Toughening and strengthening zirconia through the addition of a transient solid solution additive

A very small amount of nickel oxide (NiO), 0.18 mol%, could dissolve into yttria-stabilized zirconia (YSZ) during sintering in air at elevated temperature. The presence of Ni solutes enhances both the densification and grain growth of YSZ specimens. By heat-treating the NiO-doped YSZ specimen in a reducing atmosphere, nano-sized Ni particles are produced at the grain boundaries. The NiO thus acts as a transient solid solution additive for the YSZ-Ni nanocomposite. The formation of Ni nano-particles introduces an extra ferromagnetic performance into the YSZ specimen. Furthermore, the toughness and strength of YSZ are enhanced respectively by 120% and 40%. The toughness enhancement shows strong dependence on the size of ZrO₂ grains. Nevertheless, the strengthening is contributed by many factors.     

Improvements to the sintering of yttria-stabilized zirconia by the addition of Ni

We have studied the effect of nickel oxide (NiO) on the sintering of yttria-stabilized zirconia (YSZ) at temperatures from 1100 to 1400 °C. Differences in the densification behaviour were observed between the direct use of NiO powders and Ni metal as precursor. Our results show that with the addition of Ni into YSZ, sintering was completed at 1300 °C instead of 1400 °C, a 100 °C reduction. The addition of Ni also increased the shrinkage rate at 1200 °C from −0.29×10⁻⁶ s⁻¹ to −0.46×10⁻⁶ s⁻¹. Young's modulus of the samples heat treated at 1200 °C measured by microindentation also increased from 26 GPa for YSZ to 65 or 191 GPa for YSZ plus NiO or Ni, respectively. Addition of NiO or Ni also stabilised the cubic phase and promoted grain growth in YSZ during sintering.     

Effect of Fe2O3 doping on sintering of yttria-stabilized zirconia

This paper reports the effect of Fe₂O₃ doping on the densification and grain growth in yttria-stabilized zirconia (YSZ) during sintering at 1150 °C for 2 h. Fe₂O₃ doped 3 mol% YSZ (3YSZ) and 8 mol% YSZ (8YSZ) coatings were produced using electrophoretic deposition (EPD). For 0.5 mol% Fe₂O₃ doping, both 3YSZ and 8YSZ coatings during sintering at 1150 °C has similar densification. However, a significant grain growth occurred in 8YSZ during sintering, whereas grain size remains almost constant in 3YSZ. XRD results suggest that Fe₂O₃ addition substitutionally and interstitially dissolved into the lattice of 3YSZ and 8YSZ. In addition, colour of 3YSZ and 8YSZ changes differently with doping of Fe₂O₃. A Fe³⁺ ion interstitial diffusion mechanism is proposed to explain the densification and grain growth behaviour in the Fe₂O₃ doped 3YSZ and 8YSZ. A retard grain growth observed in the Fe₂O₃ doped 3YSZ is attributed to Fe³⁺ segregation at grain boundary.     

Sintering behavior and mechanisms of NiO-doped 8 mol% yttria stabilized zirconia

Sintering behavior and densification mechanisms of NiO-doped YSZ were investigated by using a dilatometer, combined with XRD, SEM and HRTEM characterization. The solubility of NiO in YSZ is found to be 0.5-1 mol% at 1500 °C by XRD, and TEM reveals that, beyond solubility limit, the undissolved NiO exists in the form of nano and/or micro-sized crystals depending on the doping amount. The sintering model was used to address the enhanced sintering of YSZ as a result of small additions of NiO. Lattice diffusion is examined to be the rate-determining mechanism for the intermediate-stage sintering of both undoped and NiO-doped YSZ. However, the apparent activation energy for densification of YSZ is reduced by ∼70 kJ/mol upon NiO doping. It is concluded that the dissolved NiO contributes to the lowering of the activation energy and therefore the enhanced lattice diffusivity.     

