This paper outlines the shrinkage of electrospun polyvinylpyrrolidone (PVP) fiber mats during thermal treatment. The thermal behavior and phase changes within the fibers were investigated by DSC and TGA/DTA. Five precursors with different PVP loading in ethanol were electrospun. The mats shrinkage as function of temperature was measured in the RT–200 °C range. Shrinkage rate drastically increased above the polymer glass transition point, Tg (150–180 °C), due to increase in polymer chain mobility. Mats shrinkage at 200 °C as function of PVP concentration showed a minimum at ∼10%wt. Below 10% PVP the mats morphology is non‐uniform, consisting of beads and fibers. Above 10% PVP, only flat and uniform fibers were observed. This paper outlines the dominant mechanism governing the mats shrinkage during heating. In addition, the effect of PVP concentration on the expansion of fibers diameter was investigated and found to be consistent with the linear shrinkage observing a minimum at ∼10% PVP. The effect of applied voltage on mat shrinkage was investigated, and showed a minimum at 12 kV. Understanding the interplay between fibers morphology and thermal shrinkage allows precursor composition and system optimization needed for minimizing shrinkage negative effects on the structure and properties of electrospun fiber mats. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 248–254

Anion conductive nanofiber mats from FAA-3 ionomers are obtained by electrospinning. Depending on the solvent used in the precursor solution, nanofibers with either nonhollow cylindrical or flat ribbon-like cross-sections are prepared. The anion conductivity and water uptake of the ionomeric nanofiber mats are measured as a function of the relative humidity in the 10-90% range and compared to that of a solid membrane cast from the same ionomer. In addition, the anion conductivity of an isolated single fiber of the ionomer is measured for the first time. The anion conductivity of the electrospun single fiber is found to be higher than that of the mats, which is, in turn, one order of magnitude higher than that of the solid ionomer membrane. The higher conductivity of the mats relative to the solid membrane (in both inplane and through-plane directions) is found to be related to the variation in water uptake, which stems from the morphological distinctions. These results increase the understanding of the electrospinning process of ionomers, toward the development and design of new anion conductive ionomer fibers, useful for high performance electrochemical devices.

Oxide-based ceramics offer promising thermoelectric (TE) materials for recycling high-temperature waste heat, generated extensively from industrial sources. To further improve the functional performance of TE materials, their power factor should be increased. This can be achieved by nanostructuring and texturing the oxide-based ceramics creating multiple interphases and nanopores, which simultaneously increase the electrical conductivity and the Seebeck coefficient. The aim of this work is to achieve this goal by compacting electrospun nanofibers of calcium cobaltite Ca 3 Co 4−x O 9+δ , known to be a promising p-type TE material with good functional properties and thermal stability up to 1200 K in air. For this purpose, polycrystalline Ca 3 Co 4−x O 9+δ nanofibers and nanoribbons were fabricated by sol-gel electrospinning and calcination at intermediate temperatures to obtain small primary particle sizes. Bulk ceramics were formed by sintering pressed compacts of calcined nanofibers during TE measurements. The bulk nanofiber sample pre-calcined at 973 K exhibited an improved Seebeck coefficient of 176.5 S cm −1 and a power factor of 2.47 μW cm −1 K −2 similar to an electrospun nanofiber-derived ceramic compacted by spark plasma sintering.

Ceramic Fe-Al-O nanofibers with a core-shell architecture were obtained by electrospinning. The fibers consist of an Fe-Al-O core with novel lamellar-like mesopores and an Fe-rich shell. A mechanism of this unique core and shell formation is outlined and confirmed. The described mesoporous nanofibers are highly promising for new research and applications involving catalysis, sensing and absorption of mobile components on the accessible porous core surface.

Ceramic nanobelt catalysts consisting of Fe–Al–O spinel modified with potassium were synthesized for CO2 hydrogenation into hydrocarbons. Nanobelts and hollow nanofibers were produced utilizing the internal heat released by oxidation of the organic component within the fibers. This extremely fast and short heating facilitated crystallization of the desired phase, while maintaining small grains and a large surface area. We investigated the effects of mat thickness, composition, and heating rate on the final morphology. A general transformation mechanism for electrospun nanofibers that correlates for the first time the mat’s thickness and the rate of oxidation during thermal treatment was proposed. The catalytic performance of carburized ceramic K/Fe–Al–O nanobelts was compared to the K/Fe–Al–O spinel powder. The electrospun catalyst showed a superior carbon dioxide conversion of 48% and a selectivity of 52% to light C2–C5 olefins, while the powder catalyst produced mainly C6 + hydrocarbons. Characterization of steady state catalytic materials by energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and N2-adsorption methods revealed that high olefin selectivity of the electrospun materials is related to a high extent of reduction of surface iron atoms because of more efficient interaction with the potassium promoter.