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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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    The Localization Behavior of Different CNTs in PC/SAN Blends Containing a Reactive Component
    (Basel : MDPI, 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.
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    Nanofiller dispersion, morphology, mechanical behavior, and electrical properties of nanostructured styrene-butadiene-based triblock copolymer/CNT composites
    (Basel : MDPI, 2019) Staudinger, Ulrike; Satapathy, Bhabani K.; Jehnichen, Dieter
    A nanostructured linear triblock copolymer based on styrene and butadiene with lamellar morphology is filled with multiwalled carbon nanotubes (MWCNTs) of up to 1 wt% by melt compounding. This study deals with the dispersability of the MWCNTs within the nanostructured matrix and its consequent impact on block copolymer (BCP) morphology, deformation behavior, and the electrical conductivity of composites. By adjusting the processing parameters during melt mixing, the dispersion of the MWCNTs within the BCP matrix are optimized. In this study, the morphology and glass transition temperatures (Tg) of the hard and soft phase are not significantly influenced by the incorporation of MWCNTs. However, processing-induced orientation effects of the BCP structure are reduced by the addition of MWCNT accompanied by a decrease in lamella size. The stress-strain behavior of the triblock copolymer/MWCNT composites indicate higher Young’s modulus and pronounced yield point while retaining high ductility (strain at break ~ 400%). At a MWCNT content of 1 wt%, the nanocomposites are electrically conductive, exhibiting a volume resistivity below 3 × 103 Ω·cm. Accordingly, the study offers approaches for the development of mechanically flexible functional materials while maintaining a remarkable structural property profile.
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    Bidirectional and Stretchable Piezoresistive Sensors Enabled by Multimaterial 3D Printing of Carbon Nanotube/Thermoplastic Polyurethane Nanocomposites
    (Basel : MDPI, 2018-12-21) Christ, Josef F.; Aliheidari, Nahal; Pötschke, Petra; Ameli, Amir
    Fabricating complex sensor platforms is still a challenge because conventional sensors are discrete, directional, and often not integrated within the system at the material level. Here, we report a facile method to fabricate bidirectional strain sensors through the integration of multiwalled carbon nanotubes (MWCNT) and multimaterial additive manufacturing. Thermoplastic polyurethane (TPU)/MWCNT filaments were first made using a two-step extrusion process. TPU as the platform and TPU/MWCNT as the conducting traces were then 3D printed in tandem using multimaterial fused filament fabrication to generate uniaxial and biaxial sensors with several conductive pattern designs. The sensors were subjected to a series of cyclic strain loads. The results revealed excellent piezoresistive responses with cyclic repeatability in both the axial and transverse directions and in response to strains as high as 50%. It was shown that the directional sensitivity could be tailored by the type of pattern design. A wearable glove, with built-in sensors, capable of measuring finger flexure was also successfully demonstrated where the sensors are an integral part of the system. These sensors have potential applications in wearable electronics, soft robotics, and prosthetics, where complex design, multi-directionality, embedding, and customizability are demanded.
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    Thermal conductivity and electrical resistivity of melt-mixed polypropylene composites containing mixtures of carbon-based fillers
    (Basel : MDPI, 2019) Krause, Beate; Rzeczkowski, Piotr; Pötschke, Petra
    Melt-mixed composites based on polypropylene (PP) with various carbon-based fillers were investigated with regard to their thermal conductivity and electrical resistivity. The composites were filled with up to three fillers by selecting combinations of graphite nanoplatelets (GNP), carbon fibers (CF), carbon nanotubes (CNT), carbon black (CB), and graphite (G) at a constant filler content of 7.5 vol%. The thermal conductivity of PP (0.26 W/(m·K)) improved most using graphite nanoplatelets, whereas electrical resistivity was the lowest when using multiwalled CNT. Synergistic effects could be observed for different filler combinations. The PP composite, which contains a mixture of GNP, CNT, and highly structured CB, simultaneously had high thermal conductivity (0.5 W/(m·K)) and the lowest electrical volume resistivity (4 Ohm·cm).
