Bernard A. Boukamp

A novel pulse isotopic exchange technique for rapid determination of the oxygen surface exchange rate of oxide ion conductors

We demonstrate the use of a novel pulse (18)O-(16)O isotopic exchange technique for the rapid determination of the oxygen surface exchange rate of oxide ion conductors while simultaneously providing insight into the mechanism of the oxygen exchange reaction, which contributes to the efficient development of devices incorporating these solids, such as solid oxide fuel cells and oxygen transport membranes.

Low-Cost, Large-Area, Facile, and Rapid Fabrication of Aligned ZnO Nanowire Device Arrays

Well aligned nanowires of ZnO have been made with an electrospinning technique using zinc acetate precursor solutions. Employment of two connected parallel collector plates with a separating gap of 4 cm resulted in a very high degree of nanowire alignment. By adjusting the process parameters, the deposition density of the wires could be controlled. Field effect transistors were prepared by depositing wires between two gold electrodes on top of a heavily doped Si substrate covered with a 300 nm oxide layer. These devices showed good FET characteristics and photosensitivity under UV-illumination. The method provides a fast and scalable fabrication route for functional nanowire arrays with a high degree of alignment and control over nanowire spacing.

Influence of Solution Properties and Process Parameters on the Formation and Morphology of YSZ and NiO Ceramic Nanofibers by Electrospinning

The fabrication process of ceramic yttria-stabilized zirconia (YSZ) and nickel oxide nanofibers by electrospinning is reported. The preparation of hollow YSZ nanofibers and aligned nanofiber arrays is also demonstrated. The influence of the process parameters of the electrospinning process, the physicochemical properties of the spinning solutions, and the thermal treatment procedure on spinnability and final microstructure of the ceramic fibers was determined. The fiber diameter can be varied from hundreds of nanometers to more than a micrometer by controlling the solution properties of the electrospinning process, while the grain size and surface roughness of the resulting fibers are mainly controlled via the final thermal annealing process. Although most observed phenomena are in qualitative agreement with previous studies on the electrospinning of polymeric nanofibers, one of the main differences is the high ionic strength of ceramic precursor solutions, which may hamper the spinnability. A strategy to control the effective ionic strength of precursor solutions is also presented.

Flexible Yttrium-Stabilized Zirconia Nanofibers Offer Bioactive Cues for Osteogenic Differentiation of Human Mesenchymal Stromal Cells.

Currently, the main drawback of ceramic scaffolds used in hard tissue regeneration is their low mechanical strength. Stabilized zirconia, especially the tetragonal 3% yttrium-stabilized zirconia (YSZ) phase, has been considered as a bioinert ceramic material with high mechanical strength. In the present work, flexible nanofibrous YSZ scaffolds were prepared by electrospinning. The obtained scaffolds showed remarkable flexibility at the macroscopic scale, while retaining their stiffness at the microscopic scale. The surface nanoroughness of the scaffolds could be tailored by varying the heat treatment method. Our results demonstrate that the osteogenic differentiation and mineralization of seeded human mesenchymal stromal cells were supported by the nanofibrous YSZ scaffolds, in contrast to the well-known bioinert behavior of bulk YSZ. These findings highlight that flexible ceramic scaffolds are an appealing alternative to the current brittle ceramics for bone tissue regeneration applications.

Influence of ionic conductivity of the nano-particulate coating phase on oxygen surface exchange of La0.58Sr0.4Co0.2Fe0.8O3−δ

The oxygen surface exchange kinetics of mixed-conducting perovskite La0.58Sr0.4Co0.2Fe0.8O3 d (LSCF) ceramics coated with a porous nano-particulate layer of either gadolinea (Gd2O3), ceria (CeO2) or 20 mol% Gd-doped ceria (GCO) was determined by electrical conductivity relaxation (ECR). The measurements were performed in the temperature range 700–900 C, following pO2-step changes between 0.2 and 0.4 atm. The apparent value of the surface exchange coefficient, kchem, is found to vary with the loading amount and ionic conductivity of the coated phase whilst, as expected, the chemical diffusion coefficient Dchem remains invariant with the applied coating. Partial coverage of the LSCF surface with non-ionic conductive Gd2O3 or CeO2 lowers the value of kchem relative to that observed for bare LSCF, which is attributed to surface blocking effects. In contrast, partial coverage of LSCF with GCO electrolyte particles enhances the apparent value of kchem up to a factor of 6 compared to bare LSCF. The data of pulse isotope exchange (PIE) measurements show that the surface exchange reaction on bare LSCF is predominantly limited by dissociative adsorption of O2. Different mechanisms for the improved oxygen surface exchange kinetics after partially covering the LSCF surface with GCO are discussed.

Electron transfer rates in host-guest assemblies at β-cyclodextrin monolayers

The effect of the distance between a β-cyclodextrin (βCD) host core and a conductive substrate on the electron-transfer rate of complexed guests as well as of free-diffusing electrochemically active probes has been studied. First we have evaluated a set of short-tethered βCD adsorbates bearing different anchoring groups in order to get a reliable platform for the study of short-distance electron transfer. An electrochemically active trivalent guest was immobilized on these host monolayers in a selective and reversible manner, providing information about the packing density. Iodine- and nitrile-functionalized βCD monolayers gave coverages close to maximum packing. Electron transfer in the presence of Fe(CN)63-/4- studied by impedance spectroscopy revealed that the electron transfer of the diffusing probe was 3 orders of magnitude faster than when the βCD cores were separated from the surface by undecyl chains. When an electrochemically active guest was immobilized on the surface, electron-transfer rate measurements by cyclic voltammetry and capacitance spectroscopy showed differences of up to a factor of 8 for different βCD monolayers. These results suggest that increasing the distance between the βCD core and the underlying conductive substrate leads to a diminishing of the electron-transfer rate.