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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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    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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    Nitrogen-Doped Carbon Nanotube/Polypropylene Composites with Negative Seebeck Coefficient
    (Basel : MDPI, 2020) Krause, Beate; Konidakis, Ioannis; Arjmand, Mohammad; Sundararaj, Uttandaraman; Fuge, Robert; Liebscher, Marco; Hampel, Silke; Klaus, Maxim; Serpetzoglou, Efthymis; Stratakis, Emmanuel; Pötschke, Petra
    This study describes the application of multi-walled carbon nanotubes that were nitrogen-doped during their synthesis (N-MWCNTs) in melt-mixed polypropylene (PP) composites. Different types of N-MWCNTs, synthesized using different methods, were used and compared. Four of the five MWCNT grades showed negative Seebeck coefficients (S), indicating n-type charge carrier behavior. All prepared composites (with a concentration between 2 and 7.5 wt% N-MWCNTs) also showed negative S values, which in most cases had a higher negative value than the corresponding nanotubes. The S values achieved were between 1.0 µV/K and −13.8 µV/K for the N-MWCNT buckypapers or powders and between −4.7 µV/K and −22.8 µV/K for the corresponding composites. With a higher content of N-MWCNTs, the increase in electrical conductivity led to increasing values of the power factor (PF) despite the unstable behavior of the Seebeck coefficient. The highest power factor was achieved with 4 wt% N-MWCNT, where a suitable combination of high electrical conductivity and acceptable Seebeck coefficient led to a PF value of 6.1 × 10−3 µW/(m·K2). First experiments have shown that transient absorption spectroscopy (TAS) is a useful tool to study the carrier transfer process in CNTs in composites and to correlate it with the Seebeck coefficient.
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    Mixed Carbon Nanomaterial/Epoxy Resin for Electrically Conductive Adhesives
    (Basel : MDPI, 2020) Lopes, Paulo E.; Moura, Duarte; Hilliou, Loic; Krause, Beate; Pötschke, Petra; Figueiredo, Hugo; Alves, Ricardo; Lepleux, Emmanuel; Pacheco, Louis; Paiva, Maria C.
    The increasing complexity of printed circuit boards (PCBs) due to miniaturization, increased the density of electronic components, and demanding thermal management during the assembly triggered the research of innovative solder pastes and electrically conductive adhesives (ECAs). Current commercial ECAs are typically based on epoxy matrices with a high load (>60%) of silver particles, generally in the form of microflakes. The present work reports the production of ECAs based on epoxy/carbon nanomaterials using carbon nanotubes (single and multi-walled) and exfoliated graphite, as well as hybrid compositions, within a range of concentrations. The composites were tested for morphology (dispersion of the conductive nanomaterials), electrical and thermal conductivity, rheological characteristics and deposition on a test PCB. Finally, the ECA’s shelf life was assessed by mixing all the components and conductive nanomaterials, and evaluating the cure of the resin before and after freezing for a time range up to nine months. The ECAs produced could be stored at −18 °C without affecting the cure reaction.
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    Experimental and computational analysis of thermoelectric modules based on melt-mixed polypropylene composites
    (Amsterdam : Elsevier, 2023) Doraghi, Qusay; Żabnieńska-Góra, Alina; Norman, Les; Krause, Beate; Pötschke, Petra; Jouhara, Hussam
    Researchers are constantly looking for new materials that exploit the Seebeck phenomenon to convert heat into electrical energy using thermoelectric generators (TEGs). New lead-free thermoelectric materials are being investigated as part of the EU project InComEss, with one of the anticipated uses being converting wasted heat into electric energy. Such research aims to reduce the production costs as well as the environmental impact of current TEG modules which mostly employ bismuth for their construction. The use of polymers that, despite lower efficiency, achieve increasingly higher values of electrical conductivity and Seebeck coefficients at a low heat transfer coefficient is increasingly discussed in the literature. This article presents two thermoelectric generator (TEG) models based on data previously described in the literature. Two types of designs are presented: consisting of 4- and 49-leg pairs of p- and n-type composites based on polypropylene melt-mixed with single-walled carbon nanotubes. The models being developed using COMSOL Multiphysics software and validated based on measurements carried out in the laboratory. Based on the results of the analysis, conductive polymer composites employing insulating matrices can be considered as a promising material of the future for TEG modules.
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    Messanlage zur Untersuchung des Seebeck-Effektes in Polymermaterialien
    (Berlin : De Gruyter, 2020) Jenschke, Wolfgang; Ullrich, Mathias; Krause, Beate; Pötschke, Petra
    The thermoelectric effect named after the physicist Thomas Johann Seebeck has been investigated sufficiently well for all technically relevant metals and has been used for a long time, among other things, for temperature measurement by means of thermocouples. Less well known and researched is the Seebeck effect in polymer materials, which are gaining increasing influence in the sensor industry today. This article describes a measuring system designed specifically to study the Seebeck effect in polymeric samples with the aim of developing tailored polymers for sensory engineering applications using the Seebeck effect. The special requirement of the measuring system is the realization of constant accurate temperature sources.
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    Nanocomposites with p-and n-type conductivity controlled by type and content of nanotubes in thermosets for thermoelectric applications
    (Basel : MDPI, 2020) Kröning, Katharina; Krause, Beate; Pötschke, Petra; Fiedler, Bodo
    In this work, composites based on epoxy resin and various carbon nanotubes (CNTs) were studied regarding their thermoelectric properties. The epoxy composites were prepared by infiltration of preformed CNT buckypapers. The influence of different types of CNTs on the Seebeck coefficient was investigated, namely lab-made and commercially available multi walled carbon nanotubes (MWCNTs), lab-made nitrogen doped MWCNTs (N-MWCNT) and commercially available single walled carbon nanotubes (SWCNTs). It was found that only by varying the lab-made MWCNT content could both n-and p-type composites be produced with Seebeck coefficients between -9.5 and 3.1 µV/K. The incorporation of N-MWCNTs resulted in negative Seebeck coefficients of -11.4 to -17.4 µV/K. Thus, the Seebeck coefficient of pure SWCNT changed from 37.4 to -25.5 µV/K in the epoxy/1 wt. % SWCNT composite. A possible explanation for the shift in the Seebeck coefficient is the change of the CNTs Fermi level depending on the number of epoxy molecules on the CNT surface. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.