Molecular Dynamics Approach to the Physical Mixture of In2O3 and ZrO2: Defect Formation and Ionic Diffusion.

Recent research on the use of physical mixtures In2O3-ZrO2 has raised interesting questions as to how their combination enhances catalytic activity and selectivity. Specifically, the relationship between oxygen diffusion and defect formation and the epitaxial tension in the mixture should be further investigated. In this study, we aim to clarify some of these relationships through a molecular dynamics approach. Various potentials for the two oxides are compared and selected to describe the physical mixture of In2O3 and ZrO2. Different configurations of each single crystal and their physical mixture are simulated, and oxygen defect formation and diffusion are measured and compared. Significant oxygen defect formation is found in both crystals. In2O3 seems to be stabilized by the mixture, while ZrO2 is destabilized. Similar results were found for the ZrO2 doping with In and ln2O3 doping with Zr. The results explain the high activity and selectivity catalyst activity of the mixture for the production of isobutylene from ethanol.

120 MeV swift Au9+ion induced phase transition in ZrO2: monoclinic to tetragonal and cubic to tetragonal structure.

This study reports the effect of 120 MeV swift Au9+ion irradiation on the structures of monoclinic, tetragonal and cubic ZrO2, probed through x-ray diffraction (XRD) and Raman spectroscopy. Three phases of ZrO2were prepared using the solution combustion method. The tetragonal and cubic phases of ZrO2were stabilized at room temperature by adding 6% and 10% of yttrium ions, respectively. Both the XRD and Raman results confirm the partial phase transition from monoclinic to tetragonal, which was approximately 74%. Tetragonal ZrO2is stable under 120 MeV Au9+ion irradiation. Interestingly, a phase transition from cubic to tetragonal ZrO2was observed under 120 MeV Au9+ion irradiation. The roles of transient temperature, defects and strain in the lattice induced by swift heavy ions are discussed. This study reveals the structural stability of different phases of ZrO2under swift heavy ion irradiation and should be helpful in choosing potential hosts for various applications such as inert fuel matrix inside the core of nuclear reactors, oxygen sensors and accelerators, and radiation shielding.

Zn-doping and oxygen vacancy effects on the reactivity and properties of monoclinic and tetragonal ZrO2: a DFT study.

Zirconia oxide (ZrO2) is a material that has aroused great interest in the scientific community for its general use in various technological applications, such as fuel cells, solar cells, electronic devices, catalysis, dental biomaterial and ceramics. When it is applied as a catalyst, the doping and vacancy effects of their crystalline phases are important properties to guide new developments. This work investigates tetragonal and monoclinic crystalline phases of the Zn-doped ZrO2 by periodic density functional calculations. Changes in the electronic and acid-basic properties were performed by Bader charge analysis, the density of states calculations (DOS) and the projected density of states (PDOS). The formation of oxygen vacancies was also evaluated. The calculated oxygen vacancy formation energies indicate that it is much easier to generate oxygen vacancy in the Zn-doped ZrO2 than in the pure material; in addition, oxygen vacancy formation is favored in the monoclinic phase. Bader charge analyses and projected density of states indicated that the doping of ZrO2 with Zn creates more basic and acid sites. The most stable material is the Zn-doped 3-fold coordinated Zr atom of the m-ZrO2, which can be used for future developments and applications.

Visualization of the Final Stage of Sintering in Nanoceramics with Atomic Resolution.

The deep understanding of the sintering mechanism is pivotal to optimizing denser ceramics production. Although several models explain the sintering satisfactorily on the micrometric scale, the extrapolation for nanostructured systems is not trivial. Aiming to provide additional information about the particularities of the sintering at the nanoscale, we performed in situ experiments using high-resolution transmission electron microscopy (HRTEM). We studied the pore elimination process in a ZrO2 thin film and identified a high anisotropic pore elimination. Interestingly, there is a redistribution of the atoms from the rough surface in the solid-gas surface, followed by the atom attachment in a faceted surface. Finally, we found evidence of the pore acting as a pin, reducing the GB mobility. These findings certainly can contribute to enhance the kinetic models to describe the densification process of systems at the nanoscale.

