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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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    Effect of Graphite Nanoplate Morphology on the Dispersion and Physical Properties of Polycarbonate Based Composites
    (Basel : MDPI, 2017-5-18) Müller, Michael Thomas; Hilarius, Konrad; Liebscher, Marco; Lellinger, Dirk; Alig, Ingo; Pötschke, Petra
    The influence of the morphology of industrial graphite nanoplate (GNP) materials on their dispersion in polycarbonate (PC) is studied. Three GNP morphology types were identified, namely lamellar, fragmented or compact structure. The dispersion evolution of all GNP types in PC is similar with varying melt temperature, screw speed, or mixing time during melt mixing. Increased shear stress reduces the size of GNP primary structures, whereby the GNP aspect ratio decreases. A significant GNP exfoliation to individual or few graphene layers could not be achieved under the selected melt mixing conditions. The resulting GNP macrodispersion depends on the individual GNP morphology, particle sizes and bulk density and is clearly reflected in the composite's electrical, thermal, mechanical, and gas barrier properties. Based on a comparison with carbon nanotubes (CNT) and carbon black (CB), CNT are recommended in regard to electrical conductivity, whereas, for thermal conductive or gas barrier application, GNP is preferred.
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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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    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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    Fe3O4 Nanoparticles Grown on Cellulose/GO Hydrogels as Advanced Catalytic Materials for the Heterogeneous Fenton-like Reaction
    (Washington, DC : ACS Publications, 2019) Chen, Yian; Pötschke, Petra; Pionteck, Jürgen; Voit, Brigitte; Qi, Haisong
    Cellulose/graphene oxide (GO)/iron oxide (Fe3O4) composites were prepared by coprecipitating iron salts onto cellulose/GO hydrogels in a basic solution. X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared, and X-ray diffraction characterization showed that Fe3O4 was successfully coated on GO sheets and cellulose. Cellulose/GO/Fe3O4 composites showed excellent catalytic activity by maintaining almost 98% of the removal of acid orange 7 (AO7) and showed stability over 20 consecutive cycles. This performance is attributable to the synergistic effect of Fe3O4 and GO during the heterogeneous Fenton-like reaction. Especially, the cellulose/GO/Fe3O4 composites preserve their activity by keeping the ratio of Fe3+/Fe2+ at 2 even after 20 catalysis cycles, which is supported by XPS analysis.
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    Melt-mixed thermoplastic composites containing carbon nanotubes for thermoelectric applications
    (Springfield, Mo. : AIMS Press, 2016) Luo, Jinji; Krause, Beate; Pötschke, Petra
    Flexible thermoelectric materials are prepared by melt mixing technique, which can be easily scaled up to industrial level. Hybrid filler systems of carbon nanotubes (CNTs) and copper oxide (CuO), which are environmental friendly materials and contain abundant earth elements, are melt mixed into a thermoplastic matrix, namely polypropylene (PP). With the CNT addition, an electrical network could be built up inside the insulating PP for effective charge transport. The effect of CuO addition is determined by the corresponding CNT concentration. At high CNT concentration, largely above the percolation threshold (φc, ca. 0.1 wt%), the change in the TE properties is small. In contrast, at CNT concentration close to φc, the co-addition of CuO could simultaneously increase the electrical conductivity and Seebeck coefficient. With 5 wt% CuO and 0.8 wt% CNTs where a loose percolated network is formed, the Seebeck coefficient was increased from 34.1 µV/K to 45 µV/K while the electrical conductivity was from 1.6 × 10−3 S/cm to 3.8 × 10−3 S/cm, leading to a power factor of 9.6 × 10−4 µW/mK2 (cf. 1.8 × 10−4 µW/mK2 for the composite with only 0.8 wt% CNTs).
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    Tuneable Dielectric Properties Derived from Nitrogen-Doped Carbon Nanotubes in PVDF-Based Nanocomposites
    (Washington, DC : ACS Publications, 2018) Pawar, Shital Patangrao; Arjmand, Mohammad; Pötschke, Petra; Krause, Beate; Fischer, Dieter; Bose, Suryasarathi; Sundararaj, Uttandaraman
    Nitrogen-doped multiwall carbon nanotubes (N-MWNTs) with different structures were synthesized by employing chemical vapor deposition and changing the argon/ethane/nitrogen gas precursor ratio and synthesis time, and broadband dielectric properties of their poly(vinylidene fluoride) (PVDF)-based nanocomposites were investigated. The structure, morphology, and electrical conductivity of synthesized N-MWNTs were assessed via Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy, and powder conductivity techniques. The melt compounded PVDF nanocomposites manifested significantly high real part of the permittivity (ϵ′) along with low dissipation factor (tan δϵ) in 0.1 kHz to 1 MHz frequency range, suggesting use as efficient charge-storage materials. Longer synthesis time resulted in enhanced carbon purity as well as higher thermal stability, determined via TGA analysis. The inherent electrical conductivity of N-MWNTs scaled with the carbon purity. The charge-storage ability of the developed PVDF nanocomposites was commensurate with the amount of the nitrogen heteroatom (i.e., self-polarization), carbon purity, and inherent electrical conductivity of N-MWNTs and increased with better dispersion of N-MWNTs in PVDF.
