The authors wish to dedicate this paper to the memory of Officer Sean Collier for his caring service to the MIT community and for his sacrifice.

(G. C. Rutledge). AbstractThe mechanical and tribological properties of electrospun fiber mats are of paramount importance to their utility as components in a large number of applications. Although some mechanical properties of these mats have been reported previously, reports of their tribological properties are essentially nonexistent. In this work, electrospun nanofiber mats of poly(trimethyl hexamethylene terephthalamide) (PA 6(3)T) with average fiber diameter of 463±64 nm are characterized mechanically and tribologically. Post-spin thermal annealing was used to modify the properties of the fiber mats.Morphological changes, in-plane tensile response, friction coefficient and wear rate were characterized as functions of the annealing temperature. The Young's moduli, yield stresses and toughnesses of the nonwoven mats improved by two-to ten-fold when annealed slightly above the glass transition temperature, but at the expense of mat porosity. The coefficient of friction and the wear rate decrease by factors of two and ten, respectively, under the same conditions. The wear rate correlates with the yield properties of the mat, in accord with a modified Ratner-Lancaster model. The variation in mechanical and tribological properties of the mats with increasing annealing temperature is consistent with the formation of fiber-to-fiber junctions and a mechanism of abrasive wear that involves the breakage of fibers between junctions.

Polymer electrolyte films are deposited onto highly porous electrospun mats using layer‐by‐layer (LbL) processing to fabricate composite proton conducting membranes. By simply changing the assembly conditions for generation of the LbL film on the nanofiber mat substrate, three different and unique composite film morphologies can be achieved in which the electrospun mats provide mechanical support; the LbL assembly produces highly conductive films that coat the mats in a controlled fashion, separately providing the ionic conductivity and fuel blocking characteristics of the composite membrane. Coating an electrospun mat with the LbL dipping process produces composite membranes with “webbed” morphologies that link the fibers in‐plane and give the composite membrane in‐plane proton conductivities similar to that of the pristine LbL system. In contrast, coating an electrospun mat using the spray‐LbL process without vacuum produces a uniform film that bridges across all of the pores of the mat. These membranes have methanol permeability similar to free‐standing poly(diallyl dimethyl ammonium chloride)/sulfonated poly(2,6‐dimethyl 1,4‐phenylene oxide) (PDAC/sPPO) thin films. Coating an electrospun mat with the vacuum‐assisted spray‐LbL process produces composite membranes with conformally coated fibers throughout the bulk of the mat with nanometer control of the coating thickness on each fiber. The mechanical properties of the LbL‐coated mats display composite properties, exhibiting the strength of the glassy PDAC/sPPO films when dry and the properties of the underlying electrospun polyamide mat when hydrated. By combining the different spray‐LbL fabrication techniques with electrospun fiber supports and tuning the parameters, mechanically stable membranes with high selectivity can be produced, potentially for use in fuel cell applications.

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