Mechanical properties and thermal shock in thin ZrO2–Y2O3–Al2O3 films obtained by the sol-gel method

Thin multilayer coatings of ZrO₂–Y₂O₃–Al₂O₃ were prepared using the sol-gel method and dip-coating technique in order to advance in the study of what influence the incorporation of Al₂O₃ has on films of Y₂O₃-doped ZrO₂, investigating its role in the synthesis of the solutions and in the characteristics and properties of the coatings. After the characterization of the solutions used in the process, the microstructure of the films was studied and their mechanical behaviour and resistance to thermal shock were determined so as to optimize the characteristics and functionality of these coatings. With increased alumina content, 3YSZ-Al₂O₃ (20 mol%), the cubic phase of the zirconia disappeared completely at the sintering temperature used (700 °C), resulting in the tetragonal phase with Al in solution. There was also a decrease in the coatings' hardness and Young's modulus, and an increase in toughness and resistance to thermal shock. These results allow guidelines to be established for the design of multilayer structures that are, tougher, more resistant, and have improved surface properties.     

Thermal prehistory,structure and high-temperature thermodynamic properties of Y2O3-CeO2 and Y2O3-ZrO2-CeO2 solid solutions

Ceria-based solid solutions are important materials for high- and medium-temperature electrochemical applications. However, the stabilities of both binary and ternary ceria-based solid solutions are insufficient at elevated temperatures, which limits their application as solid electrolytes or SOFC cathodes. Data on the high-temperature stability of ceria-based ceramics are unavailable in the literature. In the present study, we report a thermodynamic stability investigation of Y₂O₃-CeO₂ and Y₂O₃-ZrO₂-CeO₂ solid solutions. The thermal prehistories of binary and ternary systems were investigated using STA, XRD, and ESCA techniques. The vaporization processes were investigated in the temperature range of 1577–2227°С via the Knudsen effusion mass spectrometry technique. Using data on the component activity in solid-phase thermodynamic properties of Y₂O₃-CeO₂ solid solutions, which is represented as the Gibbs energy, the excess Gibbs energy was calculated as a function of the ceria mol. %. It was shown that the reduction of Ce⁴⁺ to Ce³⁺ in Y₂O₃-CeO₂ and Y₂O₃-ZrO₂-CeO₂ solid solutions corresponds to less-negative Gibbs energy compared to ZrO₂-CeO₂ solid solutions.     

Characterization of the structure and properties of processed alumina-graphene and alumina-zirconia composites

The onset of hybrid alumina-based composites, which combines two or more nano-particles within the alumina matrix has already shown promising improvements in the matrix material. However, variations in mechanical properties including the optimum compositions that give improved properties faced with the development of alumina-based composites require further studies to understand the underlying mechanisms and synergistic effects of the nano-particle additions on the alumina matrix. In the current study, the structure and properties of Al?O?-graphene (0.5 wt%) and Al?O?–ZrO? (4 wt% and 10 wt%) composites fabricated via hot-pressing was studied as a baseline for multiple combinations. Even though the addition of 10 wt%ZrO? resulted in a 23% reduction in the grain size of the alumina matrix, the 4 wt%ZrO? addition resulted in a 14% increase in grain size as compared to the parent alumina matrix. X-ray diffraction analysis revealed that there was approximately 85% monoclinic (m-ZrO₂) vs. 15% tetragonal (t-ZrO₂) crystal structures in the A4ZrO? sample whilst the A₁₀ZrO? had approximately 93% m-ZrO₂ vs. 7% t-ZrO₂. The high-volume fraction of the monoclinic crystal structures in the A₁₀ZrO? accounts for the induced microcracks in the sample since the transition from the ductile-tetragonal to brittle-monoclinic is associated with the exertion of compressive stresses on the alumina matrix by the associated elastic volume expansion of m-ZrO₂. Also, the addition of 0.5 wt%graphene resulted in about 37% reduction in the grain size of the alumina matrix, and approximately 10% increase in hardness as a result of the distribution of graphene along the grain boundaries of the parent alumina matrix, which restricts grain coalescence and growth during processing. Furthermore, an increase up to 115% and 164% were observed in the fracture toughness (K_IC) with the inclusion of 0.5 wt%graphene and 10 wt%ZrO? respectively, which was primarily ascribed to the fine-grained microstructures and toughening mechanisms of the intergranular graphene and ZrO? particles.     