Effect of the B2O3 addition on the sintering behavior and microwave dielectric properties of Ba3(VO4)2–Zn1.87SiO3.87 composite ceramics

The effect of the B₂O₃ addition on the low-temperature sintering, microstructure and microwave dielectric properties of the Ba₃(VO₄)₂–Zn_1.87SiO_3.87 composite ceramics was investigated. The results indicate that the addition of B₂O₃ can effectively promote the densification and further improve the microwave dielectric properties of the composite. The low-temperature sintering mechanism was ascribed to the formation of the liquid phase owing to the reaction between the additive B₂O₃ and the residual SiO₂ in the composite. B₂O₃–SiO₂ liquid phases can not only lower the sintering temperature, but also speed up the grain growth of the composite ceramics. The rapid grain growth occurs as the B₂O₃ content is more than 6 wt%. The 3 wt% B₂O₃ doped 0.5Ba₃(VO₄)₂–0.5Zn_1.87SiO_3.87 ceramics can be well sintered at 925 °C and exhibit excellent microwave dielectric properties of Q×f∼40,800 GHz, ε_r∼10 and τ_f∼0.5 ppm/°C.     

The influence of hafnium removal on the microstructure and properties of 8YSZ ceramics

The effects of hafnium removal on the sinterability, phase composition, and microstructural, mechanical, and electrical properties of 8YSZ (8 mol% yttrium stabilized zirconia) were investigated using SEM, XRD, Raman spectroscopy, EBSD, three-point bending, Vickers indentation, and impedance spectroscopy. The 8YSZ and 8YSZ₀ (8 mol% yttrium-stabilized hafnium-free zirconia) ceramics were prepared via dry pressing and atmospheric sintering, respectively. The overall mechanical properties of the 8YSZ₀ ceramic were poor. However, at a sintering temperature of 1450°C, the relative density of 8YSZ and 8YSZ₀ ceramics was almost identical. 8YSZ₀ had a slightly smaller grain size and activation energy, and its electrical properties were slightly better than those of the 8YSZ ceramics. The presence of tetragonal secondary phases in the cubic structure of 8YSZ ceramics inhibited crack propagation and led to an increase in the mechanical properties and a decrease in the ion conductivity. In terms of the crystal structure, the increase in the cubic phase lattice parameters and tetragonal phase c/a values of the 8YSZ₀ ceramics was attributed to the larger Zr⁴⁺radius, reduced local lattice distortion, and increased matrix oxygen vacancy concentration and cubic phase content. The EBSD analysis results indicated that there was no significant difference in grain orientation between the two types of ceramics, but the content of 8YSZ ceramics in large angle grain boundaries was slightly higher, especially in special grain boundaries Σ3 and Σ9. Therefore, this material can be used as a solid-state electrolyte candidate.     

Adhesion behavior between yttrium-stabilized zirconia added La0.8Ca0.2Cr0.9Co0.1O3−δ interconnector and yttrium-stabilized zirconia-based substrate

Because of the different densification characteristics of a La_0.8Ca_0.2Cr_0.9Co_0.1O_3-δ (LCCC) interconnector and a NiO added yttrium-stabilized zirconia (YSZ) anode, complete adhesion between the two layers is hardly obtainable. In this study, we have investigated the sintering behavior of LCCC with the addition of YSZ. As the amount of YSZ increases, densification of the LCCC is inhibited and the initial temperature of the densification increases. However, when the LCCC–YSZ composite layer is screen printed on the NiO–YSZ substrates, the density of the composite layer increases and the layer is firmly attached to the substrates. It is proposed that tensile stress is decreased on the composite layer due to the relatively delayed densification of the LCCC–YSZ composite, compared to the densification of the NiO–YSZ substrate.     

