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    Segregated Network Polymer Composites with High Electrical Conductivity and Well Mechanical Properties based on PVC, P(VDFTFE), UHMWPE, and rGO
    (Washington, DC : ACS Publications, 2020) Shiyanova, Kseniya A.; Gudkov, Maksim V.; Gorenberg, Arkady Ya; Rabchinskii, Maxim K.; Smirnov, Dmitry A.; Shapetina, Maria A.; Gurinovich, Tatiana D.; Goncharuk, Galina P.; Kirilenko, Demid A.; Bazhenov, Sergey L.; Melnikov, Valery P.
    The formation of a segregated network structure (wittingly uneven distribution of a filler) is one of the most promising strategies for the fabrication of electrically conductive polymer composites at present. However, the simultaneous achievement of high values of electrical conductivity with the retention of well mechanical properties within this approach remains a great challenge. Here, by means of X-ray photoelectron spectra (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectra, scanning electron microscopy (SEM), dielectric spectroscopy, and compression engineering stress-strain curve analysis, we have studied the effect of a segregated network structure on the electrical conductivity and mechanical properties of a set of polymer composites. The composites were prepared by applying graphene oxide (GO) with ultralarge basal plane size (up to 150 μm) onto the surface of polymer powder particles, namely, poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-tetrafluoroethylene) (P(VDF-TFE)), and ultrahigh-molecular-weight poly(ethylene) (UHMWPE) with the subsequent GO reduction and composite hot pressing. A strong dependence of the segregated network polymer composites' physical properties on the polymer matrix was demonstrated. Particularly, 12 orders of magnitude rise of the polymers' electrical conductivity up to 0.7 S/m was found upon the incorporation of the reduced GO (rGO). A 17% increase in the P(VDF-TFE) elastic modulus filled by 1 wt % of rGO was observed. Fracture strength of PVC/rGO at 0.5 wt % content of the filler was demonstrated to decrease by fourfold. At the same time, the change in strength was not significant for P(VDF-TFE) and UHMWPE composites in comparison with pure polymers. Our results show a promise to accelerate the development of new composites for energy applications, such as metal-free supercapacitor plates and current collectors of lithium-ion batteries, bipolar plates of proton-exchange membrane fuel cells, antistatic elements of various electronic devices, etc. © 2020 American Chemical Society.
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    Ultrathin two-dimensional conjugated metal– organic framework single-crystalline nanosheets enabled by surfactant-assisted synthesis
    (Cambridge : RSC, 2020) Wang, Zhonghao; Wang, Gang; Qi, Haoyuan; Wang, Mao; Wang, Mingchao; Park, SangWook; Wang, Huaping; Yu, Minghao; Kaiser, Ute; Fery, Andreas; Zhou, Shengqiang; Dong, Renhao; Feng, Xinliang
    Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have recently emerged for potential applications in (opto-)electronics, chemiresistive sensing, and energy storage and conversion, due to their excellent electrical conductivity, abundant active sites, and intrinsic porous structures. However, developing ultrathin 2D c-MOF nanosheets (NSs) for facile solution processing and integration into devices remains a great challenge, mostly due to unscalable synthesis, low yield, limited lateral size and low crystallinity. Here, we report a surfactant-assisted solution synthesis toward ultrathin 2D c-MOF NSs, including HHB-Cu (HHB = hexahydroxybenzene), HHB-Ni and HHTP-Cu (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). For the first time, we achieve single-crystalline HHB-Cu(Ni) NSs featured with a thickness of 4-5 nm (∼8-10 layers) and a lateral size of 0.25-0.65 μm2, as well as single-crystalline HHTP-Cu NSs with a thickness of ∼5.1 ± 2.6 nm (∼10 layers) and a lateral size of 0.002-0.02 μm2. Benefiting from the ultrathin feature, the synthetic NSs allow fast ion diffusion and high utilization of active sites. As a proof of concept, when serving as a cathode material for Li-ion storage, HHB-Cu NSs deliver a remarkable rate capability (charge within 3 min) and long-term cycling stability (90% capacity retention after 1000 cycles), superior to the corresponding bulk materials and other reported MOF cathodes. This journal is © The Royal Society of Chemistry.
