Crystallization of zirconia based thin films.

The crystallization kinetics of amorphous 3 and 8 mol% yttria stabilized zirconia (3YSZ and 8YSZ) thin films grown by pulsed laser deposition (PLD), spray pyrolysis and dc-magnetron sputtering are explored. The deposited films were heat treated up to 1000 °C ex situ and in situ in an X-ray diffractometer. A minimum temperature of 275 °C was determined at which as-deposited amorphous PLD grown 3YSZ films fully crystallize within five hours. Above 325 °C these films transform nearly instantaneously with a high degree of micro-strain when crystallized below 500 °C. In these films the t'' phase crystallizes which transforms at T > 600 °C to the t' phase upon relaxation of the micro-strain. Furthermore, the crystallization of 8YSZ thin films grown by PLD, spray pyrolysis and dc-sputtering are characterized by in situ XRD measurements. At a constant heating rate of 2.4 K min(-1) crystallization is accomplished after reaching 800 °C, while PLD grown thin films were completely crystallized already at ca. 300 °C.

Development of electron holes across the temperature-induced semiconductor-metal transition in Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-δ)(x, y = 0.2-0.8): a soft x-ray absorption spectroscopy study.

The x-ray absorption spectra of Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-δ) (BSCF) powders quenched in air from 623 and 1173 K were measured at the oxygen K and transition metal L(II,III) edges. All the samples show a predominantly Fe high spin ground state of 3d(5)L character, while the 3d(6)L Co ions are intermediate spin at 623 K and high spin at 1173 K. Further changes in the metal L(II,III) peaks caused by higher temperature quenching are attributed to changes in symmetry around the cations associated with oxygen loss. The oxygen K spectra show the development of unoccupied states just above the Fermi level for samples quenched from 1173 K. At 1173 K, Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-δ) shows metallic conductivity, while at 623 K it is a semiconductor; the states developed at high temperature with strong oxygen character are pathways for hole conductivity. Splitting of the transition metal 3d energy levels by the ligand field was observed in the oxygen K spectra, and the range for 10Dq is 1.6-1.8 eV, while the 3d bandwidth is 1.1-1.4 eV in samples quenched from 623 K. On the basis of the soft x-ray absorption results, the classification of Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-δ) as a material with a negative charge-transfer energy is proposed.

In vitro lifetime of dental ceramics under cyclic loading in water.

All-ceramic dental restorations exhibit enhanced esthetics and biocompatibility as compared to traditional metal-based prosthesis. However, long-term fatigue and subcritical crack growth in the presence of water and cyclic loading can decrease the strength of ceramic components over time. We investigated the cyclic fatigue in water of three dental materials currently used as frameworks in all-ceramic restorations: a 3 mol%-yttria partially stabilized zirconia (3Y-TZP, Cercon, Degudent GmbH), a Al(2)O(3)-ZrO(2)-Glass composite (Inceram-Zirconia, Vita Zahnfabrik GmbH) and a Li(2)O.2SiO(2) glass ceramic (Empress 2, Ivoclar Vivadent AG). Fatigue and fast fracture tests were performed to determine the Weibull distribution of lifetime and initial mechanical strength for each framework component. In spite of its noticeable susceptibility to fatigue in water, the 3Y-TZP material was found to be particularly suitable for the preparation of posterior all-ceramic bridges due to its high initial mechanical strength. Guidelines are provided for the selection of materials and the design of all-ceramic posterior bridges exhibiting lifetime longer than 20 years under severe wet and cyclic loading conditions.

Change of zeta potential of biocompatible colloidal oxide particles upon adsorption of bovine serum albumin and lysozyme.

The amounts of negatively charged bovine serum albumin and positively charged lysozyme adsorbed on alumina, silica, titania, and zirconia particles (diameters 73 to 271 nm) in aqueous suspensions are measured. The adsorbed proteins change the zeta potentials and the isoelectric points (IEP) of the oxide particles. The added to adsorbed protein ratios at pH 7.5 are compared with the protein treated particle zeta potentials. It is found that the amounts of adsorbed proteins on the alumina, silica, and titania (but not on the zirconia) particle surfaces are highly correlated with the zeta potential. For the slightly less hydrophilic zirconia particles high amounts of protein adsorption are observed even under repulsive electrostatic conditions. One reason could be that the hydrophobic effect plays a more important role for zirconia than electrostatic interaction.

Hepatocyte performance on different crystallographic faces of rutile.

The influence of crystallographic orientation of polished rutile single crystal surfaces of the (100), (110) and (111) orientation on hepatocyte performance was tested in cell culture over 3 days. Cell adhesion was observed on the titanium dioxide surfaces and their performance was measured by means of cell number attached (protein mass), cell viability (neutral red assays) and metabolic activity (thiazolyl tetrazolium bromide assay). Titanium dioxide displays no cytotoxic effects on hepatocytes, and shows a performance in the range of standard collagen-coated tissue culture polystyrene dish. The number of hepatocytes adhered on the different rutile surfaces were not significantly different to those on dense rutile polycrystalline ceramic. These findings suggest that hepatocytes do not recognize the specific differences of differently orientated rutile crystal surfaces.

