Improving the electrical properties of polyamide nanocomposites

29 January 2016
Laura Arboleda-Clemente, Ana Ares-Pernas, Xoán García, Sonia Dopico, and María José Abad
Preferential localization of multiwall carbon nanotubes at the polyamide interface gives rise to a high aspect ratio that can be maintained after processing, even at low filler contents.

The dispersion of conductive fillers, such as carbon nanotubes (CNTs), in a polymer matrix or a polymer blend can give rise to electrically conductive polymer composites (CPCs).1–3 To obtain such CPCs, melt mixing technologies (e.g., extrusion and injection molding) are often used to great advantage in industrial end-use applications. Polyamide 12 (PA12) and polyamide 6 (PA6) are both industry commodity polymers. There are, however, some drawbacks to the use of PA6 in CPCs. Such problems include a high sensitivity to notch propagation under impact test (especially at temperatures below 0°C), high moisture sorption, and poor dimensional stability.

It has been suggested that PA12/PA6 blends could be used to overcome some of the problems with PA6 composites.4 To obtain a good level of electrical conductivity, however, it is usually necessary to add large amounts of CNTs to the composites. In addition, a morphology in which the CNTs migrate to the interfaces between polymers (instead of being randomly distributed in the immiscible blend) could theoretically occur. This would lead to the formation of a segregated structure with a lower percolation threshold and thus present an alternative way to improve the electrical conductivity of the composites.5

The principal aim of our work6 was therefore to design new CNT nanocomposites—with an immiscible blend of polyamides as a matrix—that have good electrical conductivity and a low percolation threshold. We used rheological tests and alternating current (AC) measurements to determine the percolation threshold of our nanocomposites. We also conducted a detailed investigation of the electrical conductivity frequency dependence in the samples. Furthermore, we used transmission electron microscopy (TEM) to examine the morphology of the nanocomposites and the CNT localization in the polymer matrix.

We conducted the rheological measurements to characterize the percolation state of the multiwall CNTs (MWCNTs) and their dispersion within the polyamide (i.e., PA12/PA6) blends. We observe a shift to a plateau in a plot of the storage modulus (see Figure 1), which indicates that the percolated network starts to form at an MWCNT content of about 0.31 volume % (%vol). Furthermore, our dielectrical analysis results (see Figure 2) clearly show that the conductivity plateau occurs at an MWCNT content of between 0.15 and 0.31%. This means that the percolation threshold, i.e., the transition to the conducting phase, is located in the same range.


Storage modulus (G ′) measurements, as a function of angular frequency (ω), for polyamide 12/polyamide 6 (PA12/PA6) composites with varying multiwall carbon nanotube (MWCNT) contents, expressed as volume % (%vol). The measurements were obtained at 235°C, with a TA Instruments ARES rheometer (25mm parallel plate and 1mm gap).


Experimental results illustrating the frequency dependence of conductivity (σAC) for the PA12/PA6 composites with different MWCNT contents. Measurements were made on a TA Instruments dielectric analyzer (DEA 2970 iv). AC: Alternating current.

We used TEM images (see Figure 3) to localize the CNT particles within the polyamide blends. Our micrographs indicate that the two polyamides (PA12 and PA6) are distributed in two different phases (a so-called island-sea morphology) and that the CNTs are mainly found at the interface between the polyamides, as seen in Figure 3(b). This preferential localization is the desired morphology for forming a segregated network and for achieving a low percolation threshold.5 Obtaining this morphology, however, depends on two key factors: first, the viscosity ratio between the immiscible polymers and, second, the interfacial energy of the CNT/polymer composites. For our study, the viscosity ratio of the PA12/PA6 blends was 0.54 and the CNT particles were pre-dispersed within the lower viscosity polyamide (PA12). This allowed us to achieve a good dispersion of the nanotubes/agglomerates within the polymer matrix during the mixing process and, therefore, obtain a segregated network.


Transmission electron microscope images of (a) the PA12/PA6/MWCNT composite containing 0.46%vol CNT particles, and (b) a close-up image of the interface between the two polyamide phases. Images were obtained using a JEOL JEM-1010 instrument.

