Characterization and modification of electrospun fiber mats for use in composite proton exchange membranes

[摘要] Electrostatic fiber formation, or electrospinning, offers a particularly simple and robust method to create polymeric nanofibers of various sizes and morphologies. In electrospinning, a viscoelastic fluid is charged so that a liquid jet is ejected from the surface of the fluid (typically in the form of a drop supplied by a needle or spinneret) and collected on a grounded plate, creating a nonwoven fiber mat. Modification of the diameter of the fibers as well as the porosity, specific surface area, and mechanical properties of the mat allows one to tailor electrospun mats for specific applications. Despite the widespread and rapidly growing use of electrospinning in the fabrication of novel nanomaterials, there are no simple, universal methods of predicting, a priori, the properties of electrospun fibers from knowledge of the polymer solution properties and electrospinning operating conditions alone. Changing a single fluid or processing parameter can affect the jet and fiber formation through several mechanisms. For example, using a different solvent can change several properties of the electrospinning fluid, such as the dielectric constant, conductivity, surface tension, and solute-solvent interaction. The work in this thesis seeks to develop a simple relation for predicting terminal jet diameter during electrospinning, which accounts for solution viscoelasticity as well as solution conductivity and operating parameters that can be easily measured and controlled. The mechanical and tribological properties of electrospun fiber mats are of paramount importance to their utility as components in a variety of applications. Although some mechanical properties of these mats have been investigated previously, reports of their tribological properties are essentially nonexistent. In this thesis, electrospun nanofiber mats of poly(trimethyl hexamethylene terephthalamide) (PA 6(3)T) and poly(hexamethylene adipamide) (PA 6,6) are characterized mechanically and tribologically. Post-spin thermal annealing was used to modify the fiber morphology, inter-fiber welding, and crystallinity within the fibers. 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 PA 6(3)T nonwoven mats improved by two- to ten-fold when annealed slightly above the glass transition temperature, but at the expense of mat porosity. The mechanical and tribological properties of the thermally annealed PA 6,6 fiber mats exhibited significant improvements through the Brill transition temperature, comparable to the improvements observed for amorphous PA 6(3)T electrospun mats annealed near the glass transition temperature. The wear rates for both polymer systems correlate with the yield properties of the mat, in accordance 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 these junctions between fibers. A mechanically robust proton exchange membrane with high ionic conductivity and selectivity is an important component in many electrochemical energy devices such as fuel cells, batteries, and photovoltaics. The ability to control and improve independently the mechanical response, ionic conductivity, and selectivity properties of a membrane is highly desirable in the development of next generation electrochemical devices. In this thesis, the use of layer-by-layer (LbL) assembly of polyelectrolytes is used to generate three different polymer film morphologies on highly porous electrospun fiber mats: webbed, conformal coating, and pore-bridging films. Specifically, depending on whether a vacuum is applied to the backside of the mat or not, the spray-LbL assembly either fills the voids of the mat with the proton conducting material or forms a continuous fuel-blocking film. The LbL component consists of a proton-conducting, methanolimpermeable poly(diallyl dimethyl ammonium chloride)/sulfonated poly(2,6-dimethyl 1,4- phenylene oxide) (PDAC/sPPO) thin film. The electrospun fiber component consists of PA 6(3)T fibers of average diameter between 400 and 800 nm, in a nonwoven matrix of 60-90% porosity depending on the temperature of thermal annealing utilized to improve the mechanical properties. This thesis demonstrates the versatility and flexibility of this fabrication technique, since any ion conducting LbL system may be sprayed onto any electrospun fiber mat, allowing for independent control of functionality and mechanical properties. The mechanical properties of the spray coated electrospun mats are shown to be superior to the LbL-only system, and possess intrinsically greater dimensional stability and lower mechanical hysteresis than Nafion under hydration cycling. The electrochemical selectivity of the composite LbL-electrospun membrane is found to be superior to Nafion, which makes them a viable alternative proton exchange membrane for fuel cell applications. The composite proton exchange membranes fabricated in this work were tested in an operational direct methanol fuel cell, with results showing the capability for higher open circuit voltages (OCV) and comparable cell resistances when compared to Nafion.

[发布机构] Massachusetts Institute of Technology