrations (from 1.25 wt % to 5 wt % with respect to the PCL), with no signs of loss by leaching out. The PCL mats loaded with 2.5 wt % Cu (PCL-2.5Cu) almost halved the initial concentration of pesticide (40 mg/L) after 96 h. This process was performed in two unprompted and continuous steps that consisted of adsorption, followed by degradation. Interestingly, the degradation process was independent of the light conditions (i.e., not photocatalytic), expanding the application environments (e.g., groundwaters). Moreover, the PCL-2.5Cu composite presents high reusability, retaining the high elimination capability for at least five cycles and eliminating a total of 100 mg/L of chlorpyrifos, without exhibiting any sign of morphological damages.

Sub-pixel Tomographic Methods for Characterizing the Solid Architecture of Foams.

Three independent analysis methods were developed to investigate the distribution of solid mass in foams analyzed by X-ray tomography with effective pixel sizes larger than the thickness of the solid network (sub-pixel conditions). Validation of the methods was achieved by a comparison with the results obtained employing high-resolution tomography for the same set of foams. The foams showed different solid mass distribution, which varied from being preferentially located on the edges, with a fraction of mass in the struts nearing 0.6, to materials in which the fraction of mass in the struts was low, under 0.15. In all cases, the accuracy of the proposed approaches was greater for materials with a higher fraction of mass in the struts. The method based on deconvolution of the attenuation probability density function yielded the closest results to the high-resolution characterizations. In contrast, analysis of the solid matrix thickness distribution after watershed segmentation, and binarization of high thickness regions (struts segmentation) required normalization through macroscopic measurements and revealed higher deviations with respect to the high-resolution results. However, segmentation-based methods allowed investigation of the heterogeneity of the fraction of mass in the struts along the sample.

Nanostructure of PMMA/MAM Blends Prepared by Out-of-Equilibrium (Extrusion) and Near-Equilibrium (Casting) Self-Assembly and Their Nanocellular or Microcellular Structure Obtained from CO2 Foaming.

Blends of poly(methyl methacrylate) (PMMA) and a triblock copolymer poly(methyl methacrylate)-b-poly(butyl acrylate)-b-poly(methyl methacrylate) (MAM) have been obtained following both out-of-equilibrium (extrusion) and near-equilibrium (solvent casting) production routes. The self-assembly capability and the achievable nanostructures of these blends are analyzed by transmission electron microscopy (TEM) regarding their production route and potential for the achievement of nanocellular foams by CO2 gas dissolution foaming. The influence of the initial nanostructure of the solids on the obtained cellular structure of bulk and film samples is determined by high-resolution scanning electron microscopy (HRSEM) for diverse foaming conditions (saturation pressure, saturation temperature, and post-foaming stage), taking into account the required use of a foaming mold to achieve foams from films. Moreover, the influence of the nanostructuration on the presence of solid outer layers, typical of the selected foaming process, is addressed. Finally, consideration of a qualitative model and the obtained results in terms of nanostructuration, cellular structure, and foaming behavior, allow proposing a detailed cell nucleation, growth, and stabilization scheme for these materials, providing the first direct evidence of the cell nucleation happening inside the poly(butyl acrylate) phase in the PMMA/MAM blends.

Advanced Nanocellular Foams: Perspectives on the Current Knowledge and Challenges.

Nanocellular polymers (i.e., cellular polymers with cells and walls in the nanometric range) were first produced in the early 2000s, with the works of [...].

A new generation of hollow polymeric microfibers produced by gas dissolution foaming.

A new and straightforward route to produce polymeric hollow microfibers has been proposed. Polycaprolactone (PCL) hollow fibers are obtained for the first time using an environmentally friendly gas dissolution foaming approach, overcoming its limitations to induce porosity on samples in the micrometric range. Different porous morphologies are achieved from solid PCL microfibers with a well-controlled diameter obtained by conventional electrospinning. The optimization of the foaming parameters provides two sets of well-defined hollow fibers, one showing smooth surfaces and the other presenting an enhanced surface porosity. Accordingly, gas dissolution foaming proves to be not only suitable for the production of hollow polymeric microfibers, but is also capable of providing diverse porous morphologies from the same precursor, solid fibers. Moreover, a preliminary study about the suitability of this new generation of foamed hollow polymeric fibers for drug delivery is carried out, aiming to take advantage of the enhanced surface area and tunable morphology obtained by using the proposed new production method. It is found that the foamed microfibers can be loaded with up to 15 wt% of ibuprofen while preserving the morphology of each kind of fiber. Then, foamed PCL fibers presenting a hollow structure and surface porosity show a remarkable constant release of ibuprofen for almost one and a half days. In contrast, the original solid fibers do not present such behavior, releasing all the ibuprofen in about seven hours.