Sintering behavior and properties of lithium stabilized sodium β'' - alumina ceramics with YSZ addition

In this study, investigations of sintering behavior and properties were performed on lithium-stabilized Na-β''-alumina (LiSBA) ceramics with and without 15?wt% 8?mol% Y₂O₃ stabilized ZrO₂ (8YSZ) addition synthesized by solid phase reaction. Changes of phase composition, relative density, and grain size in the ceramics sintered at different temperature were analyzed. It was shown that phase transformation in sintering ceramics was controlled by relationship between the Na₂O evaporation and Li⁺ ions stabilization, while microstructure evolution was controlled by pore-boundary interaction. LiSBA with YSZ addition (Zr-LiSBA) showed more significant variation of β'' phase fractions, slower grain growth and faster densification with increasing sintering temperature, which were caused by enhanced Na₂O evaporation and gas transport by oxygen ion conductor ZrO₂ as well as the drag effect by second phase particles of YSZ in Zr-LiSBA ceramics. Zr-LiSBA specimens sintered at optimized condition achieved higher Vickers microhardness and intermediate Na⁺ ion conductivity.     

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.     

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.     

Two-step sintering of nanocrystalline 8Y2O3 stabilized ZrO2 synthesized by glycine nitrate process

Two-step sintering was employed to consolidate nanocrystalline 8 mol% yittria stabilized zirconia processed by glycine-nitrate method. Results verified the applicability of this method to suppress the final stage of grain growth in the system. The grain size of the high density compacts (>97%) produced by two-step sintering method was seven times less than the pieces made by the conventional sintering technique. Up to ∼96% increase in the fracture toughness was observed (i.e. from 1.61 to 3.16 MPa m^1/2) with decreasing of the grain size from ∼2.15 to ∼295 nm. A better densification behavior was also observed at higher compacting pressures.     

Initial sintering mechanism and additive effect in zirconia ceramics

Y₂O₃-stabilized ZrO₂ (YSZ) ceramics have been used for various engineering applications because of their excellent mechanical properties or oxide-ion conductivity applicable to solid-electrolyte. The performance of YSZ depends on the sintered texture that is directly determined by sinterability of raw powders. A new kinetic analysis method of diffusion mechanism based on an initial sintering theory (grain-boundary or volume diffusion) is theoretically derived, the initial sintering mechanism of hydrolytic YSZ powder is experimentally determined, and the effects of powder characteristics on sinterability are discussed. Furthermore, the additive-enhanced sintering is proposed. A small amount of Al₂O₃ significantly enhances the densification. Using the additive effect, the low-temperature degradation that is the fault of zirconia ceramics can be improved by decreasing the sintering temperature.     

Transparent polycrystalline MgAl2O4 ceramic fabricated by spark plasma sintering: Microwave dielectric and optical properties

The optical properties and microwave dielectric properties of transparent polycrystalline MgAl₂O₄ ceramics sintered by spark plasma sintering (SPS) through homemade nanosized MgAl₂O₄ powders at temperatures between 1250 °C and 1375 °C are discussed. The results indicate that, with increasing sintering temperatures, grain growth and densification occurred up to 1275 °C, and above 1350 °C, rapid grain and pore growth occurred. The in-line light transmission increases with the densification and decreases with the grain/pore growth, which can be as high as 70% at the wavelength of 550 nm and 82% at the wavelength of 2000 nm, respectively. As the sintering temperature increases, Q×f and dielectric constant ε_r values increase to maximum and then decrease respectively, while τ_f value is almost independent of the sintering temperatures and remains between −77 and −71 ppm/°C. The optimal microwave dielectric properties (ε_r=8.38, Q×f=54,000 GHz and τ_f=−74 ppm/°C) are achieved for transparent MgAl₂O₄ ceramics produced by spark plasma sintering at 1325 °C for 20 min.     

