Influence of flash sintering on the ionic conductivity of 8 mol% yttria stabilized zirconia

The ionic conductivity of flash-sintered, polycrystalline 8 mol% yttria stabilized zirconia (8YSZ) was enhanced compared with that of conventionally-sintered specimens. Flash sintering was carried out at a furnace temperature of 850 °C with an electric field of 100 V cm^–1 to initiate flash. The current density limit was varied between 60 and 100 mA mm^–2. Post-flash impedance measurements over the range 215–900 °C showed that both bulk and grain boundary conductivities had increased with the increased current density limit which was set prior to flash. The conductivity increases post-flash were ionic, not electronic, although electronic conductivity probably occurred, in addition to ionic conductivity, during flash. The conductivity increases were not attributable to sample densification or microstructural changes. The higher ionic conductivities are attributed to a change in YSZ defect structure that led to an increased concentration of mobile charge carriers; possible explanations for this are discussed.     

Influence of porosity on mechanical properties of tetragonal stabilized zirconia

3YSZ specimens with variable open porosity (1–57%) were fabricated, and the stiffness, strength and fracture properties (fracture toughness and R-curve) were measured to investigate their potential use as support structures for solid oxide fuel or electrolysis cells. The ball-on-ring test was used to characterize Young's modulus and Weibull strength. The variation of fracture toughness with porosity was investigated and modelled using the results from fracture mechanical testing. A distinct R-curve behaviour was observed in dense 3YSZ specimens, in samples with a porosity around 15% and in some of the highly porous samples (porosities ～45%) reflecting a transformation toughening in the material. For the most porous samples, the “R-curve behaviour” disappeared and subcritical crack growth was observed. The studies indicate that even highly porous 3YSZ structures (porosities exceeding 40%) are feasible supports for SOFC/SOECs from a mechanical point of view.     

Transparent high-strength nanosized yttria stabilized zirconia obtained by pressure-less sintering

This work describes the development of transparent high-strength Yttria-Stabilized Zirconia (YSZ) ceramics with ultra-fine grain size utilizing conventional pressure-less densification. Starting with nanoparticles with diameter < 10 nm, it was possible to achieve full densification (>99.5% of theoretical density) at a sintering temperature of 1100–1200 °C. The average grain size of the resulting dense ceramics was 75 nm in 3 mol. % YSZ and 85 nm in 8 mol. % YSZ, showing in-line light transmission of 38% and 51% at a wavelength of 800 nm and average biaxial strength (piston on three balls test on samples of diameter 12 mm and thickness 1 mm) of 1980 MPa and 680 MPa, respectively. The nano-grained structure, absence of color centers, and miniaturization of residual pores enable the excellent light transmission. The high biaxial strength is attributed to the refined microstructure, but also to the martensitic tetragonal-to-monoclinic phase transformation that remains active even in nano-sized zirconia grains.     

Micromechanical properties and microstructure evolution of magnesia partially stabilized zirconia prepared by spark plasma sintering

Magnesia partially stabilized zirconia (Mg-PSZ) is a widely used engineering ceramic owing to its high hardness and exceptional toughness. It is usually processed by conventional firing followed by subeutectoid aging. In this work, Mg-PSZ was prepared by spark plasma sintering (SPS) followed by sequential subeutectoid aging to fine-tune its mechanical properties. Mg-PSZ prepared by SPS with the rapid heating capability presents much smaller grains than conventionally prepared counterparts. After aging, a significant fraction of the matrix cubic phase transforms into tetragonal, orthorhombic, and monoclinic zirconia. Microindentation and in-situ microcompression tests reveal that aging Mg-PSZ for 4 h leads to maximum fracture toughness and fracture strain due to the tetragonal-to-monoclinic transformation toughening. Post compression TEM analyses show dominant monoclinic ZrO₂ decorated by a high density of twin boundaries and stacking faults formed to accommodate the shear deformation. Preparation of Mg-PSZ by SPS offers rapid and effective approaches in finetuning the phases and mechanical properties.     

