Tilmann Leisegang

Synthesis of nanostructured chitin–hematite composites under extreme biomimetic conditions

Chitin of poriferan origin is a unique and thermostable biological material. It also represents an example of a renewable materials source due to the high regeneration ability of Aplysina sponges under marine ranching conditions. Chitinous scaffolds isolated from the skeleton of the marine sponge Aplysina aerophoba were used as a template for the in vitro formation of Fe2O3 under conditions (pH ∼ 1.5, 90 °C) which are extreme for biological materials. Novel chitin–Fe2O3 three dimensional composites, which have been prepared for the first time using hydrothermal synthesis, were thoroughly characterized using numerous analytical methods including Raman spectroscopy, XPS, XRD, electron diffraction and HR-TEM. We demonstrate the growth of uniform Fe2O3 nanocrystals into the nanostructured chitin substrate and propose a possible mechanism of chitin–hematite interactions. Moreover, we show that composites made of sponge chitin–Fe2O3 hybrid materials with active carbon can be successfully used as electrode materials for electrochemical capacitors.

How to measure the pyroelectric coefficient

The precise quantification of the pyroelectric coefficient p is indispensable for the characterization of pyroelectric materials and the development of pyroelectric-based devices, such as radiation sensors or energy harvesters. A summary of the variety of techniques to measure p is given in the present review. It provides a classification after the thermal excitation and an outline of capabilities and drawbacks of the individual techniques. The main selection criteria are: the possibility to separate different contributions to the pyroelectric coefficient, to exclude thermally stimulated currents, the capability to measure p locally, and the requirement for metallic electrodes. This overview should enable the reader to choose the technique best suited for specific samples.

A novel chitosan/sponge chitin origin material as a membrane for supercapacitors – preparation and characterization

A new chitosan/sponge chitin – based membrane (CS/CH membrane) was prepared via the casting method for the first time. We used the demineralized skeleton of the marine demosponge Ianthella basta as a source for a chitinous network. The obtained membrane was immersed in 1 M LiOAc (lithium acetate) solution and tested in an Electric Double Layer Capacitor (EDLC) cell. For comparison, chitosan (CS) with LiOAc solution was also tested. The studies performed indicated good properties of the CS/CH membrane. Very good mechanical stability (for use in electrochemical capacitors) and electrochemical properties of the CS membrane were achieved by the addition of chitin isolated from the sponge to the polymer matrix. Their electrochemical performances were tested in EDLC cells by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge. The specific capacitances of the tested capacitor cells were found to be approximately 97 F g−1 and 88 F g−1 with CS/CH and CS membranes (in the voltage range 0–0.8 V), respectively.

Fracture patterns in thin films and multilayers

While there are many stress relief mechanisms observed in thin films, excessive residual and externally applied stresses cause film fracture. In the case of tensile stress a network of through-thickness cracks forms in the film. In the case of compressive stress thin film buckling is observed in the form of blisters. Thin film delamination is an inseparable phenomenon of buckling. The buckling delamination blisters can be either circular, straight, or form periodic buckling patterns commonly known as telephone cord delamination morphology. While excessive biaxial residual stress is the key for causing thin film fracture, either in tension, or compression, it is the influence of the external stress that can control the final fracture pattern. In this paper we consider phone cord buckling delamination observed in compressed W/Si and TiWN/GaAs thin film systems, as well as spiral and sinusoidal though-thickness cracks observed in Mo/Si multilayers under 3-point high-temperature bending in tension.

Dielectric to pyroelectric phase transition induced by defect migration

Subjecting strontium titanate single crystals to an electric field in the order of 106 V m−1 is accompanied by a distortion of the cubic crystal structure, so that inversion symmetry vanishes and a polar phase is established. Since the polar nature of the migration-induced field-stabilized polar (MFP) phase is still unclear, the present work investigates and confirms the pyroelectric structure. We present measurements of thermally stimulated and pyroelectric currents that reveal a pyroelectric coefficient pMFP in the order of 30 μC K−1m−2. Therefore, a dielectric to pyroelectric phase transition in an originally centrosymmetric crystal structure with an inherent dipole moment is found, which is induced by defect migration. From symmetry considerations, we derive space group for the MFP phase of SrTiO3. The entire electroformation cycle yields additional information about the directed movement and defect chemistry of oxygen vacancies.