Catalytic hydrogenation of nitrate in water: improvement of the activity and selectivity to N2 by using Rh(III)-hexamolybdate supported on ZrO2-Al2O3.

Catalysts prepared on ZrO2, Al2O3 and ZrO2-Al2O3 (ZrAl-10) supported with Anderson heteropolyanion (RhMo6) as active phase were investigated for the elimination of NO3- from water. Raman characterization of pure and supported RhMo6 phase showed the presence of polymolybdic species of different degrees of complexity when RhMo6 was supported. The temperature-programmed reduction study revealed the synergic effect between Rh and Mo species, through which the reducibility of Mo was promoted by Rh, and different phase/support interactions were verified. Among the supports, ZrAl-10 presented the highest acidity due to the presence of ZrO2 in the tetragonal modification and high specific surface area (due to Al2O3), favouring rhodium-molybdenum active phase/support interaction and high dispersion. All catalysts prepared were active in removing NO3-, the one prepared with the RhMo6 phase on the ZrAl-10 support being the most active. These results point to the formation of an active surface with a high dispersion of Rh and Mo. The highest selectivity to N2 (99.3) exhibited by the RhMo6/ZrAl-10 catalyst is proposed to be related to the high Rh dispersion (0.755) and to the presence of Lewis acid sites (oxygen vacancies) of the tetragonal ZrO2 modification that favour NO3- adsorption through electrostatic interactions.

Identification of refractory zirconia from catalytic converters in dust: An emerging pollutant in urban environments.

Using catalytic converters is one of the most effective methods to control vehicle emissions. A washcoat of cerium oxide-zirconia (CeO2-ZrO2) has been used to enhance the performance of the catalytic converter device. To date, the prevalence of this material in the environment has not been assessed. In this study, we present evidence of the existence of inhalable zirconia in urban dust. Samples of the washcoat, exhaust pipe, topsoil, and road dust were analyzed by X-ray fluorescence, X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, photoluminescence (PL) spectroscopy, and thermally stimulated luminescence (TSL). The results showed a CeO2-ZrO2 phase separation after sintering. This causes the emission of ZrO2, CeO2, and CeZrOx particles smaller than 1 µm, which can likely reach the alveolar macrophages in the lungs. The Ce-Zr content in road dust exceeds geogenic levels, and a significant correlation of 0.87 (p < 0.05) reflects a common anthropic source. Chronic exposure to such refractory particles may result in the development of non-occupational respiratory diseases. The inhalable crystalline compounds emitted by vehicles are a significant environmental health hazard, revealing the need for further investigation and assessment of zirconia levels generated by automobiles in urban areas worldwide.

Comparison of the flexural strength of sheets manufactured in three types of zirconium dioxide with two sintering times / Comparación de la resistencia flexural de láminas elaboradas en tres tipos de dióxido de zirconio con dos tiempos de sinterización

Abstract Introduction: yttrium-stabilized zirconium dioxide (zirconia) has been used to manufacture fixed partial prosthesis due to its high flexural strength. However, there are no available studies comparing the effect of two sintering techniques on flexural strength. This study aims to compare the flexural strength of zirconia sheets manufactured with two sintering techniques. Method: for this in vitro study, three zirconia disks were used (Upcera: Super Translucent (ST): 1200 MPa, Multi-Layer (ML): 600 MPa and High Translucent (HT): 1200 MPa), using an Isomet® cutter to prepare 60 sheets 2 mm thick, 5 mm wide and 37 mm long. These sheets were randomly distributed into two groups of 30: the first group was sintered for 8 hours at 1,530°C and the second group was subjected to fast sintering for 3 hours at 1,530°C. The flexural strength in Newton was measured on an Instrom® 3366 Universal Testing Machine. The results were converted from N to MPa and compared by ANOVA and t test. Results: no statistically significant difference was found in the flexural strength of the two groups (p>0,05). Conclusion: the two compared sintering procedures do not affect the flexural strength of zirconia sheets.

