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    Thermoelectric Properties of N-Type Poly (Ether Ether Ketone)/Carbon Nanofiber Melt-Processed Composites
    (Basel : MDPI, 2022) Paleo, Antonio Jose; Krause, Beate; Soares, Delfim; Melle-Franco, Manuel; Muñoz, Enrique; Pötschke, Petra; Rocha, Ana Maria
    The thermoelectric properties, at temperatures from 30 °C to 100 °C, of melt-processed poly(ether ether ketone) (PEEK) composites prepared with 10 wt.% of carbon nanofibers (CNFs) are discussed in this work. At 30 °C, the PEEK/CNF composites show an electrical conductivity (σ) of ~27 S m−1 and a Seebeck coefficient (S) of −3.4 μV K−1, which means that their majority charge carriers are electrons. The origin of this negative Seebeck is deduced because of the impurities present in the as-received CNFs, which may cause sharply varying and localized states at approximately 0.086 eV above the Fermi energy level (EF) of CNFs. Moreover, the lower S, in absolute value, found in PEEK/CNF composites, when compared with the S of as-received CNFs (−5.3 μV K−1), is attributed to a slight electron withdrawing from the external layers of CNFs by the PEEK matrix. At temperatures from 30 °C to 100 °C, the σ (T) of PEEK/CNF composites, in contrast to the σ (T) of as-received CNFs, shows a negative temperature effect, understood through the 3D variable-range hopping (VRH) model, as a thermally activated hopping mechanism across a random network of potential wells. Moreover, their nonlinear S (T) follows the same behavior reported before for polypropylene composites melt-processed with similar CNFs at the same interval of temperatures.
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    Influence of Polyvinylpyrrolidone on Thermoelectric Properties of Melt-Mixed Polymer/Carbon Nanotube Composites
    (Basel : MDPI, 2023) Krause, Beate; Imhoff, Sarah; Voit, Brigitte; Pötschke, Petra
    For thermoelectric applications, both p- and n-type semi-conductive materials are combined. In melt-mixed composites based on thermoplastic polymers and carbon nanotubes, usually the p-type with a positive Seebeck coefficient (S) is present. One way to produce composites with a negative Seebeck coefficient is to add further additives. In the present study, for the first time, the combination of single-walled carbon nanotubes (SWCNTs) with polyvinylpyrrolidone (PVP) in melt-mixed composites is investigated. Polycarbonate (PC), poly(butylene terephthalate) (PBT), and poly(ether ether ketone) (PEEK) filled with SWCNTs and PVP were melt-mixed in small scales and thermoelectric properties of compression moulded plates were studied. It could be shown that a switch in the S-value from positive to negative values was only possible for PC composites. The addition of 5 wt% PVP shifted the S-value from 37.8 µV/K to −31.5 µV/K (2 wt% SWCNT). For PBT as a matrix, a decrease in the Seebeck coefficient from 59.4 µV/K to 8.0 µV/K (8 wt% PVP, 2 wt% SWCNT) could be found. In PEEK-based composites, the S-value increased slightly with the PVP content from 48.0 µV/K up to 54.3 µV/K (3 wt% PVP, 1 wt% SWCNT). In addition, the long-term stability of the composites was studied. Unfortunately, the achieved properties were not stable over a storage time of 6 or 18 months. Thus, in summary, PVP is not suitable for producing long-term stable, melt-mixed n-type SWCNT composites.
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    Graphite modified epoxy-based adhesive for joining of aluminium and PP/graphite composites
    (New York, NY [u.a.] : Taylor & Francis, 2020) Rzeczkowski, P.; Pötschke, Petra; Fischer, M.; Kühnert, I.; Krause, Beate
    A graphite-modified adhesive was developed in order to simultaneously enhance the thermal conductivity and the strength of an adhesive joint. The thermal conductivity through the joint was investigated by using highly filled PP/graphite composite substrates, which were joined with an epoxy adhesive of different layer thicknesses. Similar measurements were carried out with a constant adhesive layer thickness, whilst applying an epoxy adhesive modified with expanded graphite (EG) (6, 10, and 20 wt%). By reducing the adhesive layer thickness or modifying the adhesive with conductive fillers, a significant increase of the thermal conductivity through the joint was achieved. The examination of the mechanical properties of the modified adhesives was carried out by tensile tests (adhesive only), lap-shear tests, and fracture energy tests (mode 1) with aluminium substrates. Modification of the adhesive with EG led to an increase of the tensile lap-shear strength and the adhesive fracture energy (mode 1) of the joint. In addition, burst pressure tests were performed to determine the strength of the joint in a complex component. The strength of the joint increased with the graphite content in the PP substrate and in the epoxy adhesive.