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    The influence of the blend ratio in PA6/PA66/MWCNT blend composites on the electrical and thermal properties
    (Basel : MDPI, 2019) Krause, Beate; Kroschwald, Lisa; Pötschke, Petra
    It is known that the percolation threshold of polyamide 6 (PA6)/multiwalled carbon nanotube (MWCNT) composites is higher than that of PA66/MWCNT composites under the same mixing conditions and melt viscosity. A series of blends of PA6 and PA66 containing 1 wt % MWCNTs have been prepared to investigate this phenomenon. At contents up to 20 wt % PA66, the blends were not electrically conductive. The electrical resistivity dropped to 109 Ohm∙cm for PA66/PA6 30/70 blends. The resistivity was 105 Ohm∙cm at higher PA66 contents. Differential scanning calorimetry was used to investigate the thermal behavior of blends. The glass transition temperature was almost constant for all blend compositions, indicating that the amorphous phases are miscible. The MWCNT addition influenced the crystallization of PA66 much more than the PA6 crystallization. A heterogeneous crystallization of the polyamide in PA66/PA6 blends took place, and the MWCNTs were mainly localized in the earlier crystallizing PA66 phase. Thus, the formation of the nanotube network and thus the electrical volume resistivity of the PA6/PA66 blends with 1 wt % MWCNTs is significantly influenced by the crystallization behavior. In PA66/PA6 blends up to 60 wt %, the more expensive PA66 can be replaced by the cheaper PA6 while retaining its electrical properties
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    Electrically Conductive Polyetheretherketone Nanocomposite Filaments: From Production to Fused Deposition Modeling
    (Basel : MDPI, 2018-8-18) Gonçalves, Jordana; Lima, Patrícia; Krause, Beate; Pötschke, Petra; Lafont, Ugo; Gomes, José R.; Abreu, Cristiano S.; Paiva, Maria C.; Covas, José A.
    The present work reports the production and characterization of polyetheretherketone (PEEK) nanocomposite filaments incorporating carbon nanotubes (CNT) and graphite nanoplates (GnP), electrically conductive and suitable for fused deposition modeling (FDM) processing. The nanocomposites were manufactured by melt mixing and those presenting electrical conductivity near 10 S/m were selected for the production of filaments for FDM. The extruded filaments were characterized for mechanical and thermal conductivity, polymer crystallinity, thermal relaxation, nanoparticle dispersion, thermoelectric effect, and coefficient of friction. They presented electrical conductivity in the range of 1.5 to 13.1 S/m, as well as good mechanical performance and higher thermal conductivity compared to PEEK. The addition of GnP improved the composites' melt processability, maintained the electrical conductivity at target level, and reduced the coefficient of friction by up to 60%. Finally, three-dimensional (3D) printed test specimens were produced, showing a Young's modulus and ultimate tensile strength comparable to those of the filaments, but a lower strain at break and electrical conductivity. This was attributed to the presence of large voids in the part, revealing the need for 3D printing parameter optimization. Finally, filament production was up-scaled to kilogram scale maintaining the properties of the research-scale filaments.
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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.
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    Carbon Nanotubes Hybrid Hydrogels for Environmental Remediation: Evaluation of Adsorption Efficiency under Electric Field
    (Basel : MDPI, 2021) Cirillo, Giuseppe; Curcio, Manuela; Madeo, Lorenzo Francesco; Iemma, Francesca; De Filpo, Giovanni; Hampel, Silke; Nicoletta, Fiore Pasquale
    The performance of Carbon Nanotubes hybrid hydrogels for environmental remediation was investigated using Methylene Blue (MB), Rhodamine B (RD), and Bengal Rose (BR) as model contaminating dyes. An acrylate hydrogel network with incorporated CNT was synthesized by photo-polymerization without any preliminary derivatization of CNT surface. Thermodynamics, isothermal and kinetic studies showed favorable sorption processes with the application of an external 12 V electric field found to be able to influence the amount of adsorbed dyes: stronger interactions with cationic MB molecules (qexp and q12exp of 19.72 and 33.45 mg g−1, respectively) and reduced affinity for anionic RD (qexp and q12exp of 28.93 and 13.06 mg g−1, respectively) and neutral BR (qexp and q12exp of 36.75 and 15.85 mg g−1, respectively) molecules were recorded. The influence of pH variation on dyes adsorption was finally highlighted by reusability studies, with the negligible variation of adsorption capacity after five repeated sorption cycles claiming for the suitability of the proposed systems as effective sorbent for wastewater treatment.
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    Blend Structure and n-Type Thermoelectric Performance of PA6/SAN and PA6/PMMA Blends Filled with Singlewalled Carbon Nanotubes
    (Basel : MDPI, 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.