Reliability and strength of all-ceramic dental restorations fabricated by direct ceramic machining (DCM).

All-ceramic dental bridges for the molar region are not yet available at reasonable costs. The novel direct ceramic machining (DCM) process allows an easy, reliable and rapid fabrication for all-ceramic dental restorations with high mechanical strength and good biocompatibility. In DCM, an enlarged framework is easily milled out of a pre-fabricated porous ceramic blank made of zirconia. After sintering to full density, no further time-consuming hard machining with diamond tools is needed. For individual esthetical requirements, the framework is coated with a veneer porcelain. Compared to the commercially available In-Ceram Alumina and IPS Empress2 restorations, the mechanical strength of zirconia frameworks is twice as high, allowing the restorations to bear the high mastication forces in the molar region. In terms of reliability, zirconia bridges fabricated by the DCM process are also superior to In-Ceram Alumina and IPS Empress2. A clinical study of three-unit dental bridges in the molar region found no problems after the first year of observation.

[Clinical study of zirconium oxide bridges in the posterior segments fabricated with the DCM system]. / Klinische Studie von Zirkonoxidbrücken im Seitenzahngebiet hergestellt mit dem DCM-System.

Today's dental reconstructive therapeutic concepts require restoration of high esthetic quality and excellent biocompatibility. Full ceramic reconstructions accomplish these requirements but only for anterior teeth and premolars. For all-ceramic bridges the mechanical strength was insufficient to withstand the posterior chewing forces. Frequently the interdental connectors cracked, and the only way to prevent these fractures was to overconture the connectors to a size of approx. 16 mm2. The high-tech ceramic zirconia is a potential alternative for three-to five-unit full ceramic bridges in the functionally loaded posterior segments. Experimental zirconia bridges which were fabricated using the DCM system (Direct Ceramic Machining System at the ETH Zurich, were tested in vitro. The frameworks were digitally enlarged by 20% and were easily milled from a presintered yet porous zirconia blank. After the milling process, the framework was densely sintered and shrank to its original size. Due to these positive in-vitro results a clinical investigation was started. 22 veneered zirconia bridges were luted; 19 molars and 25 premolars were prepared. The connectors, max. 7 mm2, of all these bridges, have been functionally loaded by antagonists. After a mean observation time of 385 days (307 days to 488 days), all 22 bridges did not show any cracks in the framework or in the veneering porcelain. The patients commented particularly on the low heat conduction rate of zirconia. The only endodontic problem which occurred could not be directly connected to the type of bridge framework. The reliability of zirconia bridges in this investigation was connected to the DCM-Process. No statement about other zirconia-systems can be made on the results of this study.

Syngas generation from n-butane with an integrated MEMS assembly for gas processing in micro-solid oxide fuel cell systems.

An integrated system of a microreformer and a carrier allowing for syngas generation from liquefied petroleum gas (LPG) for micro-SOFC application is discussed. The microreformer with an overall size of 12.7 mm × 12.7 mm × 1.9 mm is fabricated with micro-electro-mechanical system (MEMS) technologies. As a catalyst, a special foam-like material made from ceria-zirconia nanoparticles doped with rhodium is used to fill the reformer cavity of 58.5 mm(3). The microreformer is fixed onto a microfabricated structure with built-in fluidic channels and integrated heaters, the so-called functional carrier. It allows for thermal decoupling of the cold inlet gas and the hot fuel processing zone. Two methods for heating the microreformer are compared in this study: a) heating in an external furnace and b) heating with the two built-in heaters on the functional carrier. With both methods, high butane conversion rates of 74%-85% are obtained at around 550 °C. In addition, high hydrogen and carbon monoxide yields and selectivities are achieved. The results confirm those from classical lab reformers built without MEMS technology (N. Hotz et al., Chem. Eng. Sci., 2008, 63, 5193; N. Hotz et al., Appl. Catal., B, 2007, 73, 336). The material combinations and processing techniques enable syngas production with the present MEMS based microreformer with high performance for temperatures up to 700 °C. The functional carrier is the basis for a new platform, which can integrate the micro-SOFC membranes and the gas processing unit as subsystem of an entire micro-SOFC system.

Structural and material approaches to bone tissue engineering in powder-based three-dimensional printing.

This article reviews the current state of knowledge concerning the use of powder-based three-dimensional printing (3DP) for the synthesis of bone tissue engineering scaffolds. 3DP is a solid free-form fabrication (SFF) technique building up complex open porous 3D structures layer by layer (a bottom-up approach). In contrast to traditional fabrication techniques generally subtracting material step by step (a top-down approach), SFF approaches allow nearly unlimited designs and a large variety of materials to be used for scaffold engineering. Today's state of the art materials, as well as the mechanical and structural requirements for bone scaffolds, are summarized and discussed in relation to the technical feasibility of their use in 3DP. Advances in the field of 3DP are presented and compared with other SFF methods. Existing strategies on material and design control of scaffolds are reviewed. Finally, the possibilities and limiting factors are addressed and potential strategies to improve 3DP for scaffold engineering are proposed.