Resumen Introducción: las restauraciones de dióxido de zirconio estabilizadas con ytrio para prótesis parciales fijas e implantosoportadas se han utilizado por su alta resistencia flexional. En la revisión bibliográfica no se encontraron estudios que comparen la resistencia flexional del dióxido de zirconio con 2 tiempos de sinterización diferentes. El objetivo del presente estudio consistió en comparar la resistencia flexional de láminas elaboradas en 3 tipos de dióxido de zirconio con 2 tiempos de sinterización. Método: en este estudio in vitro, se recolectaron 3 discos de dióxido de zirconio (Upcera: Súper translúcido (ST): 1200 MPa, Multicapa (ML): 600 MPa y Alta translucidez (HT): 1200 MPa), y en un aparato de corte Isomet® se recortaron 60 láminas de 2 mm de espesor, ancho de 5 mm y longitud de 37 mm. Estas láminas se distribuyeron aleatoriamente en dos grupos de 30: el grupo uno se sinterizó por 8 horas a 1.530°C y el otro grupo se sometió a sinterización rápida por 3 horas a 1.530°C. La resistencia flexional se midió en una máquina universal Instrom® 3366. Los resultados fueron convertidos de N a MPa y se compararon mediante análisis de varianza y prueba t. Resultados: no hubo diferencia estadísticamente significativa al comparar la resistencia flexional después de dos tiempos de sinterización diferentes (p>0,05). Conclusiones: no se presentaron diferencias significativas en la resistencia flexional del dióxido de zirconio al comparar los promedios obtenidos con dos técnicas de tiempo de sinterización diferente.

Degradation of metformin in water by TiO2-ZrO2 photocatalysis.

The increasing use of pharmaceutical products also increases their release in aquatic environment. These contaminants are considered emerging pollutants, and induce adverse ecological and human health effects. The antidiabetic metformin is one example that has been detected in the aquatic environment at unusual concentrations. This fact indicates that conventional wastewater treatment is inefficient on eliminating this compound. Here we show that metformin can be effectively removed from water by photocatalysis. We found the optimised conditions for pH and concentration of catalyst on the photocatalytic process. TiO2 and TiO2-ZrO2 were successful in oxidising metformin under UV radiation following a pseudo-first order kinetics. Intermediates of metformin photodegradation appeared after photocatalytic treatment. Toxicity analysis showed that the degradation products are non-toxic to Lactuca sativa seeds.

The Effect of the ZrO2 Loading in SiO2@ZrO2-CaO Catalysts for Transesterification Reaction.

The effect of the ZrO2 loading was studied on spherical SiO2@ZrO2-CaO structures synthetized by a simple route that combines the Stöber and sol-gel methods. The texture of these materials was determined using SBET by N2 adsorption, where the increment in SiO2 spheres' surface areas was reached with the incorporation of ZrO2. Combined the characterization techniques of using different alcoholic dissolutions of zirconium (VI) butoxide 0.04 M, 0.06 M, and 0.08 M, we obtained SiO2@ZrO2 materials with 5.7, 20.2, and 25.2 wt % of Zr. Transmission electron microscopy (TEM) analysis also uncovered the shape and reproducibility of the SiO2 spheres. The presence of Zr and Ca in the core-shell was also determined by TEM. X-ray diffraction (XRD) profiles showed that the c-ZrO2 phase changed in to m-ZrO2 by incorporating calcium, which was confirmed by Raman spectroscopy. The purity of the SiO2 spheres, as well as the presence of Zr and Ca in the core-shell, was assessed by the Fourier transform infrared (FTIR) method. CO2 temperature programmed desorption (TPD-CO2) measurements confirmed the increment in the amount of the basic sites and strength of these basic sites due to calcium incorporation. The catalyst reuse in FAME production from canola oil transesterification allowed confirmation that these calcium core@shell catalysts turn out to be actives and stables for this reaction.

Flexural strength and crystalline stability of a monolithic translucent zirconia subjected to grinding, polishing and thermal challenges.

