Direct-Write Fabrication of Polymer Nanocomposite Fibers

Abstract

ABSTRACTThe unique properties of carbon-nanotube (CNT)-doped polymers have generated several promising applications including gas sensors, high-strength/light-weight materials, and electromagnetic interference shielding. The ability to process CNT-doped materials into complex architectures may enable further advancement of these devices. We have developed a direct-write technique for processing CNT-doped poly(methyl methacrylate) (PMMA) into 3D arrays of precisely-positioned fibers with micro- and sub-microscale diameters. In this method, a programmable micromanipulator-controlled syringe was loaded with solvated CNT/PMMA and utilized to draw an array of freely-suspended solution filaments on a substrate in a “connect-the-dots” fashion. As the filaments are drawn, they are thinned by surface tension-driven necking as they dry and form solid fibers. The degree of thinning can be controlled by varying the viscosity of the solution, which acts to resist the necking while the volatile solvent evaporates and solidification occurs. Multiple fibers were drawn to investigate the effects of several factors on fiber diameter and process yield. These variables included fiber length (4, 8, and 18 mm), fiber drawing velocity (5 and 20 mm/s), polymer concentration in solution (22 and 24% by wt.), and CNT concentration in solution (0, 0.5, 1, and 1.5% by wt.), with the latter two of these variables strongly influencing solution viscosity. Measurement of the fibers via scanning electron microscopy (SEM) revealed several trends: Fiber diameter was not influenced by CNT concentration, but increased with increasing PMMA concentration (P<0.001), increasing drawing rate (P<0.01), and decreasing fiber length (P<0.001), with fiber diameter ranging from 538 nm to >100 μm. Furthermore, fiber yield exceeded 75% for all tested solutions except for the lowest viscosity CNT-doped solution (24% PMMA/0.5% CNT, η=50.1 Pa*s), which experienced capillary breakup prior to solidification. The conductivities of direct-write PMMA/CNT fibers ranged from <10-7to 0.15 S/m, with shorter fibers having higher conductivities (P<10.005). Also, fibers drawn from solutions with 1.0% CNTs had higher conductivities that those drawn from solutions with 0.5% or 1.5% CNTs (P<0.01). This nonlinear trend was further investigated by cleaving fibers in liquid nitrogen and imaging their cross-sections with an SEM. This analysis illustrated that the CNTs, which were functionalized to remain dispersed in the solvent, tended to randomly aggregate within the polymer-fiber matrix, particularly for fibers drawn from solutions containing 1.5% CNTs. In conclusion, CNT/PMMA fibers were successfully drawn with the direct-write technique and CNT doping had no significant influence on fiber diameter or yield compared with fibers drawn from PMMA homopolymer. However, the CNTs were found to strongly aggregate when drawn from solutions loaded at high concentrations (1.5%), thereby hindering electrical transport.