Ralf Witte

A novel Ti-based nanoglass composite with submicron–nanometer-sized hierarchical structures to modulate osteoblast behaviors

Owing to recent progress in nanotechnology, the ability to tune the surface properties of metals has opened an avenue for creating a new generation of biomaterials. Here we demonstrate the successful development of a novel Ti-based nanoglass composite with submicron-nanometer-sized hierarchical glassy structures. A first exploratory study was performed on the application of the unique nanostructure to modulate osteoblast behaviors. Our results show that this Ti-based nanoglass composite, relative to conventional metallic glasses, exhibits significantly improved biocompatibility. In fact, a 10 times enhancement in cell proliferation has been achieved. To a great extent, this superior bioactivity (such as enhanced cell proliferation and osteogenic phenotype) is promoted by its unique hierarchical structures combining nanoglobules and submicron button-like clusters from collective packing of these nanoglobules. This nanoglass composite could be widely applicable for surface modifications by means of coating on various materials including BMGs, crystalline metals or ceramics. Therefore, our successful experimental testing of this nanostructured metallic glass may open the way to new applications in novel biomaterial design for the purpose of bone replacement.

Structural investigations of interfaces in Fe90Sc10 nanoglasses using high-energy x-ray diffraction

High-resolution diffraction experiments of Fe90Sc10 nanoglasses and rapidly quenched metallic glasses as reference materials have been performed using high-energy x-rays with a wavelength of 0.21 A from a synchrotron radiation source. Nanoglasses are amorphous alloys with a significant fraction of interfaces on the nanometer scale. The short- and intermediate-range orders of a nanoglass are different from the well known amorphousmaterials produced by rapid quenching from the melt. These structural modifications have significant influence on the physical properties. In this paper, the short- and intermediate-range orders of the nanoglass Fe90Sc10 and the reference metallic glass Fe90Sc10 alloy prepared by rapid quenching are discussed.

Evidence for enhanced ferromagnetism in an iron-based nanoglass

The possibility to synthesize bulk amorphous materials with an internal nanostructure—nanoglasses—leads to yet another class of materials potentially with modified properties. Here, evidence is presented that the nanoglass model system Fe90Sc10 exhibits enhanced magnetic properties: it is shown that this nanoglass (prepared by cold compaction of glassy nanospheres) is a ferromagnet at ambient temperature although the isolated nanospheres are paramagnetic. Structural studies reveal that it consists of glassy nanospheres connected by regions with reduced atomic density. The ferromagnetism is explained by the presence of such regions of low atomic density.

Microwave synthesis of high-quality and uniform 4 nm ZnFe2O4 nanocrystals for application in energy storage and nanomagnetics

Summary Magnetic nanocrystals with a narrow size distribution hold promise for many applications in different areas ranging from biomedicine to electronics and energy storage. Herein, the microwave-assisted sol–gel synthesis and thorough characterization of size-monodisperse zinc ferrite nanoparticles of spherical shape is reported. X-ray diffraction, 57Fe Mössbauer spectroscopy and X-ray photoelectron spectroscopy all show that the material is both chemically and phase-pure and adopts a partially inverted spinel structure with Fe3+ ions residing on tetrahedral and octahedral sites according to (Zn0.32Fe0.68)tet[Zn0.68Fe1.32]octO4±δ. Electron microscopy and direct-current magnetometry confirm the size uniformity of the nanocrystals, while frequency-dependent alternating-current magnetic susceptibility measurements indicate the presence of a superspin glass state with a freezing temperature of about 22 K. Furthermore, as demonstrated by galvanostatic charge–discharge tests and ex situ X-ray absorption near edge structure spectroscopy, the as-prepared zinc ferrite nanocrystals can be used as a high-capacity anode material for Li-ion batteries, showing little capacity fade – after activation – over hundreds of cycles. Overall, in addition to the good material characteristics, it is remarkable that the microwave-based synthetic route is simple, easily reproducible and scalable.

Tailoring magnetic frustration in strained epitaxial FeRh films

We report on a strain-induced martensitic transformation, accompanied by a suppression of magnetic order in epitaxial films of chemically disordered FeRh. X-ray diffraction, transmission electronmicroscopy, and electronic structure calculations reveal that the lowering of symmetry (from cubic to tetragonal) imposed by the epitaxial relation leads to a further, unexpected, tetragonal-to-orthorhombic transition, triggered by a band-Jahn-Teller-type lattice instability. The collapse of magnetic order is a direct consequence of this structural change, which upsets the subtle balance between ferromagnetic nearest-neighbor interactions arising from Fe-Rh hybridization and frustrated antiferromagnetic coupling among localized Fe moments at larger distances.