Effect of waste-derived MA spinel on sintering and stabilization behavior of partially stabilized double phase zirconia

Cubic-stabilized zirconia ceramic composites have been synthesized by conventional sintering, starting from commercial m-ZrO₂, Y₂O₃, and waste-derived magnesium aluminate spinel (MA) powders. In this work, the effect of sintering temperature and MA content on stabilization and densification properties of YSZ have been duly considered. MA-free YSZ0 composite sintered at 1600°C-1700°C revealed m- and t-ZrO₂ dual-phase structure where its m-ZrO₂ was partially stabilized upon temperature rising into tetragonal phase by Y³⁺ diffusion inside zirconia structure. YSZ10-50 composites containing 10-50 wt% MA demonstrated dissimilar behavior where their m-ZrO₂ was transformed and stabilized into a cubic form by diffusion of Y³⁺, Mg⁺², and Al⁺³ inside zirconia lattice. Furthermore, densification of YSZ10-50 powder mixtures by conventional sintering at 1600°C for 2 hours resulted in fully dense compacts with micrometer-sized grains. The outcomes indicate that MA has a significant effect on m-ZrO₂ stabilization into the cubic phase structure at room temperature. In this respect, this study offers huge potentials for developing fully stabilized c-ZrO₂ ceramics that could be possibly used as industrial ceramics for structural applications of harsh chemical and thermal environmental conditions.     

Structure and electrical properties of cold sintered 8mol% scandia stabilized zirconia ceramics

Scandia stabilized zirconia (ScSZ) has been considered as a promising electrolyte for solid oxide fuel cell (SOFC), but high sintering temperature was always required to achieve high density and electrical conductivity. Herein, high-performance ScSZ ceramics were prepared at low temperature by using the cold sintering process (CSP) associated with post-heat-treatment (PHT). Firstly, 8 mol% ScSZ nano powder was synthesized by an ethanol-assisted two step hydrothermal method. Then, ScSZ ceramics were prepared by using CSP and PHT (CSP-PHT). It was found that the relative density of the green body made by CSP at 180 ^○C could exceed 70%, which rose to 96.8% after post-heat-treatment at 1200 ^○C, higher than that prepared by conventional sintering method at elevated temperature of 1400 ^○C with the relative density of 95.4%. Impedance spectra measured at 800 ^○C showed the electrical conductivity of ScSZ ceramics prepared by CSP-PHT at 1200 ^○C was 0.115 S/cm, prior to that prepared by the CS at 1400 ^○C with electrical conductivity of 0.111S/cm. Our results demonstrate that the CSP is a promising method for preparing high performance ScSZ ceramics at reduced temperature.     

Influence of sintering parameters on tribological properties of ceria stabilized zirconia bio-ceramics

Nano-structured ceria stabilized zirconia powder was synthesized from their respective nitrate salts using a wet chemical co-precipitation method. Dried powder was calcined at different temperatures. Particle size of calcined powders was measured by X-ray diffraction (Scherrer equation) and high resolution transmission electron microscopy. Relative quantities of phases (e.g. monoclinic, tetragonal and cubic) were estimated using rigorous Rietveld analysis. The powder was compacted and sintered conventionally following different time and temperature schedules in order to optimize the sintering schedule for fabrication of dense material. The microstructures of the sintered samples were observed by field emission scanning electron microscopy. Vickers hardness (∼945 VHN) showed appreciable increase (>35%) in the hardness value compared to earlier reported ones. Fretting wear of some of the selected samples was carried out in un-lubricated condition. Wear volume and specific wear rate were estimated and correlated with the microstructure. Fatigue microcrack formation, plastic deformation, grain pull-out and abrasion were found to be the main wear mechanisms.     

Physicochemical properties of Ni-loaded yttrium stabilized zirconia nanotubes for solid oxide fuel cells

Yttrium-stabilized zirconia nanotubes (YSZNTs) were prepared using a conventional hydrothermal method, and their characteristics were compared with those of yttrium-stabilized zirconia nanoparticles (YSZNPs) synthesized in this study and with those of commercial YSZNPs (CYSZNPs). YSZNTs had widths and lengths of 20–30 nm and 100–700 nm respectively. The electrical conductivity of NiO (60.0 wt%)-loaded YSZNTs (40.0 wt%) was higher than those of NiO/YSZNPs and NiO/CYSZNPs at the same NiO loading. The zeta-potentials of YSZNTs in aqueous solution, determined by electrophoretic light scattering (ELS), indicated high positive surface charges at lower pH values, which is known to be related to surface stability, but negative values at high pH. The results of cyclic voltammetry (CV) and H₂-temperature-programmed reduction (H₂-TPR) confirmed that NiO(60.0 wt%)/YSZNTs (E_red = −0.445 mV) were more reduced than NiO/YSZNPs (E_red = −0.517 mV) and NiO/CYSZNPs (E_red = −0.516 mV).     

