Photocatalytic evolution of hydrogen and oxygen from ceramic wafers of commercial titanias

Several commercial titania photocatalyst powders were formed into thin (ca. 350 mu m), 25 mm diameter ceramic wafers, sputter deposited with Pt on one side. The activities of each of the ceramic wafers were tested for hydrogen and oxygen evolution from aqueous sacrificial systems. The commercial sample PC50 (Millennium Chemicals, UK) yielded reproducible ceramic wafers with high activity for water photoreduction. Many of the ceramic wafers displayed low water photo-oxidation activities; however, these were greatly increased with addition of a NiO co-catalyst. In a selected case, hydrogen evolution activity was compared between a PC50 wafer and an identical weight of platinised PC50 powder suspension. (C) 2010 Elsevier B.V. All rights reserved.

A Lead-Free and High-Energy Density Ceramic for Energy Storage Applications

In this work, we demonstrate a very high-energy density and high-temperature stability capacitor based on SrTiO3-substituted BiFeO3 thin films. An energy density of 18.6 J/cm3 at 972 kV/cm is reported. The temperature coefficient of capacitance (TCC) was below 11% from room temperature up to 200°C. These results are of practical importance, because it puts forward a promising novel and environmentally friendly, lead-free material, for high-temperature applications in power electronics up to 200°C. Applications include capacitors for low carbon vehicles, renewable energy technologies, integrated circuits, and for the high-temperature aerospace sector. © 2013 Crown copyright

Fracture strength of machined ceramic crowns as a function of tooth preparation design and the elastic modulus of the cement

Objectives: To determine, by means of static fracture testing the effect of the tooth preparation design and the elastic modulus of the cement on the structural integrity of the cemented machined ceramic crown-tooth complex. 
Methods: Human maxillary extracted premolar teeth were prepared for all-ceramic crowns using two preparation designs; a standard preparation in accordance with established protocols and a novel design with a flat occlusal design. All-ceramic feldspathic (Vita MK II) crowns were milled for all the preparations using a CAD/CAM system (CEREC-3). The machined all-ceramic crowns were resin bonded to the tooth structure using one of three cements with different elastic moduli: Super-Bond C&B, Rely X Unicem and Panavia F 2.0. The specimens were subjected to compressive force through a 4 mm diameter steel ball at a crosshead speed of 1 mm/min using a universal test machine (Loyds Instrument Model LRX.). The load at the fracture point was recorded for each specimen in Newtons (N). These values were compared to a control group of unprepared/unrestored teeth. 
Results: There was a significant difference between the control group, with higher fracture strength, and the cemented samples regardless of the occlusal design and the type of resin cement. There was no significant difference in mean fracture load between the two designs of occlusal preparation using Super-Bond C&B. For the Rely X Unicem and Panavia F 2.0 cements, the proposed preparation design with a flat occlusal morphology provides a system with increased fracture strength. 
Significance: The proposed novel flat design showed less dependency on the resin cement selection in relation to the fracture strength of the restored tooth. The choice of the cement resin, with respect to its modulus of elasticity, is more important in the anatomic design than in the flat design. © 2013 Academy of Dental Materials.

Advanced Ceramic Substrate with Ordered and Designed Micro-Structure for Applications in Automotive Catalysts

This study describes an innovative monolith structure designed for applications in automotive catalysis using an advanced manufacturing approach developed at Imperial College London. The production process combines extrusion with phase inversion of a ceramic-polymer-solvent mixture in order to design highly ordered substrate micro-structures that offer improvements in performance, including reduced PGM loading, reduced catalyst ageing and reduced backpressure.

This study compares the performance of the novel substrate for CO oxidation against commercially available 400 cpsi and 900 cpsi catalysts using gas concentrations and a flow rate equivalent to those experienced by a full catalyst brick when attached to a vehicle. Due to the novel micro-structure, no washcoat was required for the initial testing and 13 g/ft3 of Pd was deposited directly throughout the substrate structure in the absence of a washcoat.

Initial results for CO oxidation indicate that the advanced micro-structure leads to enhanced conversion efficiency. Despite an 79% reduction in metal loading and the absence of a washcoat, the novel substrate sample performs well, with a light-off temperature (LOT) only 15 °C higher than the commercial 400 cpsi sample.

To test the effects of catalyst ageing on light-off temperature, each sample was aged statically at a temperature of 1000 °C, based on the Bench Ageing Time (BAT) equation. The novel substrate performed impressively when compared to the commercial samples, with a variation in light-off temperature of only 3% after 80 equivalent hours of ageing, compared to 12% and 25% for the 400 cpsi and 900 cpsi monoliths, respectively.

