Proton conductivity of mesoporous sol-gel zirconium phosphates for fuel cell applications

Zirconium phosphate has been extensively studied as a proton conductor for proton exchange membrane (PEM) fuel cell applications. Here we report the synthesis of mesoporous, templated sol-gel zirconium phosphate for use in PEM applications in an effort to determine its suitability for use as a surface functionalised, solid acid proton conductor in the future. Mesoporous zirconium phosphates were synthesised using an acid-base pair mechanism with surface areas between 78 and 177 m(2) g(-1) and controlled pore sizes in the range of 2-4 nm. TEM characterisation confirmed the presence of a wormhole like pore structure. The conductivity of such materials was up to 4.1 x 10(-6) S cm(-1) at 22degreesC and 84% relative humidity (RH), while humidity reduction resulted in a conductivity decrease by more than an order of magnitude. High temperature testing on the samples confirmed their dependence on hydration for proton conduction and low hydroscopic nature. It was concluded that while the conductivity of these materials is low compared to Nafion, they may be a good candidate as a surface functionalised solid acid proton conductor due to their high surface area, porous structure and inherent ability to conduct protons.

Enhanced glass-forming ability of a Zr-based bulk metallic glass with yttrium doping

A significant enhancement in glass formation in a newly developed Zr51Cu20.7Ni12Al16.3 alloy has been achieved by yttrium doping. With just 0.5 at.% yttrium doping, the critical diameter of the as-cast alloys for glass formation has been increased from 3 mm to at least 10 mm. In the undoped, large-sized alloys, massive oxygen stabilized crystalline phases are observed but disappear in yttrium doped alloys. Very small amounts of stable alpha-Y2O3 phases found in the yttrium doped alloys, and their negligible effect on the metallic glasses' properties, provide a superior solution to achieve metallic glasses with a high glass formability. (c) 2006 Elsevier B.V. All rights reserved.

Zirconium alloying and grain refinement of magnesium alloys

Factors that influence alloying zirconium to magnesium with a Mg-33.3Zr master alloy and the subsequent grain refinement are discussed based on a large number of experiments conducted at the laboratory scale (up to 30 kg of melt). It is shown that the zirconium particles released from the Zirmax(R) master alloy must be brought into thorough contact with the melt by an appropriate stirring process in order to attain a good dissolution of zirconium. The influence of alloying temperature on the recovery of zirconium was found to be negligible in the range from 680 to 780 degreesC. An ideal zirconium alloying process should end up with both high soluble and high total zirconium in the melt in order to achieve the best grain refinement in the final alloy. The distribution of zirconium in the final alloy microstructure is inhomogeneous and almost all of the zirconium in solution is concentrated in zirconium-rich cores in the microstructure.

A new zirconium-rich master alloy for the grain refinement of magnesium alloys

A new zirconium-rich magnesium-zirconium master alloy (designated AM-cast) has been developed by the CRC for Cast Metals Manufacturing in collaboration with Australian Magnesium Corporation for use as a grain refiner for magnesium alloys that do not contain aluminium. This work describes the microstructural characteristics of this new grain refiner and its grain refining ability when added to different magnesium alloys under various conditions (alloying temperature from 680 °C to 750 °C; weight of melt from 1 kg to 150 kg and sample thickness from 7 mm to 62 mm). Owing to its highly alloyable microstructure, AM-cast can be readily introduced into molten magnesium at any temperature when assisted by a few minutes of stirring or puddling. Little sludge has been found at the bottom of the alloying vessel in these trials due to the fine zirconium particles contained in the master alloy. The recovery of zirconium is normally in the range from 40% to 60% with respect to 1% zirconium addition as the master alloy. It is shown that this new master alloy is an excellent grain refiner for aluminium-free magnesium alloys.

Effects of rare-earth co-doping on the local structure of rare-earth phosphate glasses using high and low energy X-ray diffraction

Rare-earth co-doping in inorganic materials has a long-held tradition of facilitating highly desirable optoelectronic properties for their application to the laser industry. This study concentrates specifically on rare-earth phosphate glasses, (R2O3)x(R'2O3)y(P2O5)1-(x+y), where (R, R') denotes (Ce, Er) or (La, Nd) co-doping and the total rare-earth composition corresponds to a range between metaphosphate, RP3O9, and ultraphosphate, RP5O14. Thereupon, the effects of rare-earth co-doping on the local structure are assessed at the atomic level. Pair-distribution function analysis of high-energy X-ray diffraction data (Qmax = 28 Å-1) is employed to make this assessment. Results reveal a stark structural invariance to rare-earth co-doping which bears testament to the open-framework and rigid nature of these glasses. A range of desirable attributes of these glasses unfold from this finding; in particular, a structural simplicity that will enable facile molecular engineering of rare-earth phosphate glasses with 'dial-up' lasing properties. When considered together with other factors, this finding also demonstrates additional prospects for these co-doped rare-earth phosphate glasses in nuclear waste storage applications. This study also reveals, for the first time, the ability to distinguish between P-O and PO bonding in these rare-earth phosphate glasses from X-ray diffraction data in a fully quantitative manner. Complementary analysis of high-energy X-ray diffraction data on single rare-earth phosphate glasses of similar rare-earth composition to the co-doped materials is also presented in this context. In a technical sense, all high-energy X-ray diffraction data on these glasses are compared with analogous low-energy diffraction data; their salient differences reveal distinct advantages of high-energy X-ray diffraction data for the study of amorphous materials. © 2013 The Owner Societies.