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    Thermal annealing to influence the vapor sensing behavior of co-continuous poly(lactic acid)/polystyrene/multiwalled carbon nanotube composites
    (Amsterdam [u.a.] : Elsevier Science, 2020) Li, Yilong; Pionteck, Jürgen; Pötschke, Petra; Voit, Brigitte
    With the main purpose of being used as vapor leakage detector, the volatile organic compound (VOC) vapor sensing properties of conductive polymer blend composites were studied. Poly(lactic acid)/polystyrene/multi-walled carbon nanotube (PLA/PS/MWCNT) based conductive polymer composites (CPCs) in which the polymer components exhibit different interactions with the vapors, were prepared by melt mixing. CPCs with a blend composition of 50/50 wt% resulted in the finest co-continuous structure and selective MWCNT localization in PLA. Therefore, these composites were selected for sensor tests. Thermal annealing was applied aiming to maintain the blend structure but improving the sensing reversibility of CPC sensors towards high vapor concentrations. Different sensing protocols were applied using acetone (good solvent for PS and PLA) and cyclohexane (good solvent for PS but poor solvent for PLA) vapors. Increasing acetone vapor concentration resulted in increased relative resistance change (Rrel) of CPCs. Saturated cyclohexane vapor resulted in lower response than nearly saturated acetone vapor. The thermal annealing at 150 °C did not change the blend morphology but increased the PLA crystallinity, making the CPC sensors more resistant to vapor stimulation, resulting in lower Rrel but better reversibility after vapor exposure.
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    A successful approach to disperse MWCNTs in polyethylene by melt mixing using polyethylene glycol as additive
    (Oxford : Elsevier Science, 2012) Müller, Michael Thomas; Krause, Beate; Pötschke, Petra
    An additive-assisted one-step melt mixing approach was developed to produce nanocomposites based on linear low density polyethylene (LLDPE) with multiwalled carbon nanotube (MWCNT). The polymer granules, nanotube powder (2 wt% Nanocyl™ NC7000) and 1-10 wt% of the non-ionic additives poly(ethylene glycol) (PEG) or poly(ethylene oxide) (PEO) with molar masses between 100 g/mol and 100,000 g/mol were simply fed together in the hopper of a small-scale DSM Xplore 15 twin-screw microcompounder. The produced MWCNT/LLDPE composites showed excellent MWCNT dispersion and highly improved electrical properties as compared to samples without the additive, whereas the effects depend on the amount and molar mass of the additive. When 7 wt% PEG (2000 g/mol) were used, a reduction of the electrical percolation threshold from 2.5 wt% to 1.5 wt% was achieved. © 2012 Elsevier Ltd. All rights reserved.
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    Electrical and melt rheological characterization of PC and co-continuous PC/SAN blends filled with CNTs: Relationship between melt-mixing parameters, filler dispersion, and filler aspect ratio
    (Hoboken, NJ [u.a.] : Wiley, 2018) Liebscher, Marco; Domurath, Jan; Krause, Beate; Saphiannikova, Marina; Heinrich, Gert; Pötschke, Petra
    Electrical and melt rheological properties of melt-mixed polycarbonate (PC) and co-continuous PC/poly(styrene–acrylonitrile) (SAN) blends with carbon nanotubes (CNTs) are investigated. Using two sets of mixing parameters, different states of filler dispersion are obtained. With increasing CNT dispersion, an increase in electrical resistivity near the percolation threshold of PC–CNT composites and (PC + CNT)/SAN blends is observed. This suggests that the higher mixing energies required for better dispersion also result in a more severe reduction of the CNT aspect ratio; this effect was proven by CNT length measurements. Melt rheological studies show higher reinforcing effects for composites with worse dispersion. The Eilers equation, describing the melt viscosity as function of filler content, was used to fit the data and to obtain information about an apparent aspect ratio change, which was in accordance with measured CNT length reduction. Such fitting could be also transferred to the blends and serves for a qualitatively based discussion. © 2017 Wiley Periodicals
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    MWCNT induced negative real permittivity in a copolyester of Bisphenol-A with terephthalic and isophthalic acids
    (Bristol : IOP Publ., 2020) Özdemir, Zeynep Güven; Daşdan, Dolunay Şakar; Kavak, Pelin; Pionteck, Jürgen; Pötschke, Petra; Voit, Brigitte; SüngüMısırlıoğlu, Banu
    In the present study, the negative real permittivity behavior of a copolyester of bisphenol-A with terephthalic acid and isophthalic acid (PAr) containing 1.5 to 7.5 wt% multi-walled carbon nanotubes (MWCNTs) have been investigated in detail. The structural and morphological analysis of the melt-mixed composites was performed by Fourier transform infrared spectroscopy using attenuated total reflection (FTIR-ATR), atomic force microscopy (AFM), X-ray diffraction (XRD), and light microscopy. The influences of the MWCNT filler on the AC impedance, complex permittivity, and AC conductivity of the PAr polymer matrix were investigated at different operating temperatures varied between 296 K and 373 K. The transition from a negative to positive real permittivity was observed at different crossover frequencies depending on the MWCNT content of the composites whereas pure PAr showed positive values at all frequencies. The negative real permittivity characteristic of the composites was discussed in the context of Drude model. © 2020 The Author(s). Published by IOP Publishing Ltd.
