Ionic and electronic conductivity of nitrogen-doped YSZ single crystals

The ionic and electronic charge transport was studied for single crystals of 9.5 mol% yttria-stabilized zirconia with additional nitrogen doping (YSZ:N) of up to 7.5 at.% (referred to the anion sublattice and formula unit Zr_0.83Y_0.17O_1.91) as a function of temperature and nitrogen content. The total conductivity being almost equivalent to the oxygen ion conductivity has been measured by AC impedance spectroscopy under vacuum conditions in order to prevent re-oxidation and loss of nitrogen. The electronic conductivity has been determined by Hebb–Wagner polarization using ion-blocking Pt microelectrodes in N₂ atmosphere. The ionic conductivity of YSZ:N decreases in the presence of nitrogen at intermediate temperatures up to 1000 °C. The mean activation energy of ionic conduction strongly increases with increasing nitrogen content, from 1.0 eV for nitrogen-free YSZ up to 1.9 eV for YSZ containing 7.3 at.% N. Compared to nitrogen-free YSZ, the electronic conductivity first decreases at nitrogen contents of 2.17 and 5.80 at.%, but then increases again for a sample with 7.53 at.%. At temperatures of 850 °C and above, the presence of the N^3? dopant fixes the electrode potential and thus the oxygen partial pressure at the Pt electrode to very low values. This corresponds to a pinning of the Fermi level at a relatively high energy in the upper half of the band gap. At 7.53 at.% N and 950 °C, the oxygen partial pressure in YSZ:N corresponds to p_O2 = 3 × 10^? 18 bar. At temperatures above 850 °C, even in the presence of a very small oxygen concentration in the surrounding gas phase, the nitrogen ion dopant becomes highly mobile and thus diffuses to the surface where it is oxidized to gaseous N₂. The results are discussed in terms of the ionic and electronic defect structures and the defect mobilities in YSZ:N.     

Thermodynamics,structure and kinetics in the system Ga–O–N

Within the ternary system Ga–O–N we performed experimental and theoretical investigations on the thermodynamics, structure and kinetics of new stable and metastable compounds.We studied the ammonolysis of β-Ga₂O₃ at elevated temperatures by means of ex situ X-ray diffraction, ex situ neutron diffraction, and in situ X-ray absorption spectroscopy (XAS). From total diffraction pattern refinement with the Rietveld method we analyzed the anionic occupancy factors and the lattice parameters of β-Ga₂O₃ during the reaction. Within the detection limits of these methods, we can rule out the existence of a crystalline oxynitride phase that is not derived from wurtzite-type GaN. The nitrogen solubility in β-Ga₂O₃ was found to be below the detection limit of about 2–3 at.% in the anionic sublattice. The kinetics of the ammonolysis of β-Ga₂O₃ to α-GaN and of the oxidation of α-GaN to β-Ga₂O₃ was studied by means of in situ X-ray absorption spectroscopy. In both cases the reaction kinetics could be described well by fitting linear combinations of β-Ga₂O₃ and α-GaN spectra only, excluding that other crystalline or amorphous phases appear during these reactions. The kinetics of the ammonolysis can be described well by an extended Johnson–Mehl–Avrami–Kolmogorow model with nucleation and growth of GaN nuclei, while the oxidation kinetics can be modeled by a shrinking core model where Ga₂O₃ grows as a layer. Investigations by means of TEM and SEM support the assumptions in both models.To investigate the structure and energetics of spinel-type gallium oxynitrides (γ-galons) we performed first-principles calculations using density-functional theory. In addition to the ideal cubic γ-Ga₃O₃N we studied gallium deficient γ-galons within the Constant-Anion-Model.In highly non-stoichiometric, amorphous gallium oxide of approximate composition GaO_1.2 we found at a temperature around 670 K an insulator–metal transition, with a conductivity jump of seven orders of magnitude. We demonstrate through experimental studies and density-functional theory calculations that the conductivity jump takes place at a critical gallium concentration and is induced by crystallization of stoichiometric β-Ga₂O₃ within the metastable oxide matrix. By doping with nitrogen the critical temperature and the conductivity in the highly conducting state can be tuned.     