A simple and low-cost method for the preparation of self-supported TiO2-WO3 ceramic heterojunction wafers

Robust, bilayer heterojunction photodiodes of TiO₂-WO₃ were prepared successfully by a simple, low-cost powder pressing technique followed by heat-treatment. Exclusive photoirradiation of the TiO₂ side of the photodiode resulted in a rapid colour change (dark blue) on the WO₃ surface as a result of reduction of W⁶⁺ to W⁵⁺ (confirmed by X-ray photoelectron spectroscopy). This colour was long lived and shown to be stable in a dry environment in air for several hours. A similar photoirradiation experiment in the presence of a mask showed that charge transfer across the heterojunction occurred approximately normal to the TiO₂ surface, with little smearing out of the mask image. As a result of the highly efficient vectorial charge separation, the photodiodes showed a tremendous increase in photocatalytic activity for the degradation of stearic acid, compared to wafers of the respective individual materials when tested separately.

Hydrogen-permeation characteristics of a SrCeO3-based ceramic separation membrane:Thermal, ageing and surface-modification effects

Dense ceramics with mixed protonic-electronic conductivity are of considerable interest for the separation and purification of hydrogen and as electrochemical reactors. In this work, the hydrogen permeability of a Sr_0.97Ce_0.9Yb_0.1O_{3 - δ} (SCYb) membrane with a porous Pt catalytic layer on the hydrogen feed-exposed side has been studied over the temperature range 500-804 °C employing Ar as the permeate sweep gas. A SiO₂-B₂O₃-BaO-MgO-ZnO-based glass-ceramic sealant was successfully employed to seal the membrane to the dual-chamber reactor. After 14 h of exposure to 10% H₂:90% N₂ at 804 °C, the H₂ flux reached a maximum of 33 nmol cm^{- 2} s^{- 1}, over an order of magnitude higher than that obtained on membranes of similar thickness without surface modification. The permeation rate then decreased slowly and moderately on annealing at 804 °C over a further 130 h. Thereafter, the flux was both reproducible and stable on thermal cycling in the range 600-804 °C. The results indicate an important role of superficial activation processes in the flux rate and suggest that hydrogen fluxes can be further optimised in cerate-based perovskites. © 2009 Elsevier B.V. All rights reserved.

Electrochemical promotion of catalysis controlled by chemical potential difference across a mixed ionic-electronic conducting ceramic membrane - An example of wireless NEMCA

A La_0.6Sr_0.4Co_0.2F_0.8O₃ mixed ionic electronic conducting (MIEC) membrane was used in a dual chamber reactor for the promotion of the catalytic activity of a platinum catalyst for ethylene oxidation. By controlling the oxygen chemical potential difference across the membrane, a driving force for oxygen ions to migrate across the membrane and backspillover onto the catalyst surface is established. The reaction is then promoted by the formation of a double layer of oxide anions on the catalyst surface. Thelectronic conductivity of the membrane material eliminates the need for an external circuit to pump the promoting oxide ion species through the membrane and onto the catalyst surface. This renders this "wireless" system simpler and more amenable for large-scale practical application. Preliminary experiments show that the reaction rate of ethylene oxidation can indeed be promoted by almost one order of magnitude upon exposure to an oxygen atmosphere on the sweep side of the membrane reactor, and thus inducing an oxygen chemical potential difference across the membrane, as compared to the rate under an inert sweep gas. Moreover, the rate does not return to its initial unpromoted value upon cessation of the oxygen flow on the sweep side, but remains permanently promoted. A number of comparisons are drawn between the classical electrochemical promotion that utilises an external circuit and the "wireless" system that utilises chemical potential differences. In addition a 'surface oxygen capture' model is proposed to explain the permanent promotion of the catalyst activity. © 2007 Springer Science+Business Media, LLC.

Anodes for protonic ceramic fuel cells (PCFCs)

