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    Current Advances in TiO2-Based Nanostructure Electrodes for High Performance Lithium Ion Batteries
    (Basel : MDPI, 2018-2-6) Madian, Mahmoud; Eychmüller, Alexander; Giebeler, Lars
    The lithium ion battery (LIB) has proven to be a very reliably used system to store electrical energy, for either mobile or stationary applications. Among others, TiO2-based anodes are the most attractive candidates for building safe and durable lithium ion batteries with high energy density. A variety of TiO2 nanostructures has been thoroughly investigated as anodes in LIBs, e.g., nanoparticles, nanorods, nanoneedles, nanowires, and nanotubes discussed either in their pure form or in composites. In this review, we present the recent developments and breakthroughs demonstrated to synthesize safe, high power, and low cost nanostructured titania-based anodes. The reader is provided with an in-depth review of well-oriented TiO2-based nanotubes fabricated by anodic oxidation. Other strategies for modification of TiO2-based anodes with other elements or materials are also highlighted in this report.
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    Auger- and X-ray Photoelectron Spectroscopy at Metallic Li Material: Chemical Shifts Related to Sample Preparation, Gas Atmosphere, and Ion and Electron Beam Effects
    (Basel : MDPI, 2022) Oswald, Steffen
    Li-based batteries are a key element in reaching a sustainable energy economy in the near future. The understanding of the very complex electrochemical processes is necessary for the optimization of their performance. X-ray photoelectron spectroscopy (XPS) is an accepted method used to improve understanding around the chemical processes at the electrode surfaces. Nevertheless, its application is limited because the surfaces under investigation are mostly rough and inhomogeneous. Local elemental analysis, such as Auger electron spectroscopy (AES), could assist XPS to gain more insight into the chemical processes at the surfaces. In this paper, some challenges in using electron spectroscopy are discussed, such as binding energy (BE) referencing for the quantitative study of chemical shifts, gas atmospheric influences, or beam damage (including both AE and XP spectroscopy). Carefully prepared and surface-modified metallic lithium material is used as model surface, considering that Li is the key element for most battery applications.
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    Floating zone growth of Bi2Sr2Ca2Cu3Oy superconductor
    (Basel : MDPI, 2016) Maljuk, Andrey; Lin, C.T.
    The crystal growth of high-temperature oxide superconductors has been hampered by the complexities of these materials and the lack of knowledge of corresponding phase diagrams. The most common crystal growth technique adopted for these materials is the so-called “Flux” method. This method, however, suffers from several drawbacks: (i) crystals are often crucible and flux contaminated; (ii) crystals are difficult to detach from solidified melt; and (iii) crystals are rather small. In most cases, these drawbacks can be overcome by the crucible-free floating zone method. Moreover, this technique is suitable for crystal growth of incongruently melting compounds, and has been thus successfully used to make large single crystals of Bi2Sr2Ca2Cu3Oy superconductor. In this review, the authors summarize the published and their own growth efforts as well as detailed characterization of as-grown and post-growth annealed samples. The optimal growth conditions that allowed one to obtain the large-size, almost single phase and homogeneous in composition Bi2Sr2Ca2Cu3Oy single crystals are presented. The effect of long lasting post-growth heat treatment on both crystal quality and superconducting properties has also been demonstrated.
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    Graphene-Like ZnO: A Mini Review
    (Basel : MDPI, 2016) Ta, Huy Q.; Zhao, Liang; Pohl, Darius; Pang, Jinbo; Trzebicka, Barbara; Rellinghaus, Bernd; Pribat, Didier; Gemming, Thomas; Liu, Zhongfan; Bachmatiuk, Alicja; Rümmeli, Mark H.
    The isolation of a single layer of graphite, known today as graphene, not only demonstrated amazing new properties but also paved the way for a new class of materials often referred to as two-dimensional (2D) materials. Beyond graphene, other 2D materials include h-BN, transition metal dichalcogenides (TMDs), silicene, and germanene, to name a few. All tend to have exciting physical and chemical properties which appear due to dimensionality effects and modulation of their band structure. A more recent member of the 2D family is graphene-like zinc oxide (g-ZnO) which also holds great promise as a future functional material. This review examines current progress in the synthesis and characterization of g-ZnO. In addition, an overview of works dealing with the properties of g-ZnO both in its pristine form and modified forms (e.g., nano-ribbon, doped material, etc.) is presented. Finally, discussions/studies on the potential applications of g-ZnO are reviewed and discussed.
