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Blend Structure and n-Type Thermoelectric Performance of PA6/SAN and PA6/PMMA Blends Filled with Singlewalled Carbon Nanotubes

2021-4-28, Krause, Beate, Liguoro, Alice, Pötschke, Petra

The present study investigates how the formation of melt-mixed immiscible blends based on PA6/SAN and PA6/PMMA filled with single walled nanotubes (SWCNTs) affects the thermoelectric (TE) properties. In addition to the detailed investigation of the blend morphology with compositions between 100/0 wt.% and 50/50 wt.%, the thermoelectric properties are investigated on blends with different SWCNT concentrations (0.25–3.0 wt.%). Both PA6 and the blend composites with the used type of SWCNTs showed negative Seebeck coefficients. It was shown that the PA6 matrix polymer, in which the SWCNTs are localized, mainly influenced the thermoelectric properties of blends with high SWCNT contents. By varying the blend composition, an increase in the absolute Seebeck coefficient, power factor (PF), and figure of merit (ZT) was achieved compared to the PA6 composite which is mainly related to the selective localization and enrichment of SWCNTs in the PA6 matrix at constant SWCNT loading. The maximum PFs achieved were 0.22 µW/m·K2 for PA6/SAN/SWCNT 70/30/3 wt.% and 0.13 µW/m·K2 for PA6/PMMA/SWCNT 60/40/3 wt.% compared to 0.09 µW/m·K2 for PA6/3 wt.% SWCNT which represent increases to 244% and 144%, respectively. At higher PMMA or SAN concentration, the change from matrix-droplet to a co-continuous morphology started, which, despite higher SWCNT enrichment in the PA6 matrix, disturbed the electrical conductivity, resulting in reduced PFs with still increasing Seebeck coefficients. At SWCNT contents between 0.5 and 3 wt.% the increase in the absolute Seebeck coefficient was compensated by lower electrical conductivity resulting in lower PF and ZT as compared to the PA6 composites.

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Effect of filler synergy and cast film extrusion parameters on extrudability and direction-dependent conductivity of PVDF/carbon nanotube/carbon black composites

2020, Krause, Beate, Kunz, Karina, Kretzschmar, Bernd, Kühnert, Ines, Pötschke, Petra

In the present study, melt-mixed composites based of poly (vinylidene fluoride) (PVDF) and fillers with different aspect ratios (carbon nanotubes (CNTs), carbon black (CB)) and their mixtures in composites were investigated whereby compression-molded plates were compared with melt-extruded films. The processing-related orientation of CNTs with a high aspect ratio leads to direction-dependent electrical and mechanical properties, which can be reduced by using mixed filler systems with the low aspect ratio CB. An upscaling of melt mixing from small scale to laboratory scale was carried out. From extruded materials, films were prepared down to a thickness of 50 µm by cast film extrusion under variation of the processing parameters. By combining CB and CNTs in PVDF, especially the electrical conductivity through the film could be increased compared to PVDF/CNT composites due to additional contact points in the sample thickness. The alignment of the fillers in the two directions within the films was deduced from the differences in electrical and mechanical film properties, which showed higher values in the extrusion direction than perpendicular to it.

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Effects of Particle Size and Surface Chemistry on the Dispersion of Graphite Nanoplates in Polypropylene Composites

2018, Santos, Raquel M., Mould, Sacha T., Formánek, Petr, Paiva, Maria C., Covas, José A.

Carbon nanoparticles tend to form agglomerates with considerable cohesive strength, depending on particle morphology and chemistry, thus presenting different dispersion challenges. The present work studies the dispersion of three types of graphite nanoplates (GnP) with different flake sizes and bulk densities in a polypropylene melt, using a prototype extensional mixer under comparable hydrodynamic stresses. The nanoparticles were also chemically functionalized by covalent bonding polymer molecules to their surface, and the dispersion of the functionalized GnP was studied. The effects of stress relaxation on dispersion were also analyzed. Samples were removed along the mixer length, and characterized by microscopy and dielectric spectroscopy. A lower dispersion rate was observed for GnP with larger surface area and higher bulk density. Significant re-agglomeration was observed for all materials when the deformation rate was reduced. The polypropylene-functionalized GnP, characterized by increased compatibility with the polymer matrix, showed similar dispersion effects, albeit presenting slightly higher dispersion levels. All the composites exhibit dielectric behavior, however, the alternate current (AC) conductivity is systematically higher for the composites with larger flake GnP.

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Electrical, mechanical, and glass transition behavior of polycarbonate-based nanocomposites with different multi-walled carbon nanotubes

2011, Castillo, Frank Yepez, Socher, Robert, Krause, Beate, Headrick, Robert, Grady, Brian P., Prada-Silvy, Ricardo, Pötschke, Petra

Five commercially available multi-walled carbon nanotubes (MWNTs), with different characteristics, were melt mixed with polycarbonate (PC) in a twin-screw micro compounder to obtain nanocomposites containing 0.25-3.0 wt.% MWNT. The electrical properties of the composites were assessed using bulk electrical conductivity measurements, the mechanical properties of the composites were evaluated using tensile tests and dynamic mechanical analysis (DMA), and the thermal properties of the composites were investigated using differential scanning calorimetry (DSC). Electrical percolation thresholds (pcs) were observed between 0.28 wt.% and 0.60 wt.%, which are comparable with other well-dispersed melt mixed materials. Based on measurements of diameter and length distributions of unprocessed tubes it was found that nanotubes with high aspect ratios exhibited lower pcs, although one sample did show higher pc than expected (based on aspect ratio) which was attributed to poorer dispersion achieved during mixing. The stress-strain behavior of the composites is only slightly altered with CNT addition; however, the strain at break is decreased even at low loadings. DMA tests suggest the formation of a combined polymer-CNT continuous network evidenced by measurable storage moduli at temperatures above the glass transition temperature (T g), consistent with a mild reinforcement effect. The composites showed lower glass transition temperatures than that of pure PC. Lowering of the height of the tanδ peak from DMA and reductions in the heat capacity change at the glass transition from DSC indicate that MWNTs reduced the amount of polymer material that participates in the glass transition of the composites, consistent with immobilization of polymer at the nanotube interface. © 2011 Elsevier Ltd. All rights reserved.