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High-Performance, Lightweight, and Flexible Thermoplastic Polyurethane Nanocomposites with Zn2+-Substituted CoFe2O4 Nanoparticles and Reduced Graphene Oxide as Shielding Materials against Electromagnetic Pollution

2021-10-11, Anju, Yadav, Raghvendra Singh, Pötschke, Petra, Pionteck, Jürgen, Krause, Beate, Kuřitka, Ivo, Vilcakova, Jarmila, Skoda, David, Urbánek, Pavel, Machovsky, Michal, Masař, Milan, Urbánek, Michal, Jurca, Marek, Kalina, Lukas, Havlica, Jaromir

The development of flexible, lightweight, and thin high-performance electromagnetic interference shielding materials is urgently needed for the protection of humans, the environment, and electronic devices against electromagnetic radiation. To achieve this, the spinel ferrite nanoparticles CoFe2O4 (CZ1), Co0.67Zn0.33Fe2O4 (CZ2), and Co0.33Zn0.67Fe2O4 (CZ3) were prepared by the sonochemical synthesis method. Further, these prepared spinel ferrite nanoparticles and reduced graphene oxide (rGO) were embedded in a thermoplastic polyurethane (TPU) matrix. The maximum electromagnetic interference (EMI) total shielding effectiveness (SET) values in the frequency range 8.2-12.4 GHz of these nanocomposites with a thickness of only 0.8 mm were 48.3, 61.8, and 67.8 dB for CZ1-rGO-TPU, CZ2-rGO-TPU, and CZ3-rGO-TPU, respectively. The high-performance electromagnetic interference shielding characteristics of the CZ3-rGO-TPU nanocomposite stem from dipole and interfacial polarization, conduction loss, multiple scattering, eddy current effect, natural resonance, high attenuation constant, and impedance matching. The optimized CZ3-rGO-TPU nanocomposite can be a potential candidate as a lightweight, flexible, thin, and high-performance electromagnetic interference shielding material.

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Thermoelectric Performance of Polypropylene/Carbon Nanotube/Ionic Liquid Composites and Its Dependence on Electron Beam Irradiation

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.

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Thermoelectric Properties of N-Type Poly (Ether Ether Ketone)/Carbon Nanofiber Melt-Processed Composites

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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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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Nonlinear Thermopower Behaviour of N-Type Carbon Nanofibres and Their Melt Mixed Polypropylene 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).

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CuxCo1-xFe2O4 (x = 0.33, 0.67, 1) Spinel Ferrite Nanoparticles Based Thermoplastic Polyurethane Nanocomposites with Reduced Graphene Oxide for Highly Efficient Electromagnetic Interference Shielding

2022-2-26, Anju, Yadav, Raghvendra Singh, Pötschke, Petra, Pionteck, Jürgen, Krause, Beate, Kuřitka, Ivo, Vilčáková, Jarmila, Škoda, David, Urbánek, Pavel, Machovský, Michal, Masař, Milan, Urbánek, Michal

CuxCo1-x Fe2O4 (x = 0.33,0.67,1)-reduced graphene oxide (rGO)-thermoplastic polyurethane (TPU) nanocomposites exhibiting highly efficient electromagnetic interference (EMI) shielding were prepared by a melt-mixing approach using a microcompounder. Spinel ferrite Cu0.33Co0.67Fe2O4 (Cu-CoF1), Cu0.67Co0.33Fe2O4 (CuCoF2) and CuFe2O4 (CuF3) nanoparticles were synthesized using the sonochemical method. The CuCoF1 and CuCoF2 exhibited typical ferromagnetic features, whereas CuF3 displayed superparamagnetic characteristics. The maximum value of EMI total shielding effectiveness (SEt) was noticed to be 42.9 dB, 46.2 dB, and 58.8 dB for CuCoF1-rGO-TPU, CuCoF2-rGO-TPU, and CuF3-rGO-TPU nanocomposites, respectively, at a thickness of 1 mm. The highly efficient EMI shielding performance was attributed to the good impedance matching, conductive, dielectric, and magnetic loss. The demonstrated nanocomposites are promising candidates for a lightweight, flexible, and highly efficient EMI shielding material.

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Polyethylene Glycol as Additive to Achieve N-Conductive Melt-Mixed Polymer/Carbon Nanotube Composites for Thermoelectric Application

2022, Krause, Beate, Pötschke, Petra

The development of thermoelectric (TE) materials based on thermoplastic polymers and carbon nanotubes is a focus of current TE research activities. For a TE module, both p- and n-conductive composites are required, whereby the production of n-conductive materials is a particular challenge. The present study investigates whether adding polyethylene glycol (PEG) as n-dopant during the melt-mixing of the conductive composites based on polycarbonate, poly(ether ether ketone), or poly(butylene terephthalate) with singlewalled carbon nanotubes (0.5 to 2 wt%) is a possible solution. It was shown that for all three polymer types, a change in the sign of the Seebeck coefficient from positive to negative could be achieved when at least 1.5 wt% PEG was added. The most negative Seebeck coefficients were determined to be −30.1 µV/K (PC), −44.1 µV/K (PEEK), and −14.5 µV/K (PBT). The maximal power factors ranged between 0.0078 µW/m·K2 (PC), 0.035 µW/m·K2 (PEEK), and 0.0051 µW/m·K2 (PBT).