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    Electron Beam-Induced Reduction of Cuprite
    (Basel : MDPI, 2022) Siudzinska, Anna; Gorantla, Sandeep M.; Serafinczuk, Jaroslaw; Kudrawiec, Robert; Hommel, Detlef; Bachmatiuk, Alicja
    Cu-based materials are used in various industries, such as electronics, power generation, and catalysis. In particular, monolayered cuprous oxide (Cu2O) has potential applications in solar cells owing to its favorable electronic and magnetic properties. Atomically thin Cu2O samples derived from bulk cuprite were characterized by high-resolution transmission electron microscopy (HRTEM). Two voltages, 80 kV and 300 kV, were explored for in situ observations of the samples. The optimum electron beam parameters (300 kV, low-current beam) were used to prevent beam damage. The growth of novel crystal structures, identified as Cu, was observed in the samples exposed to isopropanol (IPA) and high temperatures. It is proposed that the exposure of the copper (I) oxide samples to IPA and temperature causes material nucleation, whereas the consequent exposure via e-beams generated from the electron beam promotes the growth of the nanosized Cu crystals.
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    Investigating the Static Recrystallization Behavior of 22MnB5 Manganese–Boron Steel through Stress Relaxation Analysis
    (Basel : MDPI, 2023) Birnbaum, Peter; Pilz, Stefan; Neufeld, Kai; Kunke, Andreas
    A constitutive model was developed to characterize the static recrystallization (SRX) and evolution of the grain size of the industrially relevant press-hardening steel, 22MnB5, subsequent to the hot forming of sheet metal. Isothermal stress relaxation tests were conducted using the BAEHR 805 A/D thermomechanical simulator, encompassing a temperature range of 950 to 1050 °C, prestrain levels ranging from 0.01 to 0.1, and strain rates spanning from 0.01 to 0.8 s−1. The results obtained from the isothermal stress relaxation tests facilitated the formulation of an Avrami equation-based model, which aptly describes the kinetics of SRX in relation to the temperature, prestrain, and strain rate. Notably, an increase in temperature led to accelerated recrystallization kinetics, signifying temperature-dependent behavior. When the temperature increased from 950 to 1050 °C, the recrystallization time was reduced to approximately one-third. Additionally, the prestrain exhibited a positive influence on the acceleration of SRX kinetics. A quintupling of the prestrain from 0.01 to 0.05 resulted in a reduction of the static recrystallization duration to approximately one-fifth. Among the parameters studied, the strain rate had the least impact on the SRX kinetics, as doubling the strain rate from 0.01 to 0.8 only resulted in a halving of the recrystallization duration. Moreover, an analysis of the microstructural evolution in response to the forming parameters was undertaken. While the grain-size investigation post-isothermal stress relaxation tests provided results in line with the SRX kinetics calculations, the observed effects were comparatively subdued. Furthermore, a comprehensive examination was conducted using electron backscatter diffraction (EBSD) analysis, aiming to explore the effects of specific stress relaxation states on the morphology of martensite. The findings reveal fully recrystallized globulitic microstructures, characterized by relatively minor differences among them.
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    Mechanism of Skyrmion Attraction in Chiral Magnets near the Ordering Temperatures.
    (Basel : MDPI, 2023) Leonov, Andrey O.; Rößler, Ulrich K.
    Isolated chiral skyrmions are investigated within the phenomenological Dzyaloshinskii model near the ordering temperatures of quasi-two-dimensional chiral magnets with Cnv symmetry and three-dimensional cubic helimagnets. In the former case, isolated skyrmions (IS) perfectly blend into the homogeneously magnetized state. The interaction between these particle-like states, being repulsive in a broad low-temperature (LT) range, is found to switch into attraction at high temperatures (HT). This leads to a remarkable confinement effect: near the ordering temperature, skyrmions exist only as bound states. This is a consequence of the coupling between the magnitude and the angular part of the order parameter, which becomes pronounced at HT. The nascent conical state in bulk cubic helimagnets, on the contrary, is shown to shape skyrmion internal structure and to substantiate the attraction between them. Although the attracting skyrmion interaction in this case is explained by the reduction of the total pair energy due to the overlap of skyrmion shells, which are circular domain boundaries with the positive energy density formed with respect to the surrounding host phase, additional magnetization "ripples" at the skyrmion outskirt may lead to attraction also at larger length scales. The present work provides fundamental insights into the mechanism for complex mesophase formation near the ordering temperatures and constitutes a first step to explain the phenomenon of multifarious precursor effects in that temperature region.