To assess whether the observed preferential localization of CNTs at the polyamide interface reduces the percolation threshold, we made calculations using our rheological and dielectrical data. We obtained percolation threshold values of 0.258±0.001%vol and 0.09±0.01%vol for the electrical and rheological power law adjustments, respectively. Both of these values are lower than data in the literature.7, 8 To obtain electrical conductivity, it is necessary to establish a conductive percolated network across the material. This requires a CNT content greater than that which produces the rheological percolation. For this reason, the value of the electrical threshold is higher than the rheological one. It is impossible, however, to obtain such low threshold values if the high aspect ratio of the MWCNTs is not maintained after melt mixing (high levels of shear tend to break the CNTs into shorter segments). To corroborate this finding, we calculated the aspect (length to diameter) ratio for our samples. We performed these calculations using our conductivity data and a previously proposed model.6, 9 With this model, we obtained an aspect ratio of 98.1. For comparison, the initial aspect ratio of our samples was 158. Our modeled value denotes the minimum decrease in the CNT aspect ratio that occurred during the melt blending (i.e., by extrusion and subsequent nanocomposite molding).

We have conducted rheological and dielectrical measurements on a set of CNT/polyamide (PA12/PA6) composites. The low percolation thresholds we obtain are consistent with the preferential localization of the CNT particles at the interface between the two polyamides. This morphology—which we observe in TEM images of the samples—may encourage the formation of a segregated conductive network in the polymer matrix. The percolation threshold of the conductive polymer composites can thus be reduced in this way. We also observe a small decrease in the aspect ratio of the CNT particles after material processing has occurred. This could be beneficial to achieving high conductivities at low CNT contents, and therefore for producing low-cost electrical applications with improved mechanical properties. As part of our future work we plan to test whether the observed localization of the nanotubes at the interface promotes, or allows, better mechanical properties.


Authors

Laura Arboleda-Clemente
University of A Coruña

Laura Arboleda-Clemente works in the polymer group, focusing on the electrical properties and structure–property relationship of polymers.

Ana Ares-Pernas
University of A Coruña

Ana Ares-Pernas has been an associate professor since 2012. She works in the polymers group, where she specializes in the rheology and structure–property relationship of polymers.

Xoán García
University of A Coruña

Xoán García works in the polymers group, focusing on processing and the structure–property relationship of polymers.

Sonia Dopico
University of A Coruña

Sonia Dopico works in the polymers group focusing on the synthesis and structure–property relationship of polymers.

María José Abad
University of A Coruña

María José Abad has been an associate professor since 2010. She works in the polymers group, specializing in the electrical properties, rheology, processing, and structure–property relationship of polymers.


References

  1. S. Stankovich, D. A. Dikin, G. H. B. Dommett, K. M. Kohlhaas, E. J. Zimney, E. A. Stach, R. D. Piner, S. T. Nguyem and R. S. Ruoff, Graphene-based composite materials, Nature 442, pp. 282-286, 2006.

  2. H. Deng, L. Lin, M. Ji, S. Zhang, M. Yang and Q. Fu, Progress on the morphological control of conductive network in conductive polymer composites and the use as electroactive multifunctional materials, Prog. Polym. Sci. 39, pp. 627-655, 2014.

  3. M. H. Al-Saleh and U. Sundararaj, A review of vapor grown nanofiber/polymer conductive composites, Carbon 47, pp. 2-22, 2009.

  4. J. Whan and C. D. R. Paul, Glass fiber-reinforced polyamide composites toughened with ABS and EPR-g-MA, J. Appl. Polym. Sci. 80, pp. 484-497, 2001.

  5. H. Pang, L. Xu, D.-X. Yan and Z.-M. Li, Conductive polymer composites with segregated structures, Prog. Polym. Sci. 39, pp. 1908-1933, 2014.

  6. L. Arboleda-Clemente, A. Ares-Pernas, X. García, S. Dopico and M. J. Abad, Segregated conductive network of MWCNT in PA12/PA6 composites: electrical and rheological behavior, Polym. Compos., 2015. First published online: 19 November 2015

  7. E. Logakis, C. Pandis, V. Peoglos, P. Pissis, J. Pionteck, P. Pötschke, M. Mičušík and M. Omastová, Electrical/dielectric properties and conducting mechanism in melt processed polyamide/multi-walled carbon nanotubes composites, Polymer 50, pp. 5103-5111, 2009.

  8. O. Meincke, D. Kaempfer, H. Weickmann, C. Friedrich, M. Vathauer and H. Warth, Mechanical properties and electrical conductivity of carbon-nanotube filled polyamide-6 and its blends with acrylonitrile/butadiene/styrene, Polymer 45, pp. 739-748, 2004.

  9. E. J. Garboczi, K. A. Snyder, J. F. Douglas and M. F. Thorpe, Geometrical percolation threshold of overlapping ellipsoids, Phys. Rev. E 52, pp. 819-828, 1995.

DOI:  10.2417/spepro.006332