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    Melt-mixed PP/MWCNT composites: Influence of CNT incorporation strategy and matrix viscosity on filler dispersion and electrical resistivity
    (Basel : MDPI, 2019) Pötschke, Petra; Mothes, Fanny; Krause, Beate; Voit, Brigitte
    Small-scale melt mixing was performed for composites based on polypropylene (PP) and 0.5–7.5 wt % multiwalled carbon nanotubes (MWCNT) to determine if masterbatch (MB) dilution is a more effective form of nanofiller dispersion than direct nanotube incorporation. The methods were compared using composites of five different PP types, each filled with 2 wt % MWCNTs. After the determination of the specific mechanical energy (SME) input in the MB dilution process, the direct-incorporation mixing time was adjusted to achieve comparable SME values. Interestingly, the electrical resistivity of MB-prepared samples with 2 wt % MWCNTs was higher than that of those prepared using direct incorporation—despite their better dispersion—suggesting more pronounced MWCNT shortening in the two-step procedure. In summary, this study on PP suggests that the masterbatch approach is suitable for the dispersion of MWCNTs and holds advantages in nanotube dispersion, albeit at the cost of slightly increased electrical resistivity.
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    Hybrid conductive filler/polycarbonate composites with enhanced electrical and thermal conductivities for bipolar plate applications
    (Manchester, NH : Wiley, 2019) Naji, Ahmed; Krause, Beate; Pötschke, Petra; Ameli, Amir
    Conductive polymer composites (CPCs) with high electrical and thermal conductivities are demanded for bipolar plates of fuel cells. In this work, CPCs of polycarbonate (PC) filled with carbon nanotube (CNT), carbon fiber (CF), graphite (G), and their double and triple hybrids were prepared using solution casting method followed by compression molding. The results showed that the electrical percolation thresholds for the PC-CNT and PC-CF were ~1 wt% and ~10 wt%, respectively, while no clear threshold was found for PC-G composites. Addition of 3–5 wt% CNT improved the electrical conductivity of PC-CF and PC-G systems up to 6 orders of magnitude and enhanced the thermal conductivity as much as 65%. The results of triple hybrid CPCs (with constant loading of 63 wt%) indicated that the combination of highest electrical and thermal conductivities is achieved when the CF and CNT loadings were near their percolation thresholds. Therefore, a triple filler system of 3 wt% CNT, 10 wt% CF, and 50 wt% G resulted in a composite with the through-plane and in-plane electrical conductivity, and thermal conductivity values of 12.8 S/cm, 8.3 S/cm, and 1.7 W/m•K, respectively. The results offer a combination of properties surpassing the existing values and suitable for high-conductivity applications such as bipolar plates. POLYM. COMPOS., 40:3189–3198, 2019. © 2018 Society of Plastics Engineers.
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    Achieving electrical conductive tracks by laser treatment of non-conductive polypropylene/polycarbonate blends filled with MWCNTs
    (Weinheim : Wiley-VCH, 2014) Liebscher, Marco; Krause, Beate; Pötschke, Petra; Barz, Andrea; Bliedtner, Jens; Möhwald, Michael; Letzsch, Alexander
    Electrical non-conductive polymer blends consisting of a polypropylene (PP) matrix and dispersed particles of polycarbonate (PC) were melt compounded with 3 wt.% multiwalled carbon nanotubes (MWCNTs) loading and processed into plates by injection molding. The morphological analysis confirmed the selective localization of the MWCNTs in the PC component. By local irradiation with a CO2 laser beam, depending on the laser conditions, conductive tracks with dimensions of about 2 mm width, 80 to 370 μm depth and line resistances as low as 1.5 kΩ · cm-1 were created on the surface of the non-conductive plates. The factors affecting the line resistance are the PC content, the laser speed and laser power, as well as laser direction with respect to the melt flow direction. After the irradiation an enrichment of MWCNTs in the laser lines was detected indicating that conductive paths were generated by percolation of nanotubes selectively within these lines in otherwise non-conductive plates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.