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- ItemSegregated 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.
- ItemOrigami-Inspired Shape Memory Folding Microactuator(Basel : MDPI, 2020) Seigner, Lena; Bezsmertna, Olha; Fähler, Sebastian; Tshikwand, Georgino; Wendler, Frank; Kohl, ManfredThis paper presents the design, fabrication and performance of origami-based folding microactuators based on a cold-rolled NiTi foil of 20 µm thickness showing the one-way shape memory effect. Origami refers to a variety of techniques of transforming planar sheets into three-dimensional (3D) structures by folding, which has been introduced in science and engineering for, e.g., assembly and robotics. Here, NiTi microactuators are interconnected to rigid sections (tiles) forming an initial planar system that self-folds into a set of predetermined 3D shapes upon heating. While this concept has been demonstrated at the macro scale, we intend to transfer this concept into microtechnology by combining state-of-the art methods of micromachining. NiTi foils are micromachined by laser cutting or photolithography to achieve double-beam structures allowing for direct Joule heating with an electrical current. A thermo-mechanical treatment is used for shape setting of as-received specimens to reach a maximum folding angle of 180°. The bending moments, bending radii and load-dependent folding angles upon Joule heating are evaluated. The shape setting process is particularly effective for small bending radii, which, however generates residual plastic strain. After shape setting, unloaded beam structures show recoverable bending deflection between 0° and 140° for a maximum heating power of 900 mW. By introducing additional loads to account for the effect of the tiles, the smooth folding characteristic evolves into a sharp transition, whereby full deflection up to 180° is reached. The achieved results are an important step towards the development of cooperative multistable microactuator systems for 3D self-assembly.
- ItemA Rotating Spiral Micromotor for Noninvasive Zygote Transfer(Hoboke, NJ : Wiley, 2020) Schwarz, Lukas; Karnaushenko, Dmitriy D.; Hebenstreit, Franziska; Naumann, Ronald; Schmidt, Oliver G.; Medina-Sánchez, MarianaEmbryo transfer (ET) is a decisive step in the in vitro fertilization process. In most cases, the embryo is transferred to the uterus after several days of in vitro culture. Although studies have identified the beneficial effects of ET on proper embryo development in the earlier stages, this strategy is compromised by the necessity to transfer early embryos (zygotes) back to the fallopian tube instead of the uterus, which requires a more invasive, laparoscopic procedure, termed zygote intrafallopian transfer (ZIFT). Magnetic micromotors offer the possibility to mitigate such surgical interventions, as they have the potential to transport and deliver cellular cargo such as zygotes through the uterus and fallopian tube noninvasively, actuated by an externally applied rotating magnetic field. This study presents the capture, transport, and release of bovine and murine zygotes using two types of magnetic micropropellers, helix and spiral. Although helices represent an established micromotor architecture, spirals surpass them in terms of motion performance and with their ability to reliably capture and secure the cargo during both motion and transfer between different environments. Herein, this is demonstrated with murine oocytes/zygotes as the cargo; this is the first step toward the application of noninvasive, magnetic micromotor‐assisted ZIFT.
- ItemQuinoidal Azaacenes: 99 % Diradical Character(Weinheim : Wiley-VCH Verlag, 2020) Intorp, S.N.; Hodecker, M.; Müller, M.; Tverskoy, O.; Rosenkranz, M.; Dmitrieva, E.; Popov, A.A.; Rominger, F.; Freudenberg, J.; Dreuw, A.; Bunz, U.H.F.Quinoidal azaacenes with almost pure diradical character (y=0.95 to y=0.99) were synthesized. All compounds exhibit paramagnetic behavior investigated by EPR and NMR spectroscopy, and SQUID measurements, revealing thermally populated triplet states with an extremely low-energy gap ΔEST′ of 0.58 to 1.0 kcal mol−1. The species are persistent in solution (half-life≈14–21 h) and in the solid state they are stable for weeks.
- ItemMagnetic Micromotors for Multiple Motile Sperm Cells Capture, Transport, and Enzymatic Release(Weinheim : Wiley-VCH Verlag, 2020) Xu, H.; Medina-Sánchez, M.; Schmidt, O.G.An integrated system combining a magnetically-driven micromotor and a synthetized protein-based hyaluronic acid (HA) microflake is presented for the in situ selection and transport of multiple motile sperm cells (ca. 50). The system appeals for targeted sperm delivery in the reproductive system to assist fertilization or to deliver drugs. The binding mechanism between the HA microflake and sperm relies on the interactions between HA and the corresponding sperm HA receptors. Once sperm are captured within the HA microflake, the assembly is trapped and transported by a magnetically-driven helical microcarrier. The trapping of the sperm-microflake occurs by a local vortex induced by the microcarrier during rotation-translation under a rotating magnetic field. After transport, the microflake is enzymatically hydrolyzed by local proteases, allowing sperm to escape and finally reach the target location. This cargo-delivery system represents a new concept to transport not only multiple motile sperm but also other actively moving biological cargoes.