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    Towards uniform electrochemical porosification of bulk HVPE-grown GaN
    (Pennington, NJ : Electrochemical Society Inc., 2019) Monaico, E.; Moise, C.; Mihai, G.; Ursaki, V.V.; Leistner, K.; Tiginyanu, I.M.; Enachescu, M.; Nielsch, K.
    In this paper, we report on results of a systematic study of porous morphologies obtained using anodization of HVPE-grown crystalline GaN wafers in HNO3, HCl, and NaCl solutions. The anodization-induced nanostructuring is found to proceed in different ways on N-and Ga-faces of polar GaN substrates. Complex pyramidal structures are disclosed and shown to be composed of regions with the degree of porosity modulated along the pyramid surface. Depending on the electrolyte and applied anodization voltage, formation of arrays of pores or nanowires has been evidenced near the N-face of the wafer. By adjusting the anodization voltage, we demonstrate that both current-line oriented pores and crystallographic pores are generated. In contrast to this, porosification of the Ga-face proceeds from some imperfections on the surface and develops in depth up to 50 μm, producing porous matrices with pores oriented perpendicularly to the wafer surface, the thickness of the pore walls being controlled by the applied voltage. The observed peculiarities are explained by different values of the electrical conductivity of the material near the two wafer surfaces.
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    A review of electrical and thermal conductivities of epoxy resin systems reinforced with carbon nanotubes and graphene-based nanoparticles
    (Amsterdam [u.a.] : Elsevier Science, 2022) Mousavi, Seyed Rasoul; Estaji, Sara; Kiaei, Hediyeh; Mansourian-Tabaei, Mohammad; Nouranian, Sasan; Jafari, Seyed Hassan; Ruckdäschel, Holger; Arjmand, Mohammad; Khonakdar, Hossein Ali
    Epoxy (EP) resins exhibit desirable mechanical and thermal properties, low shrinkage during cuing, and high chemical resistance. Therefore, they are useful for various applications, such as coatings, adhesives, paints, etc. On the other hand, carbon nanotubes (CNT), graphene (Gr), and their derivatives have become reinforcements of choice for EP-based nanocomposites because of their extraordinary mechanical, thermal, and electrical properties. Herein, we provide an overview of the last decade's advances in research on improving the thermal and electrical conductivities of EP resin systems modified with CNT, Gr, their derivatives, and hybrids. We further report on the surface modification of these reinforcements as a means to improve the nanofiller dispersion in the EP resins, thereby enhancing the thermal and electrical conductivities of the resulting nanocomposites.
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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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    Optical, electrical and chemical properties of PEO:I2 complex composite films
    (Heidelberg [u.a.] : Springer, 2022) Telfah, Ahmad; Al-Bataineh, Qais M.; Tolstik, Elen; Ahmad, Ahmad A.; Alsaad, Ahmad M.; Ababneh, Riad; Tavares, Carlos J.; Hergenröder, Roland
    Synthesized PEO:I2 complex composite films with different I2 concentrations were deposited onto fused silica substrates using a dip-coating method. Incorporation of PEO films with I2 increases the electrical conductivity of the composite, reaching a maximum of 46 mS/cm for 7 wt% I2. The optical and optoelectronic properties of the complex composite films were studied using the transmittance and reflectance spectra in the UV-Vis region. The transmittance of PEO decreases with increasing I2 content. From this study, the optical bandgap energy decreases from 4.42 to 3.28 eV as I2 content increases from 0 to 7 wt%. In addition, the refractive index for PEO films are in the range of 1.66 and 2.00.1H NMR spectra of pure PEO film shows two major peaks at 3.224 ppm and 1.038 ppm, with different widths assigned to the mobile polymer chains in the amorphous phase, whereas the broad component is assigned to the more rigid molecules in the crystalline phase, respectively. By adding I2 to the PEO, both peaks (amorphous and crystal) are shifted to lower NMR frequencies indicating that I2 is acting as a Lewis acid, and PEO is acting as Lewis base. Hence, molecular iodine reacts favorably with PEO molecules through a charge transfer mechanism, and the formation of triiodide (I3-), the iodite (IO2-) anion, I 2· · · PEO and I2+···PEO complexes. PEO:I2 complex composite films are expected to be suitable for optical, electrical, and optoelectronic applications.