A thermal perspective of flash sintering: The effect of AC current ramp rate on microstructure evolution

In flash sintering experiments, the thermal history of the sample is key to understanding the mechanisms underlying densification rate and final properties. By combining robust temperature measurements with current-ramp-rate control, this study examined the effects of the thermal profile on the flash sintering of yttria-stabilized zirconia, with experiments ranging from a few seconds to several hours. The final density was maximized at slower heating rates, although processes slower than a certain threshold led to grain growth. The amount of grain growth observed was comparable to a similar conventional thermal process. The bulk electrical conductivity correlated with the maximum temperature and cooling rate. The only property that exhibited behavior that could not be attributed to solely the thermal profile was the grain boundary conductivity, which was consistently higher than conventional in flash sintered samples. These results suggest that, during flash sintering, athermal electric field effects are relegated to the grain boundary.     

Defect-free drying of large fine-particle zirconia compacts prepared by gelcasting method

In this work, drying of bodies prepared by gelcasting fine submicrometre-sized zirconia particles was studied and a drying process for defect-free bodies with large cross-sections was proposed. It was found that the cracking of large bodies could be prevented by reducing the monomer content and using appropriate non-volatile cosolvents. Glycerol and polyethylene glycols with different molecular weights were used as non-volatile cosolvents in aqueous ceramic suspensions. The complex effects of the individual cosolvents on the gelcasting process and, in particular, on the drying step were investigated and explained. The applicability of individual cosolvents for the gelcasting process were discussed and their optimal use was indicated.     

Femtosecond Ti: Sa ultra short-pulse laser irradiation effects on the properties and morphology of the zirconia surface after ageing

Femtosecond pulses from a Ti:Sapphire laser were used to irradiate specimens of yttria-stabilised (35% mol) tetragonal zirconia (Y-TZP) with the purpose of studying the effects of the irradiations on their surface properties and morphology after ageing. Zirconia disks were divided into eight groups (n = 32) according to their surface treatment and subsequent ageing: Control: no treatment; sandblasting: Al₂O₃ sandblasting 50 μm; and ultrashort laser pulses irradiation with 25 μJ pulses, considering two different scanning steps based on the width between two grooves. These groups were duplicated and submitted to ageing. The surfaces were analysed using scanning electron microscopy (SEM), and X-ray diffraction. A finite element analysis, a biaxial flexure test, as well as fractographic and Weibull analyses, were performed. The strengths of the disks were statistically different for the treatment factor, and the principal stresses seemed to be concentrated at the centre of the specimens, as predicted by the computer simulations. Ageing decreased the strengths for all groups and increased the Weibull modulus for the laser group with the 40 μm-width between two grooves. The sandblasting group presented the highest monoclinic phase peak. Although the most significant strength was found within the sandblasting group, the phase transformation was favourable to the laser groups. The Weibull modulus was higher for the laser group with the 60 μm-width between two grooves, confirming the highest homogeneity of its failure distribution. Regardless of the surface treatment, strength was decreased with ageing in all groups. The femtosecond Ti:Sa ultra-short pulse laser irradiation can be suggested as an alternative to the gold standard sandblasting in long-term Y-TZP zirconia rehabilitations, such as crowns and veneers.     