- ItemRare-earth-free MnAl-C-Ni permanent magnets produced by extrusion of powder milled from bulk(Amsterdam : Elsevier, 2020) Feng, Le; Freudenberger, Jens; Mix, Torsten; Nielsch, Kornelius; Woodcock, Thomas GeorgeRare-earth-free MnAl-C-Ni permanent magnets have been produced for the first time by extruding powders milled from bulk. The resulting materials, fabricated using different conditions, contained a large volume fraction (> 0.92) of the desired τ-phase. In terms of the maximum energy product, the best performance obtained for a whole, transverse section of the extruded material was (BH)max = 46 kJm−3, and was (BH)max = 49 kJm−3 for a sample taken from near the edge of this section. Analysis showed that this material was comparable to the long-established benchmark, comprising MnAl-C-based magnets extruded in industry from bulk or from gas-atomised powder. Such materials are no longer available. The microstructure of the materials produced here consisted of fine, recrystallised grains, which exhibited an <001> fibre texture with intermediate texture quality and of larger, non-recrystallised regions, which contained hierarchical twinning and a high density of defects. The volume fraction and size of the non-recrystallised regions was greatly reduced by decreasing the size of the initial powder particles. This led to a large increase in the squareness factor of the demagnetisation curve and consequently to the high (BH)max values observed.
- ItemStamping Fabrication of Flexible Planar Micro‐Supercapacitors Using Porous Graphene Inks(Hoboken : Wiley, 2020) Li, Fei; Qu, Jiang; Li, Yang; Wang, Jinhui; Zhu, Minshen; Liu, Lixiang; Ge, Jin; Duan, Shengkai; Li, Tianming; Bandari, Vineeth Kumar; Huang, Ming; Zhu, Feng; Schmidt, Oliver G.High performance, flexibility, safety, and robust integration for micro‐supercapacitors (MSCs) are of immense interest for the urgent demand for miniaturized, smart energy‐storage devices. However, repetitive photolithography processes in the fabrication of on‐chip electronic components including various photoresists, masks, and toxic etchants are often not well‐suited for industrial production. Here, a cost‐effective stamping strategy is developed for scalable and rapid preparation of graphene‐based planar MSCs. Combining stamps with desired shapes and highly conductive graphene inks, flexible MSCs with controlled structures are prepared on arbitrary substrates without any metal current collectors, additives, and polymer binders. The interdigitated MSC exhibits high areal capacitance up to 21.7 mF cm−2 at a current of 0.5 mA and a high power density of 6 mW cm−2 at an energy density of 5 µWh cm−2. Moreover, the MSCs show outstanding cycling performance and remarkable flexibility over 10 000 charge–discharge cycles and 300 bending cycles. In addition, the capacitance and output voltage of the MSCs are easily adjustable through interconnection with well‐defined arrangements. The efficient, rapid manufacturing of the graphene‐based interdigital MSCs with outstanding flexibility, shape diversity, and high areal capacitance shows great potential in wearable and portable electronics.
- ItemSelective Out‐of‐Plane Optical Coupling between Vertical and Planar Microrings in a 3D Configuration(Hoboken, NJ : Wiley, 2020) Valligatla, Sreeramulu; Wang, Jiawei; Madani, Abbas; Naz, Ehsan Saei Ghareh; Hao, Qi; Saggau, Christian Niclaas; Yin, Yin; Ma, Libo; Schmidt, Oliver G.3D photonic integrated circuits are expected to play a key role in future optoelectronics with efficient signal transfer between photonic layers. Here, the optical coupling of tubular microcavities, supporting resonances in a vertical plane, with planar microrings, accommodating in‐plane resonances, is explored. In such a 3D coupled composite system with largely mismatched cavity sizes, periodic mode splitting and resonant mode shifts are observed due to mode‐selective interactions. The axial direction of the microtube cavity provides additional design freedom for selective mode coupling, which is achieved by carefully adjusting the axial displacement between the microtube and the microring. The spectral anticrossing behavior is caused by strong coupling in this composite optical system and is excellently reproduced by numerical modeling. Interfacing tubular microcavities with planar microrings is a promising approach toward interlayer light transfer with added optical functionality in 3D photonic systems.
- ItemTunable Circular Dichroism by Photoluminescent Moiré Gratings(Weinheim : Wiley-VCH, 2020) Aftenieva, Olha; Schnepf, Max; Mehlhorn, Börge; König, Tobias A.F.In nanophotonics, there is a current demand for ultrathin, flexible nanostructures that are simultaneously easily tunable, demonstrate a high contrast, and have a strong response in photoluminescent polarization. In this work, the template-assisted self-assembly of water-dispersed colloidal core–shell quantum dots into 1D light-emitting sub-micrometer gratings on a flexible substrate is demonstrated. Combining such structures with a light-absorbing metallic counterpart by simple stacking at various angles results in a tunable Moiré pattern with strong lateral contrast. Furthermore, a combination with an identical emitter-based grating leads to a chiroptical effect with a remarkably high degree of polarization of 0.72. Such a structure demonstrates direct circular polarized photoluminescence, for the first time, without a need for an additional chiral template as an intermediary. The suggested approach allows for reproducible, large-area manufacturing at reasonable costs and is of potential use for chiroptical sensors, photonic circuit applications, or preventing counterfeit. © 2020 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH
- Item2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film(Washington, DC : ACS Publications, 2020) Molodtsova, Olga V.; Aristova, Irina M.; Potorochin, Dmitrii V.; Babenkov, Sergey V.; Khodos, Igor I.; Molodtsov, Serguei L.; Makarova, Anna A.; Smirnov, Dmitry A.; Aristov, Victor Yu.We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF4). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF4 at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis. Copyright © 2020 American Chemical Society.