Influence of interface structure on mass transport in phase boundaries between different ionic materials

Abstract  Internal and external interfaces in solids exhibit completely different transport properties compared to the bulk. Transport parallel to grain or phase boundaries is usually strongly enhanced. Transport perpendicular to an interface is usually blocked, i.e., transport across an interface is often much slower. Due to the high density of interfaces in modern micro- and nanoscaled devices, a severe influence on the total transport properties can be expected. In contrast to diffusion in metal grain boundaries, transport phenomena in boundaries of ionic materials are still less understood. The specific transport properties along metal grain boundaries are explained by structural factors like packing densities or dislocation densities in the interface region. In most studies dealing with ionic materials, the interfacial transport properties are merely explained by the influence of space charge regions. In this study the influence of the interface structure on the interfacial transport properties of ionic materials is discussed in analogy to metallic materials. A qualitative model based on the density of misfit dislocations and on interfacial strain is introduced for (untilted and untwisted) phase boundaries. For experimental verification, the interfacial ionic conductivity of different multilayer systems consisting of stabilised ZrO₂ and an insulating oxide is investigated as a funtion of structural mismatch. As predicted by the model, the interfacial conductivity increases when the lattice mismatch is increased. Graphical abstract  

Mass spectrometric characterization of lipid-modified peptides for the analysis of acylated proteins

The analysis of acylated proteins by mass spectrometry (MS) has largely been overshadowed in proteomics by the analysis of glycosylated and phosphorylated proteins; however, lipid modifications on proteins are proving to be of increasing importance in biomedical research. In order to identify the marker ions and/or neutral loss fragments that are produced upon collision-induced dissociation, providing a means to identify the common lipid modifications on proteins, peptides containing an N-terminally myristoylated glycine, a palmitoylated cysteine and a farnesylated cysteine were chemically synthesized. Matrix-assisted laser desorption/ionization time-of-flight time-of-flight (MALDI-TOF-TOF), electrospray ionization quadrupole time-of-flight (ESI Q-TOF), and electrospray ionization hybrid triple-quadrupole/linear ion trap (ESI QqQ(LIT)) mass spectrometers were used for the analysis. The peptide containing the N-terminally myristoylated glycine, upon CID, produced the characteristic fragments a1 (240.4 Th) and b1 (268.4 Th) ions as well as a low-intensity neutral loss of 210 Da (C14H26O). The peptides containing a farnesylated cysteine residue fragmented to produce a marker ion at a m/z of 205 Th (C15H25) as well as other intense farnesyl fragment ions, and a neutral loss of 204 Da (C15H24). The peptides containing a palmitoylated cysteine moiety generated neutral losses of 238 Da (C16H30O) and 272 Da (C16H32OS); however, no marker ions were produced. The neutral losses were more prominent in the MALDI-TOF-TOF spectra, whereas the marker ions were more abundant in the ESI QqQ(LIT) and Q-TOF mass spectra.     

Calibration procedure of the Δ<Emphasis Type="Italic">E</Emphasis>–<Emphasis Type="Italic">E</Emphasis> detectors for <Emphasis Type="Italic">dp</Emphasis> breakup investigation at nuclotron

Calibration procedure of ΔE ? E detectors used in dp breakup reaction measurement in the framework of DSS project is discussed. Time information from all PMTs along with amplitude information and known energy values of pp quasi elastic reaction are used to find calibration coefficients for ΔE and E detectors. Calibration coefficients are used to recover deposited particle energies. ΔE vs. E plots, energies and missing mass spectra are compared with geant4 Monte Carlo simulation. Missing mass for particular physical configuration is calculated as a test of the calibration procedure quality.     

Measurement of the vector A y and tensor A yy , A xx , A xz analyzing powers for the dd → 3H p reaction at 200 MeV

The data on the vector A _y and tensor A _yy , A _xx , A _xz analyzing powers for the d → ³H p reaction have been obtained at the energy of the initial deuteron of 200MeV in the angular range of 0–95 degrees in the c.m.s. The calculations performed within one-nucleon exchange model with the use of the standard three-nucleon bound state wave functions fail to reproduce the data on the tensor analyzing powers.     

Application of Linear and Branched Poly(Ethylene Glycol)‐Poly(Lactide) Block Copolymers for the Preparation of Films and Solution Electrospun Meshes

Poly(ethylene glycol)‐poly(lactide) (PEG‐PLA) block copolymers are processed to solvent cast films and solution electrospun meshes. The effect of polymer composition, architecture, and number of anchoring points for the plasticizer on swelling, degradation, and mechanical properties of these films and meshes is investigated as potential barrier device for the prevention of peritoneal adhesions. As a result, adequate properties are achieved for the massive films with a longer retention of the plasticizer PEG for star‐shaped block copolymers than for the linear triblock copolymers and consequently more endurable mechanical properties during degradation. For electrospun meshes fabricated using the same polymers, similar trends are observed, but with an earlier start of fragmentation and lower tensile strengths. To overcome the poor mechanical strengths and an occurring shrinkage during incubation, which may impair the coverage of the wound, further adaptions of the meshes and the fabrication process are necessary.