Microstructure-property relationships in composites of 8YSZ ceramics and in situ graphitized nanocellulose

Ceramic matrix composites (CMC) of 8 mol.% yttria-stabilized zirconia (8YSZ) mixed with natural fiber nanocellulose (0.75, 1, 2 wt%) were prepared by spark plasma sintering (SPS). Nanocellulose markedly improved the densification of the 8YSZ ceramic matrix and induced significant grain size refinement. It was demonstrated that in situ graphitization of nanocellulose during the SPS processing resulted in 6 nm thin turbostratic graphite layers homogeneously covering the 8YSZ ceramic grains. The dielectric properties were analyzed by electrical impedance spectroscopy suggesting a low percolation threshold near or below ≈ 1.6 vol% graphite, above which mixed ionic-electronic conduction dominates. The CMCs are stable under reducing conditions (5%H₂/Ar atmosphere) at least until 800 °C with a high conductivity of σ_dc = 0.17 S?cm^?1 even at 900 °C (8YSZ-2%CNF). These features make the 8YSZ-nanocellulose CMCs promising candidates for application in medium- to high-temperature electrochemical devices.     

The influence of additives on microstrucutre of sub-micron alumina ceramics prepared by two-stage sintering

For various systems two-stage sintering has been reported as a successful way of suppressing the grain growth in the final stage of densification of polycrystalline ceramics. Our previous results on two-stage sintering of high purity submicrometre polycrystalline alumina indicate limited efficiency of the process with respect to suppression of grain growth. The present work deals with the influence of deliberate additions of various metal oxides (500 ppm of MgO, Y₂O₃ or ZrO₂) whose grain growth retarding effect in conventional sintering has been well documented, on two-stage sintering of submicrometre alumina ceramics. The addition of MgO was observed to enhance densification. Addition of yttria and zirconia impaired densification, but addition of all three dopants resulted in suppression of the grain growth and microstructure refinement in comparison to undoped alumina.     

Two-step sintering of fine alumina–zirconia ceramics

This work investigates the feasibility to the fabrication of high density of fine alumina–5 wt.% zirconia ceramics by two-step sintering process. First step is carried out by constant-heating-rate (CHR) sintering in order to obtain an initial high density and a second step is held at a lower temperature by isothermal sintering aiming to increase the density without obvious grain growth. Experiments are conducted to determine the appropriate temperatures for each step. The temperature range between 1400 and 1450 °C is effective for the first step sintering (T₁) due to its highest densification rate. The isothermal sintering is then carried out at 1350–1400 °C (T₂) for various hours in order to avoid the surface diffusion and improve the density at the same time. The content of zirconia provides a pinning effect to the grain growth of alumina. A high ceramic density over 99% with small alumina size controlled in submicron level (0.62–0.88 μm) is achieved.     

Flash Spark Plasma Sintering of 3YSZ: Modified sintering pathway and impact on grain boundary formation

Yttria stabilized zirconia (3 mol% YSZ) ceramics were prepared by Flash-SPS, while allowing high heating rates up to 200 °C/s, which led to the extremely fast densification within a few seconds. The high heating rates had strong impact on sintering mechanisms, in terms of densification and grain growth. While the specimens ended with 5–15 vol% porosity and limited grain growth (< 350 nm), their hardness is higher than fully dense counterpart SPSed ceramics. Using the sintering trajectories, microstructural observations, and impedance spectroscopy, we highlight altered sintering mechanism which resulted in very thin grain boundaries compared to SPS. It appears that densification is largely advanced at grain boundary interfaces, with no residual nano-pores at the grain junctions, where some pores with size comparable to grain size were present. This opens up opportunities for the fabrication of porous lightweight ceramics with good mechanical properties.     

Studies on ionic conductivity of stabilized zirconia ceramics (8YSZ) densified through conventional and non-conventional sintering methodologies

Densification studies of 8 mol% yttria stabilized zirconia ceramics were carried out by employing the sintering techniques of conventional ramp and hold (CRH), spark plasma sintering (SPS), microwave sintering (MWS) and two-stage sintering (TSS). Sintering parameters were optimized for the above techniques to achieve a sintered density of >99% TD. Microstructure evaluation and grain size analysis indicated substantial variation in grain sizes, ranging from 4.67 μm to 1.16 μm, based on the sintering methodologies employed. Further, sample was also sintered by SPS technique at 1425 °C and grains were intