Dielectric Behavior of Thin Polymerized Composite Layers Fabricated by Inkjet-Printing.

A detailed study of the dielectric behavior of printed capacitors is given, in which the dielectric consists of a thin (<1 µm) ceramic/polymer composite layer with high permittivities of εr 20-69. The used ink contains surface-modified Ba0.6Sr0.4TiO3 (BST), a polymeric crosslinking agent and a thermal initiator, which allows the immediate polymerization of the ink during printing, leading to homogenous layers. To validate the results of the calculated permittivities, different layer thicknesses of the dielectric are printed and the capacitances, as well as the loss factors, are measured. Afterwards, the exact layer thicknesses are determined with cross sectional SEM images of ion-etched samples. Then, the permittivities are calculated with the known effective area of the capacitors. Furthermore, the ink composition is varied to obtain different ceramic/polymer ratios and thus different permittivities. The packing density of all composites is analyzed via SEM to show possible pores and validate the target ratio, respectively. The correlation between the chosen ratio and the measured permittivity is discussed using models from the literature. In addition, the leakage current of some capacitors is measured and discussed. For that, the dielectric was printed on different bottom electrodes as the nature of the electrode was found to be crucial for the performance.

Interpreting rheology and electrical conductivity: It all boils down to which particle size.

HYPOTHESIS: The electrical charges that develop on the surface of the ceramic particles upon contact with water, due to the interaction with ions in solution, result in a liquid-solid interface, which utterly modifies the properties of individual particles and the way they interact with each other to form a structure. This work explores a new approach to the relationships between structure and stability of suspensions. EXPERIMENTS: For this purpose, suspensions with a constant 0.35 volume fraction of α-alumina particles, neither spherical nor smooth, and controlled ionic strength (0-90 mM KCl) were prepared and characterized in terms of flow behaviour, electrical conductivity and particle's electrokinetic mobility. FINDINGS: Electrical conductivity (132 µS/cm < conductivity < 5730 µS/cm) and rheology measurements (10-2 Pa s < viscosity < 104 Pa s) were found to complement each other to produce a more accurate picture of the suspension's structure. Deviations of experimental data from well-accepted behavioural models were elucidated when the surface area equivalent particle size was used. With the electrical double layer thickness obtained from electrical conductivity measurements, this enabled the interpretation of the relationship between the suspension's viscosity and the particles electrical conductivity, which provides a criterion for the stability of concentrated colloidal suspensions.

Fabrication and Characterization of Fully Inkjet Printed Capacitors Based on Ceramic/Polymer Composite Dielectrics on Flexible Substrates.

The preparation of fully inkjet printed capacitors containing ceramic/polymer composites as the dielectric material is presented. Therefore, ceramic/polymer composite inks were developed, which allow a fast one-step fabrication of the composite thick films. Ba0.6Sr0.4TiO3 (BST) is used as the ceramic component and poly(methyl methacrylate) (PMMA) as the polymer. The use of such composites allows printing on flexible substrates. Furthermore, it results in improved values for the permittivity compared to pure polymers. Three composite inks with varying ratio of BST to PMMA were used for the fabrication of composite thick films consisting of 33, 50 and 66 vol% BST, respectively. All inks lead to homogeneous structures with precise transitions between the different layers in the capacitors. Besides the microstructures of the printed thick films, the dielectric properties were characterized by impedance spectroscopy over a frequency range of 100 Hz to 200 kHz. In addition, the influence of a larger ceramic particle size was investigated, to raise permittivity. The printed capacitors exhibited dielectric constants of 20 up to 55 at 1 kHz. Finally, the experimental results were compared to different theoretical models and their suitability for the prediction of εcomposite was assessed.

Ferroelectric Properties of Perovskite Thin Films and Their Implications for Solar Energy Conversion.

Whether or not methylammonium lead iodide (MAPbI3 ) is a ferroelectric semiconductor has caused controversy in the literature, fueled by many misunderstandings and imprecise definitions. Correlating recent literature reports and generic crystal properties with the authors' experimental evidence, the authors show that MAPbI3 thin-films are indeed semiconducting ferroelectrics and exhibit spontaneous polarization upon transition from the cubic high-temperature phase to the tetragonal phase at room temperature. The polarization is predominantly oriented in-plane and is organized in characteristic domains as probed with piezoresponse force microscopy. Drift-diffusion simulations based on experimental patterns of polarized domains indicate a reduction of the Shockley-Read-Hall recombination of charge carriers within the perovskite grains due to the ferroelectric built-in field and allow reproduction of the electrical solar cell properties.

Lithium Diffusion Pathway in Li(1.3)Al(0.3)Ti(1.7)(PO4)3 (LATP) Superionic Conductor.

The Al-substituted LiTi2(PO4)3 powders Li(1+x)Al(x)Ti(2-x)(PO4)3 (LATP) were successfully prepared by a water-based sol-gel process with subsequent calcination and sintering. The crystal structure of obtained samples was characterized at different temperatures using high-resolution synchrotron-based X-ray and neutron powder diffraction. Possible lithium diffusion pathways were initially evaluated using the difference bond-valence approach. Experimental 3D lithium diffusion pathway in LATP was extracted from the negative nuclear density maps reconstructed by the maximum entropy method. Evaluation of the energy landscape determining the lithium diffusion process in NASICON-type superionic conductor is shown for the first time.

High capacity vertical aligned carbon nanotube/sulfur composite cathodes for lithium-sulfur batteries.

Binder free vertical aligned (VA) CNT/sulfur composite electrodes with high sulfur loadings up to 70 wt% were synthesized delivering discharge capacities higher than 800 mAh g(-1) of the total composite electrode mass.