Synthesis, structural characterisation and proton conduction of two new hydrated phases of barium ferrite BaFeO2.5−x(OH)2x

Materials exhibiting mixed electronic and proton conductivity are of great interest for applications ranging from electrodes for proton conducting ceramic fuel cells to hydrogen separation membranes. In this work, we report a detailed investigation of the effect of water incorporation in BaFeO2.5 on the structure and conductivity. BaFeO2.5 is shown to be topochemically transformed to two different hydrated modifications, low-water (LW-) and high-water (HW-) BaFeO2.5. A combined analysis of neutron and X-ray diffraction data was used to determine the crystal structure of LW-BaFeO2.5 (BaFeO2.33(OH)0.33), which shows a unique ordering pattern of anion vacancies for perovskite type compounds, with structural relaxations around vacancies being similar to the chemically similar compound BaFeO2.33F0.33. Approximate proton positions were determined using the bond valence method. Conductivity studies of hydrated and pure BaFeO2.5 (with additional comparison to oxidized BaFeO2.5) show a significant enhancement of the conductivity on water incorporation, which can be attributed to proton conductivity. This is the first report of significant grain proton conduction (∼10−6 to 10−7 S cm−1) in an iron based perovskite. Water uptake is further shown to be completely reversible, with reformation of BaFeO2.5 when heating the compound to temperatures above ∼450 K under Ar.

Mechanical Milling Assisted Synthesis and Electrochemical Performance of High Capacity LiFeBO3 for Lithium Batteries.

Borate chemistry offers attractive features for iron based polyanionic compounds. For battery applications, lithium iron borate has been proposed as cathode material because it has the lightest polyanionic framework that offers a high theoretical capacity. Moreover, it shows promising characteristics with an element combination that is favorable in terms of sustainability, toxicity, and costs. However, the system is also associated with a challenging chemistry, which is the major reason for the slow progress in its further development as a battery material. The two major challenges in the synthesis of LiFeBO3 are in obtaining phase purity and high electrochemical activity. Herein, we report a facile and scalable synthesis strategy for highly pure and electrochemically active LiFeBO3 by circumventing stability issues related to Fe(2+) oxidation state by the right choice of the precursor and experimental conditions. Additionally, we carried out a Mössbauer spectroscopic study of electrochemical charged and charged-discharged LiFeBO3 and reported a lithium diffusion coefficient of 5.56 × 10(-14) cm(2) s(-1) for the first time.

Hybrid supercapacitors for reversible control of magnetism

Electric field tuning of magnetism is one of the most intensely pursued research topics of recent times aiming at the development of new-generation low-power spintronics and microelectronics. However, a reversible magnetoelectric effect with an on/off ratio suitable for easy and precise device operation is yet to be achieved. Here we propose a novel route to robustly tune magnetism via the charging/discharging processes of hybrid supercapacitors, which involve electrostatic (electric-double-layer capacitance) and electrochemical (pseudocapacitance) doping. We use both charging mechanisms—occurring at the La0.74Sr0.26MnO3/ionic liquid interface to control the balance between ferromagnetic and non-ferromagnetic phases of La1−xSrxMnO3 to an unprecedented extent. A magnetic modulation of up to ≈33% is reached above room temperature when applying an external potential of only about 2.0 V. Our case study intends to draw attention to new, reversible physico-chemical phenomena in the rather unexplored area of magnetoelectric supercapacitors.

Proton Conduction in Grain-Boundary-Free Oxygen-Deficient BaFeO2.5+δ Thin Films

Reduction of the operating temperature to an intermediate temperature range between 350 °C and 600 °C is a necessity for Solid Oxide Fuel/Electrolysis Cells (SOFC/SOECs). In this respect the application of proton-conducting oxides has become a broad area of research. Materials that can conduct protons and electrons at the same time, to be used as electrode catalysts on the air electrode, are especially rare. In this article we report on the proton conduction in expitaxially grown BaFeO2.5+δ (BFO) thin films deposited by pulsed laser deposition on Nb:SrTiO3 substrates. By using Electrochemical Impedance Spectroscopy (EIS) measurements under different wet and dry atmospheres, the bulk proton conductivity of BFO (between 200 °C and 300 °C) could be estimated for the first time (3.6 × 10−6 S cm−1 at 300 °C). The influence of oxidizing measurement atmosphere and hydration revealed a strong dependence of the conductivity, most notably at temperatures above 300 °C, which is in good agreement with the hydration behavior of BaFeO2.5 reported previously.

Low temperature structural stability of Fe90Sc10 nanoglasses

ABSTRACT The structural stability of Fe90Sc10 nanoglasses has been studied by means of low temperature crystallization. Specimens were annealed in situ in a transmission electron microscope, and ex situ in an ultra-high vacuum tube-furnace. Both studies led to similar results. The structure of the Fe90Sc10 nanoglasses was stable for up to 2 h when annealed at 150°C. Annealing the Fe90Sc10 nanoglasses at higher temperature resulted in the formation of the nanocrystalline bcc-Fe(Sc). Impact statement The structural evolution of Fe90Sc10 nanoglasses has been studied in detail during low temperature annealing. Our results indicate that the nanostructure of Fe90Sc10 nanoglasses is quite stable at low temperature. GRAPHICAL ABSTRACT