Comparison between microwave and conventional sintering on the properties and microstructural evolution of tetragonal zirconia

In this research, the comparison between microwave sintering and conventional sintering on the mechanical properties and microstructural evolution of 3?mol% yttria-stabilised zirconia were studied. Green bodies were compacted and sintered at various temperatures ranging from 1200?°C to 1500?°C. The results showed that microwave assisted sintering was beneficial in enhancing the densification and mechanical properties of zirconia, particularly when sintered at 1200?°C. It was revealed that as the sintering temperature was increased to 1400?°C and beyond, the grain size and mechanical properties for both microwave- and conventional-sintered ceramics were comparable thus suggesting that the sintering temperature where densification mechanism was activated, grain size was strongly influenced by the sintering temperature and not the sintering mode.     

An oscillatory pressure sintering of zirconia powder: Densification trajectories and mechanical properties

The densification trajectories and mechanical properties of zirconia ceramics obtained by oscillatory pressure sintering (OPS) process were investigated, during the sintering process an oscillatory pressure was applied at three stages. Current results indicated that at intermediate stage the oscillatory pressure revealed a favorable improvement of mechanical properties compared with conventional hot pressing (HP) and pressureless sintering (PS) procedures, while the enhancement was not obvious at initial stage. When the oscillatory pressure was applied at final stage, the OPS specimens exhibited the highest bending strength and hardness of 1455 ± 99MPa and 16.6 ± 0.31GPa compared with the PS and HP specimens. Considering the high elastic modulus and Moiré patterns observed in the OPS specimen, the oscillatory pressure applied at intermediate and final stages was detected to facilitate the sliding of grain boundary, plastic deformation of monolithic grains, the removal of pores and the strengthening of atomic bonds.     

Eight mole percent yttria stabilized zirconia powders by organic precursor route

An organic precursor-mixing route has been developed for preparation of 8 mol% yttria stabilized zirconia (8YSZ) ceramics. Polymeric salt of succinic acid with yttrium and zirconium has been prepared separately by treating sodium succinate with yttrium chloride and zirconyl chloride followed by washing with water and drying at 120 °C. Thorough mixing of the two salts in stoichiometric proportions by planetary ball milling followed by calcination at 850 °C resulted in a precursor powder containing nanocrystalline (∼40 nm) monoclinic zirconia, tetragonal YSZ, cubic YSZ and yttria. Compacts prepared after deagglomeration of powder by planetary ball milling produce 8YSZ ceramics having density 99.3% TD on sintering at 1550 °C for 2 h.     

High temperature mechanical properties of zirconia metastable t'-Phase degraded yttria stabilized zirconia

Air plasma sprayed (APS) 8 wt%-yttria stabilized zirconia (8YSZ) with metastable tetragonal prime phase (t′) has been widely applied as thermal barrier coatings (TBCs) for gas turbine blades because of its outstanding mechanical properties at high temperatures. In the present research, a carefully designed process was used to prepare 8YSZ samples with different phase composition (t′, t and c) simulating the phase degradation of the material during operation conditions. High temperature (1000–1200 °C) bending strength, elastic modulus, and thermal expansion coefficient were measured, which exhibit strong dependence on the phase degradation during heat treatment. Effect of the phase composition on high temperature thermo-mechanical properties and the enhancement of the bending strength have been discussed, providing a new perspective for further improvements.     

