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High-Quality Graphene Using Boudouard Reaction

2022, Grebenko, Artem K., Krasnikov, Dmitry V., Bubis, Anton V., Stolyarov, Vasily S., Vyalikh, Denis V., Makarova, Anna A., Fedorov, Alexander, Aitkulova, Aisuluu, Alekseeva, Alena A., Gilshtein, Evgeniia, Bedran, Zakhar, Shmakov, Alexander N., Alyabyeva, Liudmila, Mozhchil, Rais N., Ionov, Andrey M., Gorshunov, Boris P., Laasonen, Kari, Podzorov, Vitaly, Nasibulin, Albert G.

Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals. Unique features of the Boudouard reaction coupled with CO-driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene-catalyst composite production.

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Electronic Doping and Enhancement of n‐Channel Polycrystalline OFET Performance through Gate Oxide Modifications with Aminosilanes

2021, Shin, Nara, Schellhammer, Karl Sebastian, Lee, Min Ho, Zessin, Jakob, Hambsch, Mike, Salleo, Alberto, Ortmann, Frank, Mannsfeld, Stefan C.B.

Self-assembled monolayers (SAMs) are widely employed in organic field-effect transistors to modify the surface energy, surface roughness, film growth kinetics, and electrical surface potential of the gate oxide to control the device's operating voltage. In this study, amino-functionalized SAM molecules are compared to pure alkylsilane SAMS in terms of their impact on the electrical properties of organic field-effect transistors, using the n-type polycrystalline small molecule semiconductor material N,N′-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8). In order to understand the electronic impact of the amino groups, the effect of both the number of amino-containing functional groups and the SAM molecular length are systematically studied. Though amino-functionalized SAM materials have been studied previously, this study is, for the first time, able to shed light on the nature of the doping effect that occurs when the gate oxide is treated with polar aminosilane materials. By a comprehensive theoretical study of the interface on the molecular level, it is shown that the observed shift in the threshold voltage is caused by free charges, which are attracted to the PTCDI-C8 and are stabilized there by protonated aminosilanes. This attraction and the voltage shift can be systematically tuned by varying the length of the neutral terminal chain of the aminosilane. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH

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In situ detection of cracks during laser powder bed fusion using acoustic emission monitoring

2022, Seleznev, Mikhail, Gustmann, Tobias, Friebel, Judith Miriam, Peuker, Urs Alexander, Kühn, Uta, Hufenbach, Julia Kristin, Biermann, Horst, Weidner, Anja

Despite rapid development of laser powder bed fusion (L-PBF) and its monitoring techniques, there is still a lack of in situ crack detection methods, among which acoustic emission (AE) is one of the most sensitive. To elaborate on this topic, in situ AE monitoring was applied to L-PBF manufacturing of a high-strength Al92Mn6Ce2 (at. %) alloy and combined with subsequent X-ray computed tomography. By using a structure borne high-frequency sensor, even a simple threshold-based monitoring was able to detect AE activity associated with cracking, which occurred not only during L-PBF itself, but also after the build job was completed, i.e. in the cooling phase. AE data analysis revealed that crack-related signals can easily be separated from the background noise (e.g. inert gas circulation pump) through their specific shape of a waveform, as well as their energy, skewness and kurtosis. Thus, AE was verified to be a promising method for L-PBF monitoring, enabling to detect formation of cracks regardless of their spatial and temporal occurrence.

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Microstructural Characterization of a Laser Surface Remelted Cu-Based Shape Memory Alloy

2018-4-12, da Silva, Murillo Romero, Gargarella, Piter, Wolf, Witor, Gustmann, Tobias, Kiminami, Claudio Shyinti, Pauly, Simon, Eckert, Jürgen, Bolfarini, Claudemiro

Cu-based shape memory alloys (SMAs) present some advantages as higher transformation temperatures, lower costs and are easier to process than traditional Ti-based SMAs but they also show some disadvantages as low ductility and higher tendency for intergranular cracking. Several studies have sought for a way to improve the mechanical properties of these alloys and microstructural refinement has been frequently used. It can be obtained by laser remelting treatments. The aim of the present work was to investigate the influence of the laser surface remelting on the microstructure of a Cu-11.85Al-3.2Ni-3Mn (wt%) SMA. Plates were remelted using three different laser scanning speeds, i.e. 100, 300 and 500 mm/s. The remelted regions showed a T-shape morphology with a mean thickness of 52, 29 and 23 µm and an average grain size of 30, 29 and 23µm for plates remelted using scanning speed of 100, 300 and 500 mm/s, respectively. In the plates remelted with 100 and 300 mm/s some pores were found at the root of the keyhole due to the keyhole instability. We find that the instability of keyholes becomes more pronounced for lower scanning speeds. It was not observed any preferential orientation introduced by the laser treatment.

