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Abstract In this study, multifibrillar carbon and carbon/ceramic (C/SiCON) fibers consisting of thousands of single nanofibers are continuously manufactured. The process starts with electrospinning of polyacrylonitrile (PAN) and PAN/oligosilazane precursors resulting in poorly aligned polymer fibers. Subsequent stretching leads to parallel aligned multifibrillar fibers, which are continuously stabilized and pyrolyzed to C or C/SiCON hybrid fibers. The multifibrillar carbon fibers show a high tensile strength of 911 MPa and Young’s modulus of 154 GPa, whereas the multifibrillar C/SiCON fibers initially have only tensile strengths of 407 MPa and Young’s modulus of 77 GPa, due to sticking of the nanofibers during the stabilization in air. Additional curing with electron beam radiation, results in a remarkable increase in tensile strength of 707 MPa and Young's modulus of 98 GPa. The good mechanical properties are highlighted by the low linear density of the multifibrillar C/SiCON fibers (~ 1 tex) compared to conventional C and SiC fiber bundles (~ 200 tex). In combination with the large surface area of the fibers better mechanical properties of respective composites with a reduced fiber content can be achieved. In addition, the developed approach offers high potential to produce advanced endless multifibrillar carbon and C/SiCON nanofibers in an industrial scale.

Abstract The 2‐bit Lindqvist‐type polyoxometalate (POM) [V6O13((OCH2)3CCH2N3)2]2– with a diamagnetic {V6O19} core and azide termini shows six fully oxidized VV centers in solution as well as the solid state, according to 51V NMR spectroscopy. Under UV irradiation, it exhibits reversible switching between its ground S0 state and the energetically higher lying states in acetonitrile and water solutions. TD‐DFT calculations demonstrate that this process is mainly initialized by excitation from the S0 to S9 state. Pulse radiolysis transient absorption spectroscopy experiments with a solvated electron point out photochemically induced charge disproportionation of VV into VIV and electron communication between the POM molecules via their excited states. The existence of this unique POM‐to‐POM electron communication is also indicated by X‐ray photoelectron spectroscopy (XPS) studies on gold‐metalized silicon wafers (Au//SiO2//Si) under ambient conditions. The amount of reduced vanadium centers in the “confined” environment increases substantially after beam irradiation with soft X‐rays compared to non‐irradiated samples. The excited state of one POM anion seems to give rise to subsequent electron transfer from another POM anion. However, this reaction is prohibited as soon as the relaxed T1 state of the POM is reached.