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    Systematic investigations of annealing and functionalization of carbon nanotube yarns
    (Basel : MDPI AG, 2020) Scholz, M.; Hayashi, Y.; Eckert, V.; Khavrus, V.; Leonhardt, A.; Büchner, B.; Mertig, M.; Hampel, S.
    Carbon nanotube yarns (CNY) are a novel carbonaceous material and have received a great deal of interest since the beginning of the 21st century. CNY are of particular interest due to their useful heat conducting, electrical conducting, and mechanical properties. The electrical conductivity of carbon nanotube yarns can also be influenced by functionalization and annealing. A systematical study of this post synthetic treatment will assist in understanding what factors influences the conductivity of these materials. In this investigation, it is shown that the electrical conductivity can be increased by a factor of 2 and 5.5 through functionalization with acids and high temperature annealing respectively. The scale of the enhancement is dependent on the reducing of intertube space in case of functionalization. For annealing, not only is the highly graphitic structure of the carbon nanotubes (CNT) important, but it is also shown to influence the residual amorphous carbon in the structure. The promising results of this study can help to utilize CNY as a replacement for common materials in the field of electrical wiring.
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    Elucidating the chemistry behind the reduction of graphene oxide using a green approach with polydopamine
    (Basel : MDPI, 2019) Silva, Cláudia; Simon, Frank; Friedel, Peter; Pötschke, Petra; Zimmerer, Cordelia
    A new approach using X-ray photoelectron spectroscopy (XPS) was employed to give insight into the reduction of graphene oxide (GO) using a green approach with polydopamine (PDA). In this approach, the number of carbon atoms bonded to OH and to nitrogen in PDA is considered and compared to the total intensity of the signal resulting from OH groups in polydopamine-reduced graphene oxide (PDA-GO) to show the reduction. For this purpose, GO and PDA-GO with different times of reduction were prepared and characterized by Raman Spectroscopy and XPS. The PDA layer was removed to prepare reduced graphene oxide (RGO) and the effect of all chemical treatments on the thermal and electrical properties of the materials was studied. The results show that the complete reduction of the OH groups in GO occurred after 180 min of reaction. It was also concluded that Raman spectroscopy is not well suited to determine if the reduction and restoration of the sp2 structure occurred. Moreover, a significant change in the thermal stability was not observed with the chemical treatments. Finally, the electrical powder conductivity decreased after reduction with PDA, increasing again after its removal. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.
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    Characterization of highly filled PP/graphite composites for adhesive joining in fuel cell applications
    (Basel : MDPI, 2019) Rzeczkowski, Piotr; Krause, Beate; Pötschke, Petra
    In order to evaluate the suitability of graphite composite materials for use as bipolar plates in fuel cells, polypropylene (PP) was melt compounded with expanded graphite as conductive filler to form composites with different filler contents of 10–80 wt %. Electrical resistivity, thermal conductivity, and mechanical properties were measured and evaluated as a function of filler content. The electrical and thermal conductivities increased with filler content. Tensile and flexural strengths decreased with the incorporation of expanded graphite in PP. With higher graphite contents, however, both strength values remained more or less unchanged and were below the values of pure PP. Young’s-modulus and flexural modulus increased almost linearly with increasing filler content. The results of the thermogravimetric analysis confirmed the actual filler content in the composite materials. In order to evaluate the wettability and suitability for adhesive joining of graphite composites, contact angle measurements were conducted and surface tensions of composite surfaces were calculated. The results showed a significant increase in the surface tension of graphite composites with increasing filler content. Furthermore, graphite composites were adhesively joined and the strength of the joints was evaluated in the lap-shear test. Increasing filler content in the substrate material resulted in higher tensile lap-shear strength. Additionally, the influence of surface treatment (plasma and chemical) on surface tension and tensile lap-shear strength was investigated. The surface treatment led to a significant improvement of both properties.
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    Effect of filler synergy and cast film extrusion parameters on extrudability and direction-dependent conductivity of PVDF/carbon nanotube/carbon black composites
    (Basel : MDPI, 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.