One of the more promising possibilities for future “green” electrical energy generation is the protonic ceramic fuel cell (PCFC). PCFCs offer a low-pollution technology to generate electricity electrochemically with high efficiency. Reducing the operating temperature of solid oxide fuel cells (SOFCs) to the 500-700°C range is desirable to reduce fabrication costs and improve overall longevity. This aim can be achieved by using protonic ceramic fuel cells (PCFCs) due to their higher electrolyte conductivity at these temperatures than traditional ceramic oxide-ion conducting membranes. This thesis deals with the state of the art Ni-BaZr0.85Y0.15O3-δ cermet anodes for PCFCs. The study of PCFCs is in its initial stage and currently only a few methods have been developed to prepare suitable anodes via solid state mechanical mixing of the relevant oxides or by combustion routes using nitrate precursors. This thesis aims to highlight the disadvantages of these traditional methods of anode preparation and to, instead, offer a novel, efficient and low cost nitrate free combustion route to prepare Ni-BaZr0.85Y0.15O3-δ cermet anodes for PCFCs. A wide range of techniques mainly X-ray diffraction (XRD), scanning electron microscopy (SEM), environmental scanning electron microscopy, (ESEM) and electrochemical impedance spectroscopy (EIS) were employed in the cermet anode study. The work also offers a fundamental examination of the effect of porosity, redox cycling behaviour, involvement of proton conducting oxide phase in PCFC cermet anodes and finally progresses to study the electrochemical performance of a state of the art anode supported PCFC. The polarisation behaviour of anodes has been assessed as a function of temperature (T), water vapour (pH2O), hydrogen partial pressures (pH2) and phase purity for electrodes of comparable microstructure. The impedance spectra generally show two arcs at high frequency R2 and low frequency R3 at 600 °C, which correspond to the electrode polarisation resistance. Work shows that the R2 and R3 terms correspond to proton transport and dissociative H2 adsorption on electrode surface, respectively. The polarization resistance of the cermet anode (Rp) was shown to be significantly affected by porosity, with the PCFC cermet anode with the lowest porosity exhibiting the lowest Rp under standard operating conditions. This result highlights that porogens are not required for peak performance in PCFC anodes, a result contrary to that of their oxide-ion conducting anode counterparts. In-situ redox cycling studies demonstrate that polarisation behaviour was drastically impaired by redox cycling. In-situ measurements using an environmental scanning electron microscopy (ESEM) reveal that degradation proceeds due to volume expansion of the Ni-phase during the re-oxidation stage of redox cycling.The anode supported thin BCZY44 based protonic ceramic fuel cell, formed using a peak performing Ni-BaZr0.85Y0.15O3-δ cermet anode with no porogen, shows promising results in fuel cell testing conditions at intermediate temperatures with good durability and an overall performance that exceeds current literature data.

Surface reactivity enhancement of silica-based glass-ceramic scaffolds

A paradigm shift is taking place from using transplanting tissue and synthetic implants to a tissue engineering approach that aims to regenerate damaged tissues by combining cells from the body with highly porous scaffold biomaterials, which act as templates, guiding the growth of new tissue. The central focus of this thesis was to produce porous glass and glass-ceramic scaffolds that exhibits a bioactive and biocompatible behaviour with specific surface reactivity in synthetic physiological fluids and cell-scaffold interactions, enhanced by composition and thermal treatments applied. Understanding the sintering behaviour and the interaction between the densification and crystallization processes of glass powders was essential for assessing the ideal sintering conditions for obtaining a glass scaffolds for tissue engineering applications. Our main goal was to carry out a comprehensive study of the bioactive glass sintering, identifying the powder size and sintering variables effect, for future design of sintered glass scaffolds with competent microstructures. The developed scaffolds prepared by the salt sintering method using a 3CaO.P2O5 - SiO2 - MgO glass system, with additions of Na2O with a salt, NaCl, exhibit high porosity, interconnectivity, pore size distribution and mechanical strength suitable for bone repair applications. The replacement of 6 % MgO by Na2O in the glass network allowed to tailor the dissolution rate and bioactivity of the glass scaffolds. Regarding the biological assessment, the incorporation of sodium to the composition resulted in an inibition cell response for small periods. Nevertheless it was demonstrated that for 21 days the cells response recovered and are similar for both glass compositions. The in vitro behaviour of the glass scaffolds was tested by introducing scaffolds to simulated body fluid for 21 days. Energy-dispersive Xray spectroscopy and SEM analyses proved the existence of CaP crystals for both compositions. Crystallization forming whitlockite was observed to affect the dissolution behaviour in simulated body fluid. By performing different heat treatments, it was possible to control the bioactivity and biocompatability of the glass scaffolds by means of a controlled crystallization. To recover and tune the bioactivity of the glass-ceramic with 82 % crystalline phase, different methods have been applied including functionalization using 3- aminopropyl-triethoxysilane (APTES). The glass ceramic modified surface exhibited an accelerated crystalline hydroxyapatite layer formation upon immersion in SBF after 21 days while the as prepared glass-ceramic had no detected formation of calcium phosphate up to 5 months. A sufficient mechanical support for bone tissue regeneration that biodegrade later at a tailorable rate was achievable with the glass–ceramic scaffold. Considering the biological assessment, scaffolds demonstrated an inductive effect on the proliferation of cells. The cells showed a normal morphology and high growth rate when compared to standard culture plates. This study opens up new possibilities for using 3CaO.P2O5–SiO2–MgO glass to manufacture various structures, while tailoring their bioactivity by controlling the content of the crystalline phase. Additionally, the in vitro behaviour of these structures suggests the high potential of these materials to be used in the field of tissue regeneration.