Effects of two-step sintering on thermal and mechanical properties of aluminum nitride ceramics by impedance spectroscopy analysis

The effects of two-step sintering on the microstructure, mechanical and thermal properties of aluminum nitride ceramics with Yb₂O₃ and YbF₃ additives were investigated. AlN samples prepared using different sintering methods achieved almost full density with the addition of Yb₂O₃–YbF₃. Compared with the one-step sintering, the grain sizes of AlN ceramics prepared by the two-step sintering were limited, and the higher flexural strength and the larger thermal conductivity were obtained. Moreover, the electrochemical impedance spectroscopy of AlN ceramic was associated with thermal conductivity by analyzing the defects and impurities in AlN ceramics. The fitting grain resistance and the activation energy for the grain revealed the lower concentrations of aluminum vacancy in the two-step sintered AlN ceramics, which resulted in the higher thermal conductivity. Thus, mechanical and thermal properties for AlN ceramics were improved with Yb₂O₃ and YbF₃ additives sintered using two-step regimes.     

Field assisted sintering of ceramic constituted by alumina and yttria stabilized zirconia

We show that a two-phase 50 vol% 3YSZ-alumina ceramic flash-sinters at a furnace temperature of 1060 °C under an electrical field of 150 V cm⁻¹. In contrast undoped, single-phase alumina remains immune to field assisted sintering at fields up to 1000 V cm⁻¹, although single-phase 3YSZ flash sinters at 750 °C (furnace temperature). The mechanisms of field assisted sintering are divided into two regimes. At low fields the sintering rate increases gradually (FAST), while at high fields sintering occurs abruptly (FLASH). Interestingly, alumina/zirconia composites show a hybrid behavior such that early sintering occurs in FAST mode, which is then followed by flash-sintering. The specimens held in the flashed state, after they had sintered to near full density, show much higher rate of grain growth than in conventional experiments. These results are in contrast to earlier work where the rate of grain growth had been shown to be slower under weak electrical fields.     

Effect of TiO2 doping on densification and mechanical properties of hydroxyapatite by microwave sintering

Hydroxyapatite (HAP) possesses excellent bioactivity/osteointegration properties. Nevertheless, its inferior flexural strength and fracture toughness limit its use in human weight-bearing parts. We investigated a microwave sintering technology which can be effectively used to develop titanium dioxide-hydroxyapatite (TiO₂-HAP) ceramics with different amounts of TiO₂ (0.8,1.6,2.4,3.2,4.0,4.8,5.6 and 6.4 wt%), which contribute to extremely high flexural strength (90–130 MPa) along with a good combination of elastic modulus and fracture toughness. The results of the Rietveld refinement show that multiphase bioceramics (HAP, β-TCP) can be achieved by doping nano-TiO₂ under microwave sintering. Despite the fact that the main phases of the sintered TiO₂-HAP ceramics are HAP and β-TCP, X-ray diffraction confirms the formation of the CaTiO₃ and CaTi₂O₄(OH)₂ phases. Furthermore, the sintering reactions to form these phases are discussed and the results show that an appropriate amount of nano-TiO₂ can not only effectively inhibit the growth of grain, but also change the fracture mode and increase the relative density. Finally, it is found that doping nano-TiO₂ by microwave heating is an effective technique for producing HAP/β-TCP composite load-bearing implants in clinical applications without coarsening the size of grain.     

The toughening mechanism and mechanical properties of graphene-reinforced zirconia ceramics by microwave sintering

ABSTRACT

The graphene/ZrO₂ composites were fabricated by impregnating graphene dispersion into the ZrO₂ ceramic matrix and sintered by microwave, and the microstructure and mechanical properties were investigated. The results showed that the graphene was well dispersed in the ceramic matrix and refined the grain size. The fracture toughness reached 8.62?MPa?m^1/2, confirmed by single-edge notched beam, which was 42% higher than that of the pure ZrO₂. Also, the toughening mechanisms were investigated by micro-hardness testing and showed that a combination of crack deflection, micro-crack and crack bridging increased the fracture toughness.     