Precipitation studies on alloys from the system copper chromium zirconium

The precipitation reactions occurring in a series of copper-based alloys selected from the system copper-chromium-zirconium have been studied by resistometric and metallographic techniques. A survey of the factors influencing the development of copper-based alloys for high strength, high conductivity applications is followed by a more general review of contemporary materials, and illustrates that the most promising alloys are those containing chromium and zirconium. The few systematic attempts to study alloys from this system have been collated, discussed, and used as a basis for the selection of four alloy compositions viz:- Cu - 0.4% Cr Cu - 0.24. Zr Cu - 0. 3% Cr - 0.1% Zr Cu - 0.2% Cr - 0.2% Zr A description of the experimental techniques used to study the precipitation behaviour of these materials is preceeded by a discussion of the currently accepted theories relating to precipitate nucleation and growth. The experimental results are presented and discussed for each of the alloys independently, and are then treated jointly to obtain an overall assessment of the way in which the precipitation kinetics, metallography and mechanical properties vary with alloy composition and heat treatment. The metastable solid solution of copper-chromium is found to decompose by the rejection of chromium particles which maintain a coherent interface and a Kurdjumov-Sachs type crystallographic orientation relationship with the copper matrix. The addition of 0.1% zirconium to the alloy retards the rate of transformation by a factor of ten and modifies the dispersion characteristics of the precipitate without markedly altering the morphology. Further additions of zirconium lead to the growth of stacking faults during ageing, which provide favourable nucleation sites for the chromium precipitate. The partial dislocations bounding such stacking faults are also found to provide mobile heterogeneous nucleation sources for the precipitation reactions occurring in copper-zirconium.

Zirconium phosphate supported tungsten oxide solid acid catalysts for the esterification of palmitic acid

A series of zirconium phosphate supported WOx solid acid catalysts with W loadings from 1–25 wt% have been prepared on high surface area zirconium phosphate by a surface grafting method. Catalysts were characterized by N2 adsorption, FTIR, Raman, UV-Vis, 31P MAS NMR, pyridine TPD and X-ray methods. Spectroscopic measurements suggest a Keggin-type structure forms on the surface of zirconium phosphate as a ([triple bond, length as m-dash]ZrOH2+)(ZrPW11O405−) species. All catalysts show high activity in palmitic acid esterification with methanol. These materials can be readily separated from the reaction system for re-use, and are resistant to leaching of the active heteropolyacid, suggesting potential industrial applications in biodiesel synthesis. © The Royal Society of Chemistry 2006.

Heavy ion irradiation effects in zirconium nitride

Polycrystalline zirconium nitride (ZrN) samples were irradiated with He +, Kr ++, and Xe ++ ions to high (>1·10 16 ions/cm 2) fluences at ∼100 K. Following ion irradiation, transmission electron microscopy (TEM) and grazing incidence X-ray diffraction (GIXRD) were used to analyze the microstructure and crystal structure of the post-irradiated material. For ion doses equivalent to approximately 200 displacements per atom (dpa), ZrN was found to resist any amorphization transformation, based on TEM observations. At very high displacement damage doses, GIXRD measurements revealed tetragonal splitting of some of the diffraction maxima (maxima which are associated with cubic ZrN prior to irradiation). In addition to TEM and GIXRD, mechanical property changes were characterized using nanoindentation. Nanoindentation revealed no change in elastic modulus of ZrN with increasing ion dose, while the hardness of the irradiated ZrN was found to increase significantly with ion dose. Finally, He + ion implanted ZrN samples were annealed to examine He gas retention properties of ZrN as a function of annealing temperature. He gas release was measured using a residual gas analysis (RGA) spectrometer. RGA measurements were performed on He-implanted ZrN samples and on ZrN samples that had also been irradiated with Xe ++ ions, in order to introduce high levels of displacive radiation damage into the matrix. He evolution studies revealed that ZrN samples with high levels of displacement damage due to Xe implantation, show a lower temperature threshold for He release than do pristine ZrN samples.

