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

Model thermoplastic polyurethanes (TPUs) are prepared with the aim of investigating the effect of soft‐to‐hard segment ratio on the phase transition and the resulting structure that forms upon isothermal exposure to temperatures near their phase transition temperature. The dynamic rheological properties of TPUs before exposure to these isothermal conditions show a phase transition at high temperatures that is directly related to the content of hard segments. The extensional viscosity data indicate a strain‐hardening behavior that becomes less pronounced with the increase of hard segments. After isothermal treatment, the DSC results show that the high‐temperature endotherm peak narrows and shifts to higher temperatures, suggesting a transition in structure. Small angle X‐ray scattering, wide angle X‐ray scattering, and atomic force microcopy results indicate a phase‐separated system in which the hard domain sizes and crystallinity change during this process. The rheological data collected after recrystallization show a significant increase in both moduli, transitioning from viscoelastic fluid‐like to glassy behavior. Concurrently, the uniaxial elongation viscosity presents a significant increase in absolute values, but with a shift from strain‐hardening to strain‐softening behavior for all strain rates. A transition from traditional phase separated viscoelastic melt behavior to more brittle rupture is also observed, marking a significant fundamental difference in properties before and after recrystallization.

This research work presents the first continuous multilayer coextrusion system for high viscosity elastomeric materials. Three unvulcanized rubber materials were chosen to validate the system: two butyl rubbers and a polyisoprene. The elastomers were characterized under oscillatory shear and the results used to perform computational flow simulations to investigate the effect of geometry on the flow path and flow rate. Successful extrudates of 8 and 32 layers were extruded at two different throughput rates for rheologically matched and rheologically mismatched material pairs. The results show good layering performance for both systems with little existence of viscous encapsulation and acceptable pressure drops. Computational and experimental results both show a nonuniform layer thickness distribution due to the geometric design of the layer multiplier extrusion dies, which were designed to minimize pressure drop in the system. This nonuniformity decreases with increasing number of layers. POLYM. ENG. SCI., 55:1520-1527, 2015