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Tailoring Intermolecular Interactions Towards High‐Performance Thermoelectric Ionogels at Low Humidity

2022, Zhao, Wei, Sun, Tingting, Zheng, Yiwei, Zhang, Qihao, Huang, Aibin, Wang, Lianjun, Jiang, Wan

Development of ionic thermoelectric (iTE) materials is of immense interest for efficient heat-to-electricity conversion due to their giant ionic Seebeck coefficient (Si), but challenges remain in terms of relatively small Si at low humidity, poor stretchability, and ambiguous interaction mechanism in ionogels. Herein, a novel ionogel is reported consisting of polyethylene oxide (PEO), polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), and 1-ethyl-3-methylimidazolium acetate (Emim:OAC). By delicately designing the interactions between ions and polymers, the migration of anions is restricted due to their strong binding with the hydroxyl groups of polymers, while the transport of cations is facilitated through segmental motions due to the increased amorphous regions, thereby leading to enlarged diffusion difference between the cations and anions. Moreover, the plasticizing effect of P123 and Emim:OAC can increase the elongation at break. As a consequence, the ionogel exhibits excellent properties including high Si (18 mV K−1 at relative humidity of 60%), good ionic conductivity (1.1 mS cm−1), superior stretchability (787%), and high stability (over 80% retention after 600 h). These findings show a promising strategy to obtain multifunctional iTE materials by engineering the intermolecular interactions and demonstrate the great potential of ionogels for harvesting low-grade heat in human-comfortable humidity environments.

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Self‐Patterning of Multifunctional Heusler Membranes by Dewetting

2021, Lünser, Klara, Diestel, Anett, Nielsch, Kornelius, Fähler, Sebastian

Ni-Mn-based Heusler alloys are an emerging class of materials which enable actuation by (magnetic) shape memory effects, magnetocaloric cooling, and thermomagnetic energy harvesting. Multifunctional materials have a particular advantage for miniaturization since their functionality is already built within the material. However, often complex microtechnological processing is required to bring these materials into shape. Here, self-organized formation of single crystalline membranes having arrays of rectangular holes with high aspect ratio is demonstrated. Dewetting avoids the need for complicated processing and allows to prepare freestanding Ni–Mn–Ga–Co membranes. These membranes are martensitic and magnetic, and their functional properties are not disturbed by self-patterning. Feature sizes of these membranes can be tailored by film thickness and heat treatment, and the tendencies can be explained with dewetting. As an outlook, the advantages of these multifunctional membranes for magnetocaloric and thermomagnetic microsystems are sketched. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH

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Development and characterization of a metastable Al-Mn-Ce alloy produced by laser powder bed fusion

2021, Gabrysiak, Katharina, Gustmann, Tobias, Freudenberger, Jens, Neufeld, Kai, Giebeler, Lars, Leyens, Christoph, Kühn, Uta

Laser powder bed fusion (LPBF) can help to overcome two challenges occurring by casting of metastable Al alloys: (1) the high amount of casting defects and (2) the limited part size while maintaining rapid solidification of the whole cross-section. In this study, an Al92Mn6Ce2 alloy was processed crack-free without baseplate heating by LPBF. The high cooling rate during fabrication has a significant impact on the microstructure, which was characterized by SEM, TEM and XRD. The processing through LPBF causes a high amount and a strong refinement of the intermetallic Al20Mn2Ce precipitates. This leads, compared to suction-cast specimens, to a higher hardness (180 HV 5) and a higher tolerable compressive stress (>1200 MPa) associated with a pronounced plasticity without failure up to a strain of 40%. The extraordinary mechanical properties of additively manufactured Al92Mn6Ce2 can extend the possibilities of producing novel LPBF lightweight structures for potential applications under harsh conditions.

