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    Thermoelectric Performance of Polypropylene/Carbon Nanotube/Ionic Liquid Composites and Its Dependence on Electron Beam Irradiation
    (Basel : MDPI, 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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    Does the Type of Polymer and Carbon Nanotube Structure Control the Electromagnetic Shielding in Melt-Mixed Polymer Nanocomposites?
    (Basel : MDPI, 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.
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    Screening of Different Carbon Nanotubes in Melt-Mixed Polymer Composites with Different Polymer Matrices for Their Thermoelectrical Properties
    (Basel : MDPI, 2019-12-7) Krause, Beate; Barbier, Carine; Levente, Juhasz; Klaus, Maxim; Pötschke, Petra
    The aim of this study is to reveal the influences of carbon nanotube (CNT) and polymer type as well as CNT content on electrical conductivity, Seebeck coefficient (S), and the resulting power factor (PF) and figure of merit (ZT). Different commercially available and laboratory made CNTs were used to prepare melt-mixed composites on a small scale. CNTs typically lead to p-type composites with positive S-values. This was found for the two types of multi-walled CNTs (MWCNT) whereby higher Seebeck coefficient in the corresponding buckypapers resulted in higher values also in the composites. Nitrogen doped MWCNTs resulted in negative S-values in the buckypapers as well as in the polymer composites. When using single-walled CNTs (SWCNTs) with a positive S-value in the buckypapers, positive (polypropylene (PP), polycarbonate (PC), poly (vinylidene fluoride) (PVDF), and poly(butylene terephthalate) (PBT)) or negative (polyamide 66 (PA66), polyamide 6 (PA6), partially aromatic polyamide (PARA), acrylonitrile butadiene styrene (ABS)) S-values were obtained depending on the matrix polymer and SWCNT type. The study shows that the direct production of n-type melt-mixed polymer composites from p-type commercial SWCNTs with relatively high Seebeck coefficients is possible. The highest Seebeck coefficients obtained in this study were 66.4 µV/K (PBT/7 wt % SWCNT Tuball) and −57.1 µV/K (ABS/0.5 wt % SWCNT Tuball) for p-and n-type composites, respectively. The highest power factor and ZT of 0.28 µW/m·K2 and 3.1 × 10−4, respectively, were achieved in PBT with 4 wt % SWCNT Tuball.
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    Remarkable Mechanochromism in Blends of a π-Conjugated Polymer P3TEOT: The Role of Conformational Transitions and Aggregation
    (Weinheim : Wiley-VCH, 2020) Zessin, Johanna; Schnepf, Max; Oertel, Ulrich; Beryozkina, Tetyana; König, Tobias A.F.; Fery, Andreas; Mertig, Michael; Kiriy, Anton
    A novel mechanism for well-pronounced mechanochromism in blends of a π-conjugated polymer based on reversible conformational transitions of a chromophore rather than caused by its aggregation state, is exemplified. Particularly, a strong stretching-induced bathochromic shift of the light absorption, or hypsochromic shift of the emission, is found in blends of the water-soluble poly(3-tri(ethylene glycol)) (P3TEOT) embedded into the matrix of thermoplastic polyvinyl alcohol. This counterintuitive phenomenon is explained in terms of the concentration dependency of the P3TEOT's aggregation state, which in turn results in different molecular conformations and optical properties. A molecular flexibility, provided by low glass transition temperature of P3TEOT, and the fact that P3TEOT adopts an intermediate, moderately planar conformation in the solid state, are responsible for the unusual complex mechanochromic behavior. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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    Lasing by Template-Assisted Self-Assembled Quantum Dots
    (Weinheim : Wiley-VCH, 2023) Aftenieva, Olha; Sudzius, Markas; Prudnikau, Anatol; Adnan, Mohammad; Sarkar, Swagato; Lesnyak, Vladimir; Leo, Karl; Fery, Andreas; König, Tobias A.F.