Alkaline-earth aluminosilicate-based glass and glass-ceramic sealants for functional applications

The planar design of solid oxide fuel cell (SOFC) is the most promising one due to its easier fabrication, improved performance and relatively high power density. In planar SOFCs and other solid-electrolyte devices, gas-tight seals must be formed along the edges of each cell and between the stack and gas manifolds. Glass and glass-ceramic (GC), in particular alkaline-earth alumino silicate based glasses and GCs, are becoming the most promising materials for gas-tight sealing applications in SOFCs. Besides the development of new glass-based materials, new additional concepts are required to overcome the challenges being faced by the currently existing sealant technology. The present work deals with the development of glasses- and GCs-based materials to be used as a sealants for SOFCs and other electrochemical functional applications. In this pursuit, various glasses and GCs in the field of diopside crystalline materials have been synthesized and characterized by a wide array of techniques. All the glasses were prepared by melt-quenching technique while GCs were produced by sintering of glass powder compacts at the temperature ranges from 800−900 ºC for 1−1000 h. Furthermore, the influence of various ionic substitutions, especially SrO for CaO, and Ln2O3 (Ln=La, Nd, Gd, and Yb), for MgO + SiO2 in Al-containing diopside on the structure, sintering and crystallization behaviour of glasses and properties of resultant GCs has been investigated, in relevance with final application as sealants in SOFC. From the results obtained in the study of diopside-based glasses, a bilayered concept of GC sealant is proposed to overcome the challenges being faced by (SOFCs). The systems designated as Gd−0.3 (in mol%: 20.62MgO−18.05CaO−7.74SrO−46.40SiO2−1.29Al2O3 − 2.04 B2O3−3.87Gd2O3) and Sr−0.3 (in mol%: 24.54 MgO−14.73 CaO−7.36 SrO−0.55 BaO−47.73 SiO2−1.23 Al2O3−1.23 La2O3−1.79 B2O3−0.84 NiO) have been utilized to realize the bi-layer concept. Both GCs exhibit similar thermal properties, while differing in their amorphous fractions, revealed excellent thermal stability along a period of 1,000 h. They also bonded well to the metallic interconnect (Crofer22APU) and 8 mol% yttrium stabilized zirconium (8YSZ) ceramic electrolyte without forming undesirable interfacial layers at the joints of SOFC components and GC. Two separated layers composed of glasses (Gd−0.3 and Sr−0.3) were prepared and deposited onto interconnect materials using a tape casting approach. The bi-layered GC showed good wetting and bonding ability to Crofer22APU plate, suitable thermal expansion coefficient (9.7–11.1 × 10–6 K−1), mechanical reliability, high electrical resistivity, and strong adhesion to the SOFC componets. All these features confirm the good suitability of the investigated bi-layered sealant system for SOFC applications.

Al-doped ZnO ceramic sputtering targets based on nanocrystalline powders produced by emulsion detonation synthesis – deposition and application as a transparent conductive oxide material

Transparent conducting oxides (TCOs) have been largely used in the optoelectronic industry due to their singular combination of low electrical resistivity and high optical transmittance. They are usually deposited by magnetron sputtering systems being applied in several devices, specifically thin film solar cells (TFSCs). Sputtering targets are crucial components of the sputtering process, with many of the sputtered films properties dependent on the targets characteristics. The present thesis focuses on the development of high quality conductive Al-doped ZnO (AZO) ceramic sputtering targets based on nanostructured powders produced by emulsion detonation synthesis method (EDSM), and their application as a TCO. In this sense, the influence of several processing parameters was investigated from the targets raw-materials synthesis to the application of sputtered films in optoelectronic devices. The optimized manufactured AZO targets present a final density above 99 % with controlled grain size, an homogeneous microstructure with a well dispersed ZnAl2O4 spinel phase, and electrical resistivities of ~4 × 10-4 Ωcm independently on the Al-doping level among 0.5 and 2.0 wt. % Al2O3. Sintering conditions proved to have a great influence on the properties of the targets and their performance as a sputtering target. It was demonstrated that both deposition process and final properties of the films are related with the targets characteristics, which in turn depends on the initial powder properties. In parallel, the influence of several deposition parameters in the film´s properties sputtered from these targets was investigated. The sputtered AZO TCOs showed electrical properties at room temperature that are superior to simple oxides and comparable to a reference TCO – indium tin oxide (ITO), namely low electrical resistivity of 5.45 × 10-4 Ωcm, high carrier mobility (29.4 cm2V-1s-1), and high charge carrier concentration (3.97 × 1020 cm-3), and also average transmittance in the visible region > 80 %. These superior properties allowed their successful application in different optoelectronic devices.

Dielectric Properties of Ba5Nb4O15 Ceramic

Ceramic dielectrics with high dielectric constant in the microwave frequency range are used as filters, oscillators [I], etc. in microwave integrated circuits (MICs) particularly in modern communication systems like cellular telephones and satellite communications. Such ceramics, known as 'dielectric resonators (DRs),donot only offer miniaturisation and reduce the weight of the microwave components. but also improve the efficiency of MICs