The thermoelectric behavior of polypropylene (PP) based nanocomposites containing single walled carbon nanotubes (SWCNTs) and five kinds of ionic liquids (Ils) dependent on composite composition and electron beam irradiation (EB) was studied. Therefore, several samples were melt-mixed in a micro compounder, while five Ils with sufficiently different anions and/or cations were incorporated into the PP/SWCNT composites followed by an EB treatment for selected composites. Extensive investigations were carried out considering the electrical, thermal, mechanical, rheological, morphological and, most significantly, thermoelectric properties. It was found that it is possible to prepare n-type melt-mixed polymer composites from p-type commercial SWCNTs with relatively high Seebeck coefficients when adding four of the selected Ils. The highest Seebeck coefficients achieved in this study were +49.3 µV/K (PP/2 wt.% SWCNT) for p-type composites and −27.6 µV/K (PP/2 wt.% SWCNT/4 wt.% IL type AMIM Cl) for n-type composites. Generally, the type of IL is decisive whether p- or n-type thermoelectric behavior is achieved. After IL addition higher volume conductivity could be reached. Electron beam treatment of PP/SWCNT leads to increased values of the Seebeck coefficient, whereas the EB treated sample with IL (AMIM Cl) shows a less negative Seebeck coefficient value.
This study followed the approach of dispersing and localizing carbon nanotubes (CNTs) in nanostructured domains of block copolymers (BCPs) by shortening the CNTs via ball milling. The aim was to selectively tune the electrical and mechanical properties of the resulting nanocomposites, e.g., for use as sensor materials. Multiwalled carbon nanotubes (MWCNTs) were ground into different size fractions. The MWCNT length distribution was evaluated via transmission electron microscopy and dynamic light scattering. The nanostructure of the BCPs and the glass transition temperatures of the PB-rich and PS phases were not strongly affected by the addition of CNTs up to 2 wt%. However, AFM and TEM investigations indicated a partial localization of the shortened CNTs in the soft PB-rich phase or at the interface of the PB-rich and PS phase, respectively. The stress-strain behavior of the solution-mixed composites differed little from the mechanical property profile of the neat BCP and was largely independent of CNT amount and CNT size fraction. Significant changes could only be observed for Young’s modulus and strain at break and may be attributed to CNT localization and small changes in morphology. For nanocomposites with unmilled CNTs, the electrical percolation threshold was less than 0.1 wt%. As the CNTs were shortened, the resistivity increased and the percolation threshold shifted to higher CNT contents. Composites with CNTs ground for 7.5 h and 13.5 h showed no bulk conductivity but significantly decreased surface resistivity on the bottom side of the films, which could be attributed to a sedimentation process of the grind and thereby highly compressed CNT agglomerates during evaporation.
In this bipartite study, waste products of die-sink electro discharge machining (die-sink EDM) are investigated. EDM is based on an erosive character of discharges leading to material removal and molten material congeals in the dielectric. The aim is to show a theoretical suitability of these particles for a further usage as a secondary, recycled material in additive manufacturing (AM). Due to the energy- and cost-intensive process of gas atomization for AM powders, there is a need for alternative concepts for particle generation. The first part deals with an intensive review of references from the literature regarding particle size and circularity using image analysis. Secondly, real waste streams were investigated after washing and cleaning processes for oil removal via laser diffraction, dynamic image analysis, SEM with energy dispersive X-ray spectroscopy (EDX) as well as optical emission spectroscopy (ICP OES), categorized within the literature and compared to commercial AM powders. In general, it could be shown that, in principle, recycled particles fulfill main requirements for an AM usage regarding size and shape. Reference powders show median particle sizes of 30 µm to 34 µm and circularities of 0.90 to 0.93, whereas eroded particles exhibit an x50 value of 27 µm and circularity of 0.90, too. However, chemical purity, mainly caused by carbon contamination (5.4 wt% in eroded powder compared to 0.4 wt% in reference powder), must be improved before printing via AM machines. Additionally, several separation techniques have to be applied to remove undesired elements (alumina).
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