Melamine Foams Decorated with In-Situ Synthesized Gold and Palladium Nanoparticles.

A versatile and straightforward route to produce polymer foams with functional surface through their decoration with gold and palladium nanoparticles is proposed. Melamine foams, used as polymeric porous substrates, are first covered with a uniform coating of polydimethylsiloxane, thin enough to assure the preservation of their original porous structure. The polydimethylsiloxane layer allows the facile in-situ formation of metallic Au and Pd nanoparticles with sizes of tens of nanometers directly on the surface of the struts of the foam by the direct immersion of the foams into gold or palladium precursor solutions. The effect of the gold and palladium precursor concentration, as well as the reaction time with the foams, to the amount and sizes of the nanoparticles synthesized on the foams, was studied and the ideal conditions for an optimized functionalization were defined. Gold and palladium contents of about 1 wt.% were achieved, while the nanoparticles were proven to be stably adhered to the foam, avoiding potential risks related to their accidental release.

Non-Invasive Approaches for the Evaluation of the Functionalization of Melamine Foams with In-Situ Synthesized Silver Nanoparticles.

The use of polymeric nanocomposites has arisen as a promising solution to take advantage of the properties of nanoparticles (NPs) in diverse applications (e.g., water treatment, catalysis), while overcoming the drawbacks of free-standing nanoparticles (e.g., aggregation or accidental release). In most of the cases, the amount and size of the NPs will affect the stability of the composite as well as their performance. Therefore, a detailed characterization of the NPs present on the nanocomposites, including their quantification, is of vital importance for the optimization of these systems. However, the determination of the NPs load is often carried out by destructive techniques such as TGA or ICP-OES, the development of non-invasive approaches to that aim being necessary. In this work, the amount of silver NPs synthesized directly on the surface of melamine (ME) foams is studied using two non-invasive approaches: colorimetry and X-ray radiography. The obtained results show that the amount of silver NPs can be successfully determined from the luminosity and global color changes of the surface of the foams, as well as from the X-ray attenuance.

Facile Oil Removal from Water-in-Oil Stable Emulsions Using PU Foams.

Superhydrophobic and oleophilic polyurethane foams were obtained by spray-coating their surfaces with solutions of thermoplastic polyurethane and hydrophobic silicon oxide nanoparticles. The developed functionalized foams were exploited as reusable oil absorbents from stable water-in-oil emulsions. These foams were able to remove oil efficiently from a wide range of emulsions with oil contents from 10 to 80 v.%, stabilized using Span80. The modified foams could reach oil absorption capacities up to 29 g/g, becoming a suitable candidate for water-in-oil stable emulsions separation.

Antibacterial Melamine Foams Decorated with in Situ Synthesized Silver Nanoparticles.

A new and straightforward single-step route to decorate melamine foams with silver nanoparticles (ME/Ag) is proposed. Uniform coatings of silver nanoparticles with diameters less than 10 nm are formed in situ directly on the struts surface of the foams, after their dipping in an AgNO3 solution. We prove that the nanoparticles are stably adhered on the foams, and that their amount can be directly controlled by the concentration of the AgNO3 solution and the dipping time. Following this production route, ME/Ag foams can be obtained with silver content ranging between 0.2 and 18.6 wt % and excellent antibacterial performance, making them appropriate for various applications. Herein we explore the possibility to use them as antibacterial filters for water treatment, proving that they are able to remove completely Escherichia coli bacteria from water when filtered at flow rates up to 100 mL/h·cm2 due to the release of less than 1 ppm of Ag+ ions by the foams. No bacterial regrowth was observed after further dilution of the treated water, to arrive below the safety threshold of Ag+ for drinking water (0.1 ppm), demonstrating the excellent bactericide performance of the ME/Ag filters.