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    Dispersability and particle size distribution of CNTs in an aqueous surfactant dispersion as a function of ultrasonic treatment time
    (New York, NY [u.a.] : Pergamon Press, 2010) Krause, Beate; Mende, Mandy; Pötschke, Petra; Petzold, Gudrun
    The dispersability of carbon nanotubes (CNTs) was assessed by studying the sedimentation of CNTs dispersed in aqueous surfactant solutions at different ultrasonication treatment times using a LUMiSizer® apparatus under centrifugal forces. Different commercially available multiwalled CNTs, namely Baytubes® C150P, Nanocyl™ NC7000, Arkema Graphistrength® C100, and FutureCarbon CNT-MW showing quite different kinetics were compared. In addition, the particle size distributions were analyzed using dynamic light scattering and centrifugal separation analysis. The best dispersabilities were found for Nanocyl™ NC7000 and FutureCarbon CNT-MW; to prepare stable dispersions of Baytubes® C150P or Graphistrength® C100 five times the energy was needed. As a result of the centrifugal separation analysis, it was concluded that Nanocyl™ NC7000 and Baytubes® C150P were dispersed as single nanotubes using ultrasonic treatment whereas small agglomerates or bundles are existing in dispersions containing FutureCarbon CNT-MW and Graphistrength® C100. © 2010 Elsevier Ltd. All rights reserved.
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    Graphene Derivatives Doped with Nickel Ferrite Nanoparticles as Excellent Microwave Absorbers in Soft Nanocomposites
    (Weinheim : Wiley-VCH, 2017) Pawar, Shital Patangrao; Gandi, Mounika; Arief, Injamamul; Krause, Beate; Pötschke, Petra; Bose, Suryasarathi
    Herein, we report the development of soft polymeric composites containing multiwall carbon nanotubes (MWNTs, 1–3 wt%) and graphene derivatives doped with nickel ferrite nanoparticles (rGO@NF, 10 wt%) as lightweight microwave absorbers. The soft nanocomposites were designed using melt-mixed blends of varying compositions of PC (polycarbonate) and SAN (poly styrene acrylonitrile) by compartmentalized functional nanoparticles in one of the components of the blend (here PC). Maximum attenuation of the incoming electromagnetic (EM) radiation mainly through absorption was achieved. The hetero-dielectric media at microscopic length scale in the PC component provided large interfaces which facilitated multiple scattering thereby attenuating the incoming EM radiation. This strategy of positioning the functional nanoparticles in one of the components in the blends resulted in significantly enhanced shielding effectiveness (SE), at any given concentration of MWNTs, in contrast to PC based composites. This enhancement in SE was realized in the special morphology of the bicomponent PC/SAN=60/40 wt% blends where both the components are continuous. The enhanced SE in co-continuous blends is due to combined effect of enhanced electrical conductivity (more precisely due to interconnected network of the nanoparticles) and the presence of a hetero-dielectric media generating large scattering interfaces. For instance, the PC/SAN (60/40 wt%) co-continuous blend containing 3 wt% MWNTs and 10 wt% rGO@NF manifested in a total shielding effectiveness (SET) of −32.3 dB (i. e. more than 99.9 % attenuation of incoming EM radiation) mainly through absorption.
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    Effects of synthesis catalyst and temperature on broadband dielectric properties of nitrogen-doped carbon nanotube/polyvinylidene fluoride nanocomposites
    (New York, NY [u.a.] : Pergamon Press, 2016) Ameli, A.; Arjmand, M.; Pötschke, Petra; Krause, Beate; Sundararaj, U.
    This study reports on nitrogen-doped carbon nanotube (N-CNT)/polymer nanocomposites exhibiting relatively high and frequency independent real permittivity (ϵ′) together with low dielectric loss (tan δ). N-CNTs were synthesized by chemical vapor deposition, and their nanocomposites were prepared by melt-mixing with polyvinylidene fluoride (PVDF). In the synthesis of N-CNTs, three catalysts of Co, Fe and Ni, and three temperatures of 650, 750 and 950 °C were employed. The morphology, aspect ratio, synthesis yield, remaining residue, nitrogen content, nitrogen bonding type, and powder conductivity of N-CNTs, and the morphology, polar crystalline phase, and broadband dielectric properties of N-CNT/PVDF nanocomposites were investigated. The results revealed that by proper selection of synthesis catalyst (Fe) and temperature (650 °C and 950 °C), nitrogen doping generated polarizable nanotubes via providing local polarization sites, and resulted in nanocomposites with favorable dielectric properties for charge storage applications at N-CNT loadings as low as 1.0 wt%. As a result, 3.5 wt% (N-CNT)Fe/950°C/PVDF nanocomposites exhibited an insulative behavior with ϵ' = 23.12 and tan δ = 0.05 at 1 kHz, a combination superior to that of PVDF, i.e., ϵ' = 8.4 and tan δ = 0.03 and to those of percolative nanocomposites, e.g., ϵ' = 71.20 and tan δ = 63.20 for 3.5 wt% (N-CNT)Fe/750°C/PVDF. Also, the relationships between the dielectric properties, N-CNT structure, and nanocomposite morphology were identified.