Field-Assisted Sintering/Spark Plasma Sintering of Gadolinium-Doped Ceria with Controlled Re-oxidation for Crack Prevention.

Gadolinium-Doped Ceria (GDC) is a prospective material for application in electrochemical devices. Free sintering in air of GDC powder usually requires temperatures in the range of 1400 to 1600 °C and dwell time of several hours. Recently, it was demonstrated that sintering temperature can be significantly decreased, when sintering was performed in reducing atmosphere. Following re-oxidation at elevated temperatures was found to be a helpful measure to avoid sample failure. Sintering temperature and dwell time can be also decreased by use of Spark Plasma Sintering, also known as Field-Assisted Sintering Technique (FAST/SPS). In the present work, we combined for the first time the advantages of FAST/SPS technology and re-oxidation for sintering of GDC parts. However, GDC samples sintered by FAST/SPS were highly sensitive to fragmentation. Therefore, we investigated the factors responsible for this effect. Based on understanding of these factors, a special tool was designed enabling pressureless FAST/SPS sintering in controlled atmosphere. For proof of concept, a commercial GDC powder was sintered in this tool in reducing atmosphere (Ar-2.9%H2), followed by re-oxidation. The fragmentation of GDC samples was avoided and the number of micro-cracks was reduced to a minimum. Prospects of GDC sintering by FAST/SPS were discussed.

Increasing Fracture Toughness and Transmittance of Transparent Ceramics using Functional Low-Thermal Expansion Coatings.

Transparent polycrystalline ceramics have the potential to enable applications no other materials can, but to do so their strength and toughness must be improved. However, surface strengthening treatments like those used for glasses have so far remained elusive. Here for the first time, we report on engineering unprecedented surface compression, of the magnitude achieved for ion-exchange strengthened glasses (~750 MPa) in transparent ceramics. This was achieved by applying functional, low thermal-expansion yttria coatings onto yttria-stabilized zirconia substrates and thermally treating. In some instances, the treatment more than doubled the fracture toughness while simultaneously increasing light transmittance.

Li7La3Zr2O12 Interface Modification for Li Dendrite Prevention.

Al-contaminated Ta-substituted Li7La3Zr2O12 (LLZ:Ta), synthesized via solid-state reaction, and Al-free Ta-substituted Li7La3Zr2O12, fabricated by hot-press sintering (HP-LLZ:Ta), have relative densities of 92.7% and 99.0%, respectively. Impedance spectra show the total conductivity of LLZ:Ta to be 0.71 mS cm(-1) at 30 °C and that of HP-LLZ:Ta to be 1.18 mS cm(-1). The lower total conductivity for LLZ:Ta than HP-LLZ:Ta was attributed to the higher grain boundary resistance and lower relative density of LLZ:Ta, as confirmed by their microstructures. Constant direct current measurements of HP-LLZ:Ta with a current density of 0.5 mA cm(-2) suggest that the short circuit formation was neither due to the low relative density of the samples nor the reduction of Li-Al glassy phase at grain boundaries. TEM, EELS, and MAS NMR were used to prove that the short circuit was from Li dendrite formation inside HP-LLZ:Ta, which took place along the grain boundaries. The Li dendrite formation was found to be mostly due to the inhomogeneous contact between LLZ solid electrolyte and Li electrodes. By flatting the surface of the LLZ:Ta pellets and using thin layers of Au buffer to improve the contact between LLZ:Ta and Li electrodes, the interface resistance could be dramatically reduced, which results in short-circuit-free cells when running a current density of 0.5 mA cm(-2) through the pellets. Temperature-dependent stepped current density galvanostatic cyclings were also carried out to determine the critical current densities for the short circuit formation. The short circuit that still occurred at higher current density is due to the inhomogeneous dissolution and deposition of metallic Li at the interfaces of Li electrodes and LLZ solid electrolyte when cycling the cell at large current densities.

Fatigue behavior of highly porous titanium produced by powder metallurgy with temporary space holders.

Porous titanium cylinders were produced with a constant amount of temporary space holder (70 vol.%). Different interstitial contents were achieved by varying the starting powders (HDH vs. gas atomized) and manufacturing method (cold compaction without organic binders vs. warm compaction of MIM feedstocks). Interstitial contents (O, C, and N) as a function of manufacturing were measured by chemical analysis. Samples contained 0.34-0.58 wt.% oxygen, which was found to have the greatest effect on mechanical properties. Quasi-static mechanical tests under compression at low strain rate were used for reference and to define parameters for cyclic compression tests. Not unexpectedly, increased oxygen content increased the yield strength of the porous titanium. Cyclic compression fatigue tests were conducted using sinusoidal loading in a servo-hydraulic testing machine. Increased oxygen content was concomitant with embrittlement of the titanium matrix, resulting in significant reduction of compression cycles before failure. For samples with 0.34 wt.% oxygen, R, σ(min) and σ(max) were varied systematically to estimate the fatigue limit (~4 million cycles). Microstructural changes induced by cyclic loading were then characterized by optical microscopy, SEM and EBSD.

The Sulphur Poisoning Behaviour of Gadolinia Doped Ceria Model Systems in Reducing Atmospheres.

An array of analytical methods including surface area determination by gas adsorption using the Brunauer, Emmett, Teller (BET) method, combustion analysis, XRD, ToF-SIMS, TEM and impedance spectroscopy has been used to investigate the interaction of gadolinia doped ceria (GDC) with hydrogen sulphide containing reducing atmospheres. It is shown that sulphur is incorporated into the GDC bulk and might lead to phase changes. Additionally, high concentrations of silicon are found on the surface of model composite microelectrodes. Based on these data, a model is proposed to explain the multi-facetted electrochemical degradation behaviour encountered during long term electrochemical measurements. While electrochemical bulk properties of GDC stay largely unaffected, the surface polarisation resistance is dramatically changed, due to silicon segregation and reaction with adsorbed sulphur.

Operation of Thin-Film Electrolyte Metal-Supported Solid Oxide Fuel Cells in Lightweight and Stationary Stacks: Material and Microstructural Aspects.

In this study we report on the development and operational data of a metal-supported solid oxide fuel cell with a thin film electrolyte under varying conditions. The metal-ceramic structure was developed for a mobile auxiliary power unit and offers power densities of 1 W/cm² at 800 °C, as well as robustness under mechanical, thermal and chemical stresses. A dense and thin yttria-doped zirconia layer was applied to a nanoporous nickel/zirconia anode using a scalable adapted gas-flow sputter process, which allowed the homogeneous coating of areas up to 100 cm². The cell performance is presented for single cells and for stack operation, both in lightweight and stationary stack designs. The results from short-term operation indicate that this cell technology may be a very suitable alternative for mobile applications.

Easy assessment of the biocompatibility of Ni-Ti alloys by in vitro cell culture experiments on a functionally graded Ni-NiTi-Ti material.

The biocompatibility of nickel-titanium alloys was investigated by single-culture experiments on functionally graded samples with a stepwise change in composition from pure nickel to pure titanium, including an Ni-Ti shape memory alloy for a 50:50 mixture. This approach permitted a considerable decrease of experimental resources by simultaneously studying a full variation of composition. The results indicate a good biocompatibility for a nickel content up to about 50%. The cells used in the biocompatibility studies comprised osteoblast-like osteosarcoma cells (SAOS-2, MG-63), primary human osteoblasts (HOB), and murine fibroblasts (3T3).