Microcrack healing in zirconia ceramics under a DC electric field/current

Flash event caused by a DC electric field/current was applied to the crack healing in 8 mol % Y₂O₃ stabilized cubic ZrO₂ polycrystals (8Y-CSZ). The flash event, which occurred by applying the DC power higher than a critical value of 100 mW/mm³, successfully healed the microcrack within several minutes without any healing agents at a furnace temperature of 800 °C. As compared to the healing treatment under static annealing, the healing phenomena were accelerated about 2 times under the flash treatment even at the same temperatures, suggesting that the enhanced healing phenomena cannot be explained only by the temperature effect. Since the rate of grain growth was accelerated under the flash treatment, the flash healing would be accelerated through the current-enhanced diffusional processes. This study shows for the first time that the flash event has a potential to apply to the crack healing process in the ceramic materials and composites.     

Simple and novel synthesis of zirconia whiskers from a phosphate flux

High quality zirconia whiskers have been successfully prepared by molten salt method, using zirconium oxychloride (ZrOCl₂·8H₂O) and sodium phosphate tribasic dodecahydrate (Na₃PO₄·12H₂O) as precursor and molten salt, respectively. The effects of types of molten salt and heat treatment temperature on the formation of zirconia whiskers were characterized by XRD, Raman, DTA-TG, FE-SEM, TEM, SAED and HR-TEM. When Na₃PO₄·12H₂O is utilized as molten salt and the heat treatment temperature is 900?°C, the as-prepared zirconia whiskers with length ranging from 4?µm to 8?µm show an average aspect ratio of 25. The obtained ZrO₂ whiskers with monoclinic structure are elongated along [010] direction and exhibit a smooth surface with no distinct defects. The XRD and Raman results reveal that the phase transformation from tetragonal zirconia to monoclinic zirconia occurs with the increased crystal size and the water quenching treatment can significantly reduce the content of sodium zirconium phosphate [Na_9–4×Zr_x(PO₄)₃] in the final product. The growth mechanism of zirconia whiskers is supposed to be a dissolution-precipitation process. Since the sodium zirconium phosphate [Na_9–4×Zr_x(PO₄)₃] effectively promotes the dissolution of zirconia in liquid molten salt, zirconia can grow into zirconia whiskers according to its anisotropy.     

Role of a low level of La2O3 dopant on the tetragonal-to-monoclinic phase transformation of ceria-yttria co-stabilized zirconia

Yttria, yttria-ceria and yttria-ceria-lanthana stabilized zirconia powders were prepared by coprecipitation. Their tetragonal-to-monoclinic phase (t→m) transformation was investigated by calcining the powders in a temperature range of 400–1400 °C for 2 h. The results show that after doping with 0.1 to 0.3 mol.% La₂O₃ and calcining at 1400 °C in air, unusual redox behaviours of cerium were detected in the 1.5 mol.% Y₂O₃+5.5 mol.% CeO₂ co-stabilized zirconia. Grain refinement and a sharp reduction in oxygen vacancy concentration were observed simultaneously. The t→m transition was not found in the 0.1 mol.% La₂O₃ doped zirconia but appeared in the cases with a higher dopant content. The changes are discussed with regards to the grain size, valence change of cerium, presence of oxygen vacancies, and segregation of the dopants at grain boundaries.     

Joining zirconia with nickel-based superalloys for extreme applications by using a pressure-free high-temperature resistant adhesive

In order to meet the high demand for joining ceramic/superalloy composite structure in extreme environments, a novel high-temperature resistant adhesion technique was developed for joining ZrO₂ and Inconel 625 by applying an aluminum phosphate emulsion/zirconium sol based adhesive. With increasing temperature, a series of reactions occurred in adhesive, and its high-temperature bonding was attributed to the formation of a composite structure containing various ceramics and intermetallics. The adhesive after RT curing could find direct applications in extreme environments, and provide bonding strength no less than 2.5 MPa in the temperature range of RT-1100 °C. The bonding strength was higher than 4 MPa in the temperature range of 800–1000 °C, which was further attributed to the formation of an effective CTE-gradient relationship among ZrO₂, adhesive and Inconel 625, as well as the interfacial reactions between the two substrates. The work broadened the application of adhesion technique and brought new ideas for joining dissimilar engineering materials.