The objective of this study is to investigate the magnitude of structural degradation of a monolithic translucent zirconia caused by clinically relevant grinding and polishing procedures, when associated or not with low temperature degradation (LTD), induced by accelerated hydrothermal aging using autoclave or thermocycling Ninety disks (Ø12 × 1 mm) were prepared from dental zirconia for monolithic restorations (Vipi Block Zirconn Translucent, Vipi). The specimens were divided into 3 groups (n = 30) according to surface treatment: As Sintered (untreated), Grind (diamond bur), Grind + Polish (diamond bur + polish); and then subdivided according to aging method (n = 10): Baseline (no aging), Autoclave (134°C, 2.2 kgf/cm2 pressure for 5 h), and Thermocycling (200,000 cycles, 5°C and 55°C, for 15 s each). Roughness, biaxial flexural strength and percentage of monoclinic phase were evaluated. Regarding surface treatment, the Grind group presented higher roughness and greater flexural strength compared to As Sintered group, while Grind + Polish showed intermediate roughness and flexural strength similar to Grind group. Aging had little effect on roughness, but yielded a significant reduction in flexural strength. Tetragonal to monoclinic phase transformation was observed in all groups, caused by both mechanical stresses (grinding and polishing) and LTD, which was similarly induced by the traditional autoclave method, as well as the thermocycling method The use of diamond burs to grind zirconia surface may result in deleterious effects on the surface quality of monolithic zirconia restorations, yet has a potential toughening effect by phase transformation. However, when zirconia is exposed to LTD, regardless of the surface treatment, degradation of the surface quality and strength are observed.

Adapted Pechini method to prepare DSA type electrodes of RuO2-ZrO2 doped with Sb2O5 over titanium plates.

This paper describes a thermal method to obtain metal oxides on a titanium substrate surface. This adapted Pechini method is a versatile, easy to handle and scalable technique to obtain electrodes for industrial uses, such as Dimensionally Stable Anodes (DSA). This method has advantages over other thermal methods like dip coating or sputtering, as it needs a smaller amount of polymeric mixture than dip coating method to cover the same area and is less expensive than sputtering method. The thermal method described herein to prepare DSA type electrodes of RuO2-ZrO2 doped with Sb2O5 over titanium plates needs no sophisticated equipment as spray pyrolysis technique does; a muffle, ultrasonic equipment, and a hot plate magnetic stirrer are the principal apparatus necessary to carry out the adapted Pechini method. On the other hand, this method allows metal oxides to disperse homogeneously. The cyclic voltammograms showed the stability of DSA, and the accelerated life test allowed establishing its useful life (18.18 years) at a current density of 10 mA cm-2.

Comparative Study of the Optical and Textural Properties of Tetrapyrrole Macrocycles Trapped Within ZrO2, TiO2, and SiO2 Translucent Xerogels.

The entrapping of physicochemical active molecules inside mesoporous networks is an appealing field of research due to the myriad of potential applications in optics, photocatalysis, chemical sensing, and medicine. One of the most important reasons for this success is the possibility of optimizing the properties that a free active species displays in solution but now trapped inside a solid substrate. Additionally it is possible to modulate the textural characteristics of substrates, such as pore size, specific surface area, polarity and chemical affinity of the surface, toward the physical or chemical adhesion of a variety of adsorbates. In the present document, two kinds of non-silicon metal alkoxides, Zr and Ti, are employed to prepare xerogels containing entrapped tetrapyrrolic species that could be inserted beforehand in analogue silica systems. The main goal is to develop efficient methods for trapping or binding tetrapyrrole macrocycles inside TiO2 and ZrO2 xerogels, while comparing the properties of these systems against those of the SiO2 analogues. Once the optimal synthesis conditions for obtaining translucent monolithic xerogels of ZrO2 and TiO2 networks were determined, it was confirmed that these substrates allowed the entrapment, in monomeric form, of macrocycles that commonly appear as aggregates within the SiO2 network. From these experiments, it could be determined that the average pore diameters, specific surface areas, and water sorption capacities depicted by each one of these substrates, are a consequence of their own nature combined with the particular structure of the entrapped tetrapyrrole macrocycle. Furthermore, the establishment of covalent bonds between the intruding species and the pore walls leads to the obtainment of very similar pore sizes in the three different metal oxide (Ti, Zr, and Si) substrates as a consequence of the templating effect of the encapsulated species.