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Highly Symmetric and Extremely Compact Multiple Winding Microtubes by a Dry Rolling Mechanism

2020, Moradi, Somayeh, Naz, Ehsan Saei Ghareh, Li, Guodong, Bandari, Nooshin, Bandari, Vineeth Kumar, Zhu, Feng, Wendrock, Horst, Schmidt, Oliver G.

Rolled-up nanotechnology has received significant attention to self-assemble planar nanomembranes into 3D micro and nanotubular architectures. These tubular structures have been well recognized as novel building blocks in a variety of applications ranging from microelectronics and nanophotonics to microbatteries and microrobotics. However, fabrication of multiwinding microtubes with precise control over the winding interfaces, which is crucial for many complex applications, is not easy to achieve by existing materials and technologies. Here, a dry rolling approach is introduced to tackle this challenge and create tight windings in compact and highly symmetric cylindrical microstructures. This technique exploits hydrophobicity of fluorocarbon polymers and the thermal expansion mismatch of polymers and inorganic films upon thermal treatment. Quality parameters for rolled-up microtubes, against which different fabrication technologies can be benchmarked are defined. The technique offers to fabricate long freestanding multiwinding microtubes as well as hierarchical architectures incorporating rolled-up wrinkled nanomembranes. This work presents an important step forward toward the fabrication of more complex but well-controlled microtubes for advanced high-quality device architectures. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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Advances and Trends in Chemically Doped Graphene

2020, Ullah, Sami, Shi, Qitao, Zhou, Junhua, Yang, Xiaoqin, Ta, Huy Q., Hasan, Maria, Ahmad, Nasir Mahmood, Fu, Lei, Bachmatiuk, Alicja, Rümmeli, Mark H.

Chemically doped graphene materials are fascinating because these have different desirable attributes with possible synergy. The inert and gapless nature of graphene can be changed by adding a small number of heteroatoms to substitute carbon in the lattice. The doped material may display superior catalytic activities; durable, fast, and selective sensing; improved magnetic moments; photoresponses; and activity in chemical reactions. In the current review, recent advances are covered in chemically doped graphene. First, the different types of heteroatoms, their bonding configurations, and briefly their properties are discussed. This is followed by the description of various synthesis and analytical methods essential for assessing the characteristics of heterographene with specific focus on the selected graphene materials of different dopants (particularly, single dopants, including N, B, S, P, first three halogens, Ge, and Ga, and codopants, such as N/O), and more importantly, up-to-date applications enabled by the intentional doping. Finally, outlook and perspectives section review the existing challenges, future opportunities, and possible ways to improve the graphitic materials. The goal is to update and inspire the readers to establish novel doped graphene with valuable properties and for current and futuristic applications. © 2020 The Authors. Published by Wiley-VCH GmbH

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Beyond Janus Geometry: Characterization of Flow Fields around Nonspherical Photocatalytic Microswimmers

2022, Heckel, Sandra, Bilsing, Clemens, Wittmann, Martin, Gemming, Thomas, Büttner, Lars, Czarske, Jürgen, Simmchen, Juliane

Catalytic microswimmers that move by a phoretic mechanism in response to a self-induced chemical gradient are often obtained by the design of spherical janus microparticles, which suffer from multi-step fabrication and low yields. Approaches that circumvent laborious multi-step fabrication include the exploitation of the possibility of nonuniform catalytic activity along the surface of irregular particle shapes, local excitation or intrinsic asymmetry. Unfortunately, the effects on the generation of motion remain poorly understood. In this work, single crystalline BiVO4 microswimmers are presented that rely on a strict inherent asymmetry of charge-carrier distribution under illumination. The origin of the asymmetrical flow pattern is elucidated because of the high spatial resolution of measured flow fields around pinned BiVO4 colloids. As a result the flow from oxidative to reductive particle sides is confirmed. Distribution of oxidation and reduction reactions suggests a dominant self-electrophoretic motion mechanism with a source quadrupole as the origin of the induced flows. It is shown that the symmetry of the flow fields is broken by self-shadowing of the particles and synthetic surface defects that impact the photocatalytic activity of the microswimmers. The results demonstrate the complexity of symmetry breaking in nonspherical microswimmers and emphasize the role of self-shadowing for photocatalytic microswimmers. The findings are leading the way toward understanding of propulsion mechanisms of phoretic colloids of various shapes.