Local variations in defect polarization and covalent bonding in ferroelectric Cu(2+)-doped PZT and KNN functional ceramics at the morphotropic phase boundary.

Cu(2+)-doped Pb[Zr(0.54)Ti(0.46)]O(3) (PZT) and Cu(2+)-doped [K(0.5)Na(0.5)]NbO(3) (KNN) ferroelectrics with a dopant concentration of 0.25 mol% were investigated by means of multi-frequency and multi-pulse electron paramagnetic resonance (EPR) spectroscopy. Through the use of high magnetic fields and pulsed microwave fields an enhanced resolution was achieved yielding valuable information about the structural distortion at the dopant site. The results obtained suggest that Cu(2+) substitutes for both systems as an acceptor centre for the perovskite B-site. For reasons of local charge compensation, different kinds of defect associates invoking one and two oxygen vacancies are formed. These two kinds of extended defects differ in their electric and elastic properties. The results obtained are analyzed in order to characterize differences of the local structure in the Cu(2+)-defect center for morphotropic phase boundary compositions between the two systems. In particular, it is found that Cu(2+)-doping in KNN creates 50% more oxygen vacancies than the same amount of copper in PZT. Furthermore, local differences in covalent and ionic bonding are monitored.

Defect-Dipole Formation in Copper-Doped PbTiO3 Ferroelectrics.

The defect structure of hard copper-modified polycrystalline PbTiO3 ferroelectrics is investigated by means of electron paramagnetic resonance and hyperfine sublevel correlation spectroscopy, as well as density functional theory calculations. Special emphasis is put on the 207Pb-hyperfine couplings, which are resolved up to the third coordination sphere. The results prove that copper is incorporated at the octahedrally coordinated Ti site, acting as an acceptor. Because of charge compensation the formation of Cu impurity-oxygen vacancy pairs is energetically very favorable. The corresponding (CuTi''-VO)x defect dipole is found to be orientated along the [001] axis.

A device for noninvasive assessment of vascular impairment risk in the lower extremity.

The repeatability and resolution of the clinical gold standard of vascular assessment, the ankle-brachial index (ABI), was compared to that of a new device that dynamically assesses tissue perfusion during external loading utilizing laser Doppler flowmetry. Eight subjects of varying levels of vascular impairment were tested in successive weeks using two different sites on the subject's posterior calf. These new measures included the perfusion decrease as well as the unloading delay during cyclic loading. Some new dynamic tissue perfusion measures demonstrated comparable levels of reproducibility with the ABI (e.g., 10%-20%). Only the unloading delay showed potentially enhanced resolution over ABI measures. The perfusion decrease showed little resolution, and the remaining parameters exhibited too great variability (25%-90%). The unloading delay associated with the reperfusion response during cyclic loading displayed the greatest combination of reproducibility and differentiation between subject groups of varying levels of vascular impairment. The preliminary results of this pilot study were also used to estimate sample sizes necessary to detect possible significant (P<0.05) differences between subject groups for all measured perfusion parameters. From these calculations, at least 30 subjects are needed for future study in each of the five subject groups.

Measuring electrostatic potential profiles across amorphous intergranular films by electron diffraction.

Amorphous 1-2-nm-wide intergranular films in ceramics dictate many of their properties. The detailed investigation of structure and chemistry of these films pushes the limits of today's transmission electron microscopy. We report on the reconstruction of the one-dimensional potential profile across the film from an experimentally acquired tilt series of energy-filtered electron diffraction patterns. Along with the potential profile, the specimen thickness, film orientation with respect to the grain lattice and specimen surface, and the absolute specimen orientation with respect to the laboratory frame of reference are retrieved.

High-field/high-frequency EPR of paramagnetic functional centers in Cu2+- and Fe3+-modified polycrystalline Pb[Zr(x)Ti(1-x)]O3 ferroelectrics.

Copper(II)- and iron(III)-modified Pb[Zr(x)Ti(1-x)]O3 ferroelectrics were investigated by means of high-field/high-frequency EPR. The results obtained suggest that Cu2+ and Fe3+ both substitute as acceptor centers for [Zr,Ti]4+. Whereas for the iron-doped system the charge compensating oxygen vacancies (V(O)**) lead to the formation of charged (Fe'(Ti-)V(O)**)* defect associates, no such associates have been observed for the copper-modified system. As regards the morphotropic phase boundary, the model of a mesoscopic mixing of the pure-member phases has been refined to a picture in which a nanoscale composition distribution prevails.

Electrical conductivity and stability of concentrated aqueous alumina suspensions.

This work describes the effect of solids load and ionic strength on the electrical conductivity (K(S)) of concentrated aqueous suspensions of commercial alpha-alumina (1-35 vol% solids). The results obtained show that the dependency of the electrical conductivity of the suspending liquid (K(L)) on the volume fraction of solids is well described by Maxwell's model. The change in the conductivity of the suspensions relative to that of the suspending liquid (K(S)/K(L)) was found to be inversely proportional to the solids content, as predicted by Maxwell's model. The relative conductivity rate, DeltaK, could be interpreted in terms of the DLVO theory and the particles double layer parameter, kappaa, and used as a stability criterion. As kappaa changes, in response to the changes in ionic strength, so does the conducting to insulating character of the particles and, as such, their contribution to the overall suspension conductivity (expressed by DeltaK). When the particles become insulating, the suspension conductivity decreases when the solids load increases. The turning point in this particle behaviour corresponds to a critical concentration of ions in the solution that destabilises the suspension and is associated with the critical coagulation concentration (ccc). It is the electrical double layer that ultimately determines the conducting or insulating character of the particles, and that character can be made to change, as required for suspension stability, and accessed by the relative conductivity rate.