Abstract

It is well established that dramatic increases in conductivity occur upon the addition of conductive filler materials to highly resistive polymeric matrices in experimental settings. However, the mechanisms responsible for the observed behavior at low filler loadings, below theoretical percolation limits, of even high aspect ratio fillers such as carbon nanotubes (CNT) are not completely understood. In this study, conductive composites were fabricated using CNT bundles dispersed in epoxy resins at diverse loadings, using different dispersion and curing protocols. Based on electron microscopy observation of the CNTs strands distribution in the polymeric matrices and the corresponding electrical conductivities of those specimens, we concluded that no single electron transfer model can accurately explain the conductive behavior for all the loading values. We propose the existence of two different conductive mechanisms; one that exists close to the percolation limit, from ‘low loadings’ to higher CNT contents (CNT % wt > 0.1) and a second for ‘extremely low loadings’, near the percolation threshold (CNT % wt < 0.1). The high conductivity observed for composites at low CNT loading values can be explained by the existence of a percolative CNT network that coexists with micron size regions of non-conductive material. In contrast, samples with extremely low CNT loading values, which present no connectivity or close proximity between CNT bundles, show an electrical conductivity characterized by a current/voltage dependence. Data suggests that at these loadings, conduction may occur via a material breakdown mechanism, similar to dielectric breakdown in a capacitor. The lessons learned from the data gathered in here could guide future experimental research aimed to control the conductivity of CNT composites.

Highlights

  • Conductive carbon nanotubes (CNT) composites are in high demand due to the broad range of applications that they could enable; from anti-static materials used in fuel tanks, housing materials and containers, aerospace structures and electromagnetic interference shielding systems, to sensors and conductors used as metal replacements and thermoelectric materials among others [1,2,3,4]

  • It is generally agreed that the high conductivity observed even at low loadings of the conductive phase is related to (i) percolation, that is, to the formation of continuous strings of conductive material spanning in a non-conductive matrix material [5,6,7,8], (ii) a combined percolation-tunneling effect that allows electrons to hop from one conductive particle to another in close proximity [5,7,9], and/or (iii) the existence of excluded volumes in the matrix where no conductive material exists [10]

  • In prior conductive composite work, the implicit assumption of the experimental design was that conductivity tracks the concentration of the conductive component as it relates to the presence of percolation networks given the filler aspect ratio or other geometrical factors and how ‘well’ dispersed those are in the polymeric matrix [8,15,20,21,22]

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Summary

Introduction

Conductive CNT composites are in high demand due to the broad range of applications that they could enable; from anti-static materials used in fuel tanks, housing materials and containers, aerospace structures and electromagnetic interference shielding systems, to sensors and conductors used as metal replacements and thermoelectric materials among others [1,2,3,4]. The influence of non-spherical conductive inclusions, high aspect ratio fillers such as CNT, and how those disperse in the matrix have been scrutinized by diverse research groups, with reports of conductive samples (σ = 10−2 Sm−1) achieved at loadings that decrease the percolation threshold to values as low as 0.1% vol [5,6,9,14,15,16]. In the present work it is argued that a model consistent with all observations of conductivity over a range of CNT loadings must include consideration of: (i) properties of the conductive phase, (ii) impact of processing protocols on dispersion, (iii) the effective percolation volume of high aspect ratio conductors, (iv) excluded volumes, and (v) mechanisms of dielectric electron transport over short distances

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