The pyroelectric coefficient of free standing GaN grown by HVPE

The present study reports on the temperature dependent pyroelectric coefficient of free-standing and strain-free gallium nitride (GaN) grown by hydride vapor phase epitaxy (HVPE). The Sharp-Garn method is applied to extract the pyroelectric coefficient from the electrical current response of the crystals subjected to a sinusoidal temperature excitation in a range of 0 °C to 160 °C. To avoid compensation of the pyroelectric response by an internal conductivity, insulating GaN crystals were used by applying C, Mn, and Fe doping during HVPE growth. The different pyroelectric coefficients observed at room temperature due to the doping correlate well with the change of the lattice parameter c. The obtained data are compared to previously published theoretical and experimental values of thin film GaN and discussed in terms of a strained lattice.

The anisotropy of oxygen vacancy migration in SrTiO3.

Oxygen migration in perovskites is well known to occur via vacancies along the TiO6 octahedron edges. Ionic conduction depends further on the orientation of the crystal in the electric field. To study the anisotropy in cubic SrTiO3 single crystals, temperature-dependent electroformation measurements ranging from 11 °C to 50 °C have been conducted for representative crystallographic directions within the crystal system. Electroformation of pure SrTiO3 follows an Arrhenius behavior, implying an ionic migration process of intrinsic oxygen defects. Activation energies E A for oxygen vacancy migration have been determined to 0.70 eV for [Formula: see text] and [Formula: see text] directions in contrast to 0.77 eV for [Formula: see text]. Mobility of oxygen vacancies is enhanced in [Formula: see text] compared to [Formula: see text] and [Formula: see text] by up to half an order of magnitude. A migration model based on atomistic migration paths and their multiplicities accounts for these experimental variations in mobility.

Large piezoelectricity in electric-field modified single crystals of SrTiO3

Defect engineering is an effective and powerful tool to control the existing material properties and produce completely new ones, which are symmetry-forbidden in a defect-free crystal. For example, the application of a static electric field to a single crystal of SrTiO3 forms a strained near-surface layer through the migration of oxygen vacancies out of the area beneath the positively charged electrode. While it was previously shown that this near-surface phase holds pyroelectric properties, which are symmetry-forbidden in centrosymmetric bulk SrTiO3, this paper reports that the same phase is strongly piezoelectric. We demonstrate the piezoelectricity of this phase through stroboscopic time-resolved X-ray diffraction under alternating electric field and show that the effective piezoelectric coefficient d33 ranges between 60 and 100 pC/N. The possible atomistic origins of the piezoelectric activity are discussed as a coupling between the electrostrictive effect and spontaneous polarization of this near-sur...

Incommensurately modulated CeSi1.82

Abstract An incommensurately modulated structure of CeSi1.82 as determined by single-crystal X-ray diffraction at room temperature is reported. The observed satellite reflections reduce the orthorhombic symmetry of the X-ray pattern to a monoclinic one. This suggests the description of the modulated structure in the monoclinic superspace group I2/b(αβ0)00. The modulation wave vector was determined to q = 0.410(1) · a* + 0.610(1) · b*. The refinement was done using harmonic modulation functions for the displacement and the occupation probability of the atoms, the quality parameters converged to Robs = 3.33% (Robs = 2.56% for the main reflections, Robs = 8.88% for the 1st order satellite reflections and Robs = 33.06% for the 2nd order satellite reflections). The origin of the observed satellite reflections is attributed to a modulation of the partly occupied Si site caused by composition changes within the crystal.

On the Way to New Possible Na-Ion Conductors: The Voronoi-Dirichlet Approach, Data Mining and Symmetry Considerations in Ternary Na Oxides.

With the constant growth of the lithium battery market and the introduction of electric vehicles and stationary energy storage solutions, the low abundance and high price of lithium will greatly impact its availability in the future. Thus, a diversification of electrochemical energy storage technologies based on other source materials is of great relevance. Sodium is energetically similar to lithium but cheaper and more abundant, which results in some already established stationary concepts, such as Na-S and ZEBRA cells. The most significant bottleneck for these technologies is to find effective solid ionic conductors. Thus, the goal of this work is to identify new ionic conductors for Na ions in ternary Na oxides. For this purpose, the Voronoi-Dirichlet approach has been applied to the Inorganic Crystal Structure Database and some new procedures are introduced to the algorithm implemented in the programme package ToposPro. The main new features are the use of data mined values, which are then used for the evaluation of void spaces, and a new method of channel size calculation. 52 compounds have been identified to be high-potential candidates for solid ionic conductors. The results were analysed from a crystallographic point of view in combination with phenomenological requirements for ionic conductors and intercalation hosts. Of the most promising candidates, previously reported compounds have also been successfully identified by using the employed algorithm, which shows the reliability of the method.