Influence of La-doping on phase transformation and photocatalytic properties of ZnTiO3 nanoparticles synthesized via modified sol-gel method

Non-doped and La-doped ZnTiO3 nanoparticles were successfully synthesized via a modified sol–gel method. The synthesized nanoparticles were structurally characterized by PXRD, UV-vis DRS, FT-IR, SEM-EDS, TEM, Raman and photoluminescence spectroscopy. The results show that doping of La into the framework of ZnTiO3 has a strong influence on the physico-chemical properties of the synthesized nanoparticles. XRD results clearly show that the non-doped ZnTiO3 exhibits a hexagonal phase at 800 °C, whereas the La-doped ZnTiO3 exhibits a cubic phase under similar experimental conditions. In spite of the fact that it has a large ionic radius, the La is efficiently involved in the evolution process by blocking the crystal growth and the cubic to hexagonal transformation in ZnTiO3. Interestingly the absorption edge of the La-doped ZnTiO3 nanoparticles shifted from the UV region to the visible region. The photocatalytic activity of the La-doped ZnTiO3 nanoparticles was evaluated for the degradation of Rhodamine B under sunlight irradiation. The optimum photocatalytic activity was obtained for 2 atom% La-doped ZnTiO3, which is much higher than that of the non-doped ZnTiO3 as well as commercial N-TiO2. A possible mechanism for the degradation of Rhodamine B over La-doped ZnTiO3 was also discussed by trapping experiments. More importantly, the reusability of these nanoparticles is high. Hence La-doped ZnTiO3 nanoparticles can be used as efficient photocatalysts for environmental applications.

Treinta años del control del doping en los hipódromos españoles: 1983-2014

El deseo de lograr la victoria con el menor esfuerzo o la garantía de la derrota segura del rival, es un sentimiento tan antiguo como la historia del deporte, para conseguirlo a lo largo del tiempo los métodos, las formas, las sustancias para alterar el rendimiento físico han evolucionado, aunque la intención se mantiene de forma invariable. En nuestros días el doping está presente en la mayoría de los deportes y las carreras de caballos no son una excepción. Por esta razón con el fin de salvaguardar el bienestar animal, la limpieza del deporte y la protección del juego en los hipódromos españoles se realiza “el control del doping”, se practica a los caballos PSI de carreras, hasta ahora, siguiendo las directrices del “Código de la Sociedad Fomento de la Cría Caballar en España” (SFCCE), de esta forma tratamos de impedir el uso fraudulento de sustancias dopantes o el abuso de las sustancias medicamentosas. El control del doping en los hipódromos españoles empezó en 1960, gracias a un acuerdo entre la SFCCE y la Cátedra de Farmacología y Toxicología de la Facultad de Veterinaria de la Universidad Complutense, de lo sucedido en estos primeros años incluimos en nuestro trabajo un estudio crítico. En 1983 la SFCCE se modernizó y delegó la responsabilidad de los análisis de orina y sangre a un laboratorio homologado por la International Federation of Horseracing Authorities (IFHA). Por esta razón, en nuestro trabajo aportamos los datos correspondientes al control del doping de los caballos de carreras en España desde 1983 y hasta diciembre de 2014...

Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius

In this paper, we use density functional theory corrected for on-site Coulomb interactions (DFT + U) and hybrid DFT (HSE06 functional) to study the defects formed when the ceria (110) surface is doped with a series of trivalent dopants, namely, Al3+, Sc3+, Y3+, and In 3+. Using the hybrid DFT HSE06 exchange-correlation functional as a benchmark, we show that doping the (110) surface with a single trivalent ion leads to formation of a localized MCe / + O O • (M = the 3+ dopant), O- hole state, confirming the description found with DFT + U. We use DFT + U to investigate the energetics of dopant compensation through formation of the 2MCe ′ +VO ̈ defect, that is, compensation of two dopants with an oxygen vacancy. In conjunction with earlier work on La-doped CeO2, we find that the stability of the compensating anion vacancy depends on the dopant ionic radius. For Al3+, which has the smallest ionic radius, and Sc3+ and In3+, with intermediate ionic radii, formation of a compensating oxygen vacancy is stable. On the other hand, the Y3+ dopant, with an ionic radius close to that of Ce4+, shows a positive anion vacancy formation energy, as does La3+, which is larger than Ce4+ (J. Phys.: Condens. Matter 2010, 20, 135004). When considering the resulting electronic structure, in Al3+ doping, oxygen hole compensation is found. However, Sc 3+, In3+, and Y3+ show the formation of a reduced Ce3+ cation and an uncompensated oxygen hole, similar to La3+. These results suggest that the ionic radius of trivalent dopants strongly influences the final defect formed when doping ceria with 3+ cations. In light of these findings, experimental investigations of these systems will be welcome.