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    Surface Modified β-Ti-18Mo-6Nb-5Ta (wt%) Alloy for Bone Implant Applications: Composite Characterization and Cytocompatibility Assessment
    (Basel : MDPI, 2023) Escobar, Michael; Careta, Oriol; Fernández Navas, Nora; Bartkowska, Aleksandra; Alberta, Ludovico Andrea; Fornell, Jordina; Solsona, Pau; Gemming, Thomas; Gebert, Annett; Ibáñez, Elena; Blanquer, Andreu; Nogués, Carme; Sort, Jordi; Pellicer, Eva
    Commercially available titanium alloys such as Ti-6Al-4V are established in clinical use as load-bearing bone implant materials. However, concerns about the toxic effects of vanadium and aluminum have prompted the development of Al- and V-free β-Ti alloys. Herein, a new alloy composed of non-toxic elements, namely Ti-18Mo-6Nb-5Ta (wt%), has been fabricated by arc melting. The resulting single β-phase alloy shows improved mechanical properties (Young’s modulus and hardness) and similar corrosion behavior in simulated body fluid when compared with commercial Ti-6Al-4V. To increase the cell proliferation capability of the new biomaterial, the surface of Ti-18Mo-6Nb-5Ta was modified by electrodepositing calcium phosphate (CaP) ceramic layers. Coatings with a Ca/P ratio of 1.47 were obtained at pulse current densities, −jc, of 1.8–8.2 mA/cm2, followed by 48 h of NaOH post-treatment. The thickness of the coatings has been measured by scanning electron microscopy from an ion beam cut, resulting in an average thickness of about 5 μm. Finally, cytocompatibility and cell adhesion have been evaluated using the osteosarcoma cell line Saos-2, demonstrating good biocompatibility and enhanced cell proliferation on the CaP-modified Ti-18Mo-6Nb-5Ta material compared with the bare alloy, even outperforming their CaP-modified Ti-6-Al-4V counterparts.
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    Acid Treatments of Ti-Based Metallic Glasses for Improving Corrosion Resistance in Implant Applications
    (Basel : MDPI, 2024) Fernández-Navas, Nora; Shtefan, Viktoriia; Hantusch, Martin; Gebert, Annett
    Ti-based bulk metallic glasses are promising materials for metallic bone implants, mainly due to their mechanical biofunctionality. A major drawback is their limited corrosion resistance, with high sensitivity to pitting. Thus, effective surface treatments for these alloys must be developed. This work investigates the electrochemical treatment feasibility of nitric acid (HNO3) solution for two bulk glass-forming alloys. The surface states obtained at different anodic potentials are characterized with electron microscopy and Auger electron spectroscopy. The corrosion behavior of the treated glassy alloys is analyzed via comparison to non-treated states in phosphate-buffered saline solution (PBS) at 37 °C. For the glassy Ti47Zr7.5Cu38Fe2.5Sn2Si1Ag2 alloy, the pre-treatment causes pseudo-dealloying, with a transformation from naturally passivated surfaces to Ti- and Zr-oxide nanoporous layers and Cu-species removal from the near-surface regions. This results in effective suppression of chloride-induced pitting in PBS. The glassy Ti40Zr10Cu34Pd14Sn2 alloy shows lower free corrosion activity in HNO3 and PBS due to Pd stabilizing its strong passivity. However, this alloy undergoes pitting under anodic conditions. Surface pre-treatment results in Cu depletion but causes enrichment of Pd species and non-homogeneous surface oxidation. Therefore, for this glassy alloy, pitting cannot be completely inhibited in PBS. Concluding, anodic treatments in HNO3 are more suitable for Pd-free glassy Ti-based alloys.
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    Revealing the Role of Cross Slip for Serrated Plastic Deformation in Concentrated Solid Solutions at Cryogenic Temperatures
    (Basel : MDPI, 2022) Tirunilai, Aditya Srinivasan; Weiss, Klaus-Peter; Freudenberger, Jens; Heilmaier, Martin; Kauffmann, Alexander
    Serrated plastic deformation is an intense phenomenon in CoCrFeMnNi at and below 35 K with stress amplitudes in excess of 100 MPa. While previous publications have linked serrated deformation to dislocation pile ups at Lomer–Cottrell (LC) locks, there exist two alternate models on how the transition from continuous to serrated deformation occurs. One model correlates the transition to an exponential LC lock density–temperature variation. The second model attributes the transition to a decrease in cross-slip propensity based on temperature and dislocation density. In order to evaluate the validity of the models, a unique tensile deformation procedure with multiple temperature changes was carried out, analyzing stress amplitudes subsequent to temperature changes. The analysis provides evidence that the apparent density of LC locks does not massively change with temperature. Instead, the serrated plastic deformation is likely related to cross-slip propensity.