a b s t r a c tIn this study, the fabrication of crosslinked nonwoven fibers via simultaneous thiol-ene photopolymerization and spinning of monomer jets has been demonstrated in centrifugal Forcespinning for the first time. We observed that simultaneous Forcespinning and photopolymerization resulted in a wide variety of fiber morphologies including beads, beads-on-string, uniform fiber, fused fibers, and wellcured fibers. To elucidate the underlying mechanisms and parameter interactions that give rise to these morphologies, we systematically varied the light intensity, solution elasticity, and spin speed of the Forcespinning process. From these experimental results, an operating diagram was constructed based on the measured process parameters, their respective timescales, and observed effects on fiber morphology. While numerous parameters can individually affect fiber formation and morphology, the interplay between curing kinetics, solution viscoelasticity, and orifice-to-collector processing time window is also crucial in this process. Smooth and well-cured fibers were formed only when the photopolymerization occurred sufficiently quickly, before both the breakup of fibers into droplets due to a surface tension driven Rayleigh instability and the deposition of fibers on the collector. Our findings can serve as a predictive guideline for the fabrication of crosslinked fibers with desired morphology, the implementation of the in-situ polymerization and spinning concept into other commercial fiber manufacturing technologies, and the adaptation of other functional or high performance monomer systems.

In this study, key factors for controlling the average fiber diameter and diameter distribution of fibers made via simultaneous centrifugal spinning and UV initiated polymerization are elucidated. Through systematic investigation, it was found that average fiber diameter has a strong dependence on monomer delivery rate through the orifice, which can be intuitively linked to both the orifice diameter and monomer mixture viscosity. On the other hand, the breadth of the fiber diameter distribution can be controlled by the spin speed of the rotating spinneret. Carefully tuning these process parameters allows near independent control of fiber diameter and its distribution, which could provide access to a widely tailorable range of fiber diameters and diameter distributions appropriate for different applications. Finally, under optimized process conditions, crosslinked fibers with average diameters of approximately 1.5 µm can be produced, which are one to two orders of magnitude smaller than photocured fibers fabricated in previous reports and comparable with the smallest melt blown nonwoven fibers produced commercially. Coupled with the advantages of cross-linked fibers made by in-situ photopolymerization, the capability to produce small fibers with tailored

A thin layer of fibers was attached to the SEM sample holder with double sided carbon tape and sputter coated with Au/Pd to minimize charging. The coated samples were imaged by Hitachi S-4500 SEM at an accelerating voltage of 15 kV. Several low and high magnification images were

Polyhedral oligomeric silsesquioxanes (POSS) are versatile inorganic-organic hybrid building blocks that have potential applications as reinforcement nanofillers, thermal stabilizers, and catalyst supports for metal nanoparticles. However, fabrication of fibrous materials with high POSS content has been a challenge because of the aggregation and solubility limits of POSS units. In this paper, we describe a robust and environmentally friendly fabrication approach of inorganic-organic hybrid POSS fibers by integrating UV initiated thiol-ene polymerization and centrifugal fiber spinning. The use of monomeric liquids in this approach not only reduces the consumption of heat energy and solvent, but it also promotes homogeneous mixing of organic and inorganic components that allows integration of large amount of POSS (up to 80 wt %) into the polymer network. The POSS containing thiol-ene fibers exhibited enhanced thermomechanical properties compared to purely organic analogs as revealed by substantial increases in residual weight and a factor of 4 increase in modulus after thermal treatment at 1000 °C. This simple fabrication approach combined with the tunability in fiber properties afforded by tailoring monomer composition make POSS containing thiol-ene fibers attractive candidates for catalyst supports and filtration media, particularly in high-temperature and harsh environments.

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