Effect of high-speed sintering on the microstructure,mechanical properties and ageing resistance of stereolithographic additive-manufactured zirconia

Digital light processing (DLP) demonstrates significant application potential in the fine printing of dental zirconia. However, its complicated print process and post-treatments, such as sintering, are time consuming and sensitive to technical details. Therefore, the feasibility of using a high-speed sintering (HS) method for the fabrication of DLP-based zirconia was investigated in this study. Zirconia samples fabricated using DLP and conventional subtractive manufacturing techniques were all sintered following the different protocols: HS and conventional sintering (CS). Then, the density, Vickers hardness, fracture toughness, surface micro-topography, phase assemblage, and ageing resistance were assessed. The results showed that samples fabricated using the HS technique presented moderate Vickers hardness, fracture toughness, and ageing sensitivity in comparison with the other groups of specimens; moreover, they exhibited moderate initial cubic phase content and average grain size. Conversely, specimens sintered using the CS protocol with a peak temperature of 1580 °C showed high ageing sensitivity and unbalanced mechanical properties. The DLP- and SM-fabricated specimens showed similar trends for the studied properties. Overall, sintering parameters can significantly affect the macro- and micro-properties of DLP specimens, and the proposed HS method showed potential for producing DLP-based zirconia that is acceptable for clinical applications.     

Enhancement of mechanical properties of ceria-calcia stabilized zirconia by alumina reinforcement

Zirconia ceramics stabilized using 10 mol% CeO₂ and 1 mol% CaO were studied with the addition of small amounts of α-alumina. The elaboration process of five different compositions was done by wet mixing of powders using 0, 2.5, 5, 10, and 15 wt% alumina, followed by pressing and sintering. The 2.5 wt% alumina addition reduced the grain size, which led to an increase in hardness and the 10 wt% alumina samples showed the maximum mechanical strength (around 1000 GPa), measured by the ball on three balls bending test. The fraction of monoclinic phase around Vickers indentations is reduced by the presence of alumina, but the transformability and resistance to cracking by Vickers indentations are still much higher than for 3Y-TZP. The hydrothermal degradation resistance was also improved by the addition of alumina, with only a very small increase of monoclinic phase of about 1 % in volume after aging for 30 h in standard autoclaved conditions. The enhancement in mechanical properties and LTD resistance leads the path to explore the use of these materials in biomedical applications.     

Effect of sintering temperature on mechanical properties of magnesia partially stabilized zirconia refractory

The optimized sintering conditions for a 3.5 wt% magnesia partially stabilized zirconia (Mg-PSZ) refractory were proposed in our recent research. The influence of the sintering temperature on the development of phase composition, microstructure, densification, thermal expansion and mechanical strength was studied in detail by X-ray diffraction (XRD), scanning electron microscope (SEM), He-pycnometer, high temperature dilatometry and three-point bending test. The samples sintered at 1670 °C had the highest bend strength, the maximum densification, the lowest thermal expansion coefficient (CTE), a homogeneous microstructure and a linear change in thermal expansion.     

Valence state and ionic conduction in Mn‐doped MgO partially stabilized zirconia

The mechanism of the enhancement in the ionic conductivity resulting from cubic phase stabilization in MgO partially stabilized zirconia (MgPSZ) by Mn doping was studied by examining the local Zr‐O structure. Cubic phase (14 vol%) in MgPSZ was increased with the addition of MnO₂, and 10 mol% Mn‐doped MgPSZ exhibited the highest cubic phase fraction (98.72%), which was analyzed by Rietveld refinement. In addition, only the cubic phase, not the monoclinic and tetragonal phases, was observed in the TEM‐SAED pattern of 10 mol% Mn‐doped MgPSZ. Doped Mn exhibited a high Mn²⁺/Mn⁴⁺ ratio, which was identified by X‐ray photoelectron spectroscopy (XPS). In addition, it indicates that oxygen vacancy formation by substitution of Mn²⁺ in the Zr⁴⁺ site in MgPSZ increased cubic phase fraction. Ionic conductivity of MgPSZ was improved by the cubic phase increase attributed to Mn doping, and 10 mol% Mn‐doped MgPSZ exhibited higher ionic conductivity than MgPSZ. To investigate the mechanism of the ionic conductivity improvement, Zr‐O local structure in Mn‐doped MgPSZ was analyzed by Zr K‐edge EXAFS of MgPSZ, and the number of bonding of the Zr‐O first shell decreased with increased Mn substitution. Therefore, it was considered that the oxygen vacancy generation led to an increase in the cubic phase and the number of ionic conduction sites.