    Miniaturized laser sources with low threshold power are required for integrated photonic devices. Photostable core/shell nanocrystals are well suited as gain material and their laser properties can be exploited by direct patterning as distributed feedback (DFB) lasers. Here, the 2nd-order DFB resonators tuned to the photoluminescence wavelength of the QDs are used. Soft lithography based on template-assisted colloidal self-assembly enables pattern resolution in the subwavelength range. Combined with the directional Langmuir–Blodgett arrangement, control of the waveguide layer thickness is further achieved. It is shown that a lasing threshold of 5.5 mJ cm−2 is reached by a direct printing method, which can be further reduced by a factor of ten (0.6 mJ cm−2) at an optimal waveguide thickness. Moreover, it is discussed how one can adjust the DFB geometries to any working wavelength. This colloidal approach offers prospects for applications in bioimaging, biomedical sensing, anti-counterfeiting, or displays.
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    Colloidal Self-Assembly Concepts for Plasmonic Metasurfaces
    (Weinheim : Wiley-VCH, 2019) Mayer, Martin; Schnepf, Max J.; König, Tobias A.F.; Fery, Andreas
    Metallic nanostructures exhibit strong interactions with electromagnetic radiation, known as the localized surface plasmon resonance. In recent years, there is significant interest and growth in the area of coupled metallic nanostructures. In such assemblies, short- and long-range coupling effects can be tailored and emergent properties, e.g., metamaterial effects, can be realized. The term “plasmonic metasurfaces” is used for this novel class of assemblies deposited on planar surfaces. Herein, the focus is on plasmonic metasurfaces formed from colloidal particles. These are formed by self-assembly and can meet the demands of low-cost manufacturing of large-area, flexible, and ultrathin devices. The advances in high optical quality of the colloidal building blocks and methods for controlling their self-assembly on surfaces will lead to novel functional devices for dynamic light modulators, pulse sharpening, subwavelength imaging, sensing, and quantum devices. This progress report focuses on predicting optical properties of single colloidal building blocks and their assemblies, wet-chemical synthesis, and directed self-assembly of colloidal particles. The report concludes with a discussion of the perspectives toward expanding the colloidal plasmonic metasurfaces concept by integrating them with quantum emitters (gain materials) or mechanically responsive structures. © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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    Plasmonic Properties of Colloidal Assemblies
    (Weinheim : Wiley-VCH, 2021) Rossner, Christian; König, Tobias A.F.; Fery, Andreas
    The assembly of metal nanoparticles into supracolloidal structures unlocks optical features, which can go beyond synergistic combinations of the properties of their primary building units. This is due to inter-particle plasmonic coupling effects, which give rise to emergent properties. The motivation for this progress report is twofold: First, it is described how simulation approaches can be used to predict and understand the optical properties of supracolloidal metal clusters. These simulations may form the basis for the rational design of plasmonic assembly architectures, based on the desired functional cluster properties, and they may also spark novel material designs. Second, selected scalable state-of-the-art preparative strategies based on synthetic polymers to guide the supracolloidal assembly are discussed. These routes also allow for equipping the assembly structures with adaptive properties, which in turn enables (inter-)active control over the cluster optical properties. © 2021 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH
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    Exploiting Combinatorics to Investigate Plasmonic Properties in Heterogeneous Ag-Au Nanosphere Chain Assemblies
    (Weinheim : Wiley-VCH, 2021) Schletz, Daniel; Schultz, Johannes; Potapov, Pavel L.; Steiner, Anja Maria; Krehl, Jonas; König, Tobias A.F.; Mayer, Martin; Lubk, Axel; Fery, Andreas
    Chains of coupled metallic nanoparticles are of special interest for plasmonic applications because they can sustain highly dispersive plasmon bands, allowing strong ballistic plasmon wave transport. Whereas early studies focused on homogeneous particle chains exhibiting only one dominant band, heterogeneous assemblies consisting of different nanoparticle species came into the spotlight recently. Their increased configuration space principally allows engineering multiple bands, bandgaps, or topological states. Simultaneously, the challenge of the precise arrangement of nanoparticles, including their distances and geometric patterns, as well as the precise characterization of the plasmonics in these systems, persists. Here, the surface plasmon resonances in heterogeneous Ag-Au nanoparticle chains are reported. Wrinkled templates are used for directed self-assembly of monodisperse gold and silver nanospheres as chains, which allows assembling statistical combinations of more than 109 particles. To reveal the spatial and spectral distribution of the plasmonic response, state-of-the-art scanning transmission electron microscopy coupled with electron energy loss spectroscopy accompanied by boundary element simulations is used. A variety of modes in the heterogeneous chains are found, ranging from localized surface plasmon modes occurring in single gold or silver spheres, respectively, to modes that result from the hybridization of the single particles. This approach opens a novel avenue toward combinatorial studies of plasmonic properties in heterosystems. © 2021 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH
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    Increased pore size of scaffolds improves coating efficiency with sulfated hyaluronan and mineralization capacity of osteoblasts
    (London : Biomed Central, 2019) Krieghoff, Jan; Picke, Ann-Kristin; Salbach-Hirsch, Juliane; Rother, Sandra; Heinemann, Christiane; Bernhardt, Ricardo; Kascholke, Christian; Möller, Stephanie; Rauner, Martina; Schnabelrauch, Matthias; Hintze, Vera; Scharnweber, Dieter; Schulz-Siegmund, Michaela; Hacker, Michael C.; Hofbauer, Lorenz C.; Hofbauer, Christine
    Background: Delayed bone regeneration of fractures in osteoporosis patients or of critical-size bone defects after tumor resection are a major medical and socio-economic challenge. Therefore, the development of more effective and osteoinductive biomaterials is crucial. Methods: We examined the osteogenic potential of macroporous scaffolds with varying pore sizes after biofunctionalization with a collagen/high-sulfated hyaluronan (sHA3) coating in vitro. The three-dimensional scaffolds were made up from a biodegradable three-armed lactic acid-based macromer (TriLA) by cross-polymerization. Templating with solid lipid particles that melt during fabrication generates a continuous pore network. Human mesenchymal stem cells (hMSC) cultivated on the functionalized scaffolds in vitro were investigated for cell viability, production of alkaline phosphatase (ALP) and bone matrix formation. Statistical analysis was performed using student's t-test or two-way ANOVA. Results: We succeeded in generating scaffolds that feature a significantly higher average pore size and a broader distribution of individual pore sizes (HiPo) by modifying composition and relative amount of lipid particles, macromer concentration and temperature for cross-polymerization during scaffold fabrication. Overall porosity was retained, while the scaffolds showed a 25% decrease in compressive modulus compared to the initial TriLA scaffolds with a lower pore size (LoPo). These HiPo scaffolds were more readily coated as shown by higher amounts of immobilized collagen (+ 44%) and sHA3 (+ 25%) compared to LoPo scaffolds. In vitro, culture of hMSCs on collagen and/or sHA3-coated HiPo scaffolds demonstrated unaltered cell viability. Furthermore, the production of ALP, an early marker of osteogenesis (+ 3-fold), and formation of new bone matrix (+ 2.5-fold) was enhanced by the functionalization with sHA3 of both scaffold types. Nevertheless, effects were more pronounced on HiPo scaffolds about 112%. Conclusion: In summary, we showed that the improvement of scaffold pore sizes enhanced the coating efficiency with collagen and sHA3, which had a significant positive effect on bone formation markers, underlining the promise of using this material approach for in vivo studies. © 2019 The Author(s).
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    Comparison of nanotubes produced by fixed bed and aerosol-CVD methods and their electrical percolation behaviour in melt mixed polyamide 6.6 composites
    (Barking : Elsevier, 2010) Krause, Beate; Ritschel, M.; Täschner, C.; Oswald, S.; Gruner, W.; Leonhardt, A.; Pötschke, Petra
    The electrical percolation behaviour of five different kinds of carbon nanotubes (CNTs) synthesised by two CVD techniques was investigated on melt mixed composites based on an insulating polyamide 6.6 matrix. The electrical percolation behaviour was found to be strongly dependent on the properties of CNTs which varied with the synthesis conditions. The lowest electrical percolation threshold (0.04 wt.%) was determined for as grown multi-walled carbon nanotubes without any purification or chemical treatment. Such carbon nanotubes were synthesised by the aerosol method using acetonitrile as ferrocene containing solvent and show relatively low oxygen content near the surface, high aspect ratio, and good dispersability. Similar properties could be found for nanotubes produced by the aerosol method using cyclohexane, whereas CNTs produced by the fixed bed method using different iron contents in the catalyst material showed much higher electrical percolation thresholds between 0.35 and 1.02 wt.%. © 2009 Elsevier Ltd. All rights reserved.