2021-3-1, Gültner, Marén, Boldt, Regine, Formanek, Petr, Fischer, Dieter, Simon, Frank, Pötschke, Petra

Co-continuous blend systems of polycarbonate (PC), poly(styrene-co-acrylonitrile) (SAN), commercial non-functionalized multi-walled carbon nanotubes (MWCNTs) or various types of commercial and laboratory functionalized single-walled carbon nanotubes (SWCNTs), and a reactive component (RC, N-phenylmaleimide styrene maleic anhydride copolymer) were melt compounded in one step in a microcompounder. The blend system is immiscible, while the RC is miscible with SAN and contains maleic anhydride groups that have the potential to reactively couple with functional groups on the surface of the nanotubes. The influence of the RC on the localization of MWCNTs and SWCNTs (0.5 wt.%) was investigated by transmission electron microscopy (TEM) and energy-filtered TEM. In PC/SAN blends without RC, MWCNTs are localized in the PC component. In contrast, in PC/SAN-RC, the MWCNTs localize in the SAN-RC component, depending on the RC concentration. By adjusting the MWCNT/RC ratio, the localization of the MWCNTs can be tuned. The SWCNTs behave differently compared to the MWCNTs in PC/SAN-RC blends and their localization occurs either only in the PC or in both blend components, depending on the type of the SWCNTs. CNT defect concentration and surface functionalities seem to be responsible for the localization differences.

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.

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.

2022-1-10, Paleo, Antonio J., Krause, Beate, Cerqueira, Maria F., Muñoz, Enrique, Pötschke, Petra, Rocha, Ana M.

The temperature dependent electrical conductivity σ (T) and thermopower (Seebeck coeffi-cient) S (T) from 303.15 K (30◦ C) to 373.15 K (100◦ C) of an as-received commercial n-type vapour grown carbon nanofibre (CNF) powder and its melt-mixed polypropylene (PP) composite with 5 wt.% of CNFs have been analysed. At 30◦ C, the σ and S of the CNF powder are ~136 S m−1 and −5.1 µV K−1, respectively, whereas its PP/CNF composite showed lower conductivities and less negative S-values of ~15 S m−1 and −3.4 µV K−1, respectively. The σ (T) of both samples presents a dσ/dT < 0 character described by the 3D variable range hopping (VRH) model. In contrast, their S (T) shows a dS/dT > 0 character, also observed in some doped multiwall carbon nanotube (MWCNT) mats with nonlinear thermopower behaviour, and explained here from the contribution of impurities in the CNF structure such as oxygen and sulphur, which cause sharply varying and localized states at approximately 0.09 eV above their Fermi energy level (EF).

2020, Fritsch, Marco, Coeler, Matthias, Kunz, Karina, Krause, Beate, Marcinkowski, Peter, Pötschke, Petra, Wolter, Mareike, Michaelis, Alexander

A hermetic dense polymer-carbon composite-based current collector foil (PCCF) for lithium-ion battery applications was developed and evaluated in comparison to state-of-the-art aluminum (Al) foil collector. Water-processed LiNi0.5Mn1.5O4 (LMNO) cathode and Li4Ti5O12 (LTO) anode coatings with the integration of a thin carbon primer at the interface to the collector were prepared. Despite the fact that the laboratory manufactured PCCF shows a much higher film thickness of 55 µm compared to Al foil of 19 µm, the electrode resistance was measured to be by a factor of 5 lower compared to the Al collector, which was attributed to the low contact resistance between PCCF, carbon primer and electrode microstructure. The PCCF-C-primer collector shows a sufficient voltage stability up to 5 V vs. Li/Li+ and a negligible Li-intercalation loss into the carbon primer. Electrochemical cell tests demonstrate the applicability of the developed PCCF for LMNO and LTO electrodes, with no disadvantage compared to state-of-the-art Al collector. Due to a 50% lower material density, the lightweight and hermetic dense PCCF polymer collector offers the possibility to significantly decrease the mass loading of the collector in battery cells, which can be of special interest for bipolar battery architectures. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.

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.

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.

2022-1-11, Voigt, Oliver, Krause, Beate, Pötschke, Petra, Müller, Michael T., Wießner, Sven

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.

2021-3-15, Silva, Mariana M., Lopes, Paulo E., Li, Yilong, Pötschke, Petra, Ferreira, Fernando N., Paiva, Maria C.

Polylactic acid (PLA) is a bio-based, biodegradable polymer that presents high potential for biomedical and sensing applications. Ongoing works reported in the literature concern mainly applications based on 3D printing, while textile applications are hindered by the limited flexibility of PLA and its composite filaments. In the present work, PLA/multiwall carbon nanotube (MWCNT) composite filaments were produced with enhanced flexibility and electrical conductivity, which may be applied on a textile structure. A biodegradable plasticizer was incorporated in the nanocomposites, aiming at improving MWCNT dispersion and increasing the flexibility of the filaments. Filaments were produced with a range of compositions and their morphology was characterized as well as their thermal, thermomechanical, and electrical properties. Selected compositions were tested for sensing activity using saturated acetone vapor, demonstrating a suitable response and potential for the application in fabrics with sensing capacity.

2020-1-15, Biswas, Sourav, Muzata, Tanyaradzwa S., Krause, Beate, Rzeczkowski, Piotr, Pötschke, Petra, Bose, Suryasarathi

A suitable polymer matrix and well dispersed conducting fillers forming an electrically conducting network are the prime requisites for modern age electromagnetic shield designing. An effective polymer-based shield material is designed that can attenuate 99.9% of incident electromagnetic (EM) radiation at a minimum thickness of <0.5 mm. This is accomplished by the choice of a suitable partially crystalline polymer matrix while comparing non-polar polypropylene (PP) with polar polyvinylidene fluoride (PVDF) and a best suited filler nanomaterial by comparing different types of carbon nanotubes such as; branched, single-walled and multi-walled carbon nanotubes, which were added in only 2 wt %. Different types of interactions (polar-polar and CH-π and donor-acceptor) make b-MWCNT more dispersible in the PVDF matrix, which together with high crystallinity resulted in the best electrical conductivity and electromagnetic shielding ability of this composite. This investigation additionally conceals the issues related to the thickness of the shield material just by stacking individual thin nanocomposite layers containing different carbon nanotube (CNT) types with 0.3 mm thickness in a simple manner and finally achieves 99.999% shielding efficiency at just 0.9 mm thickness when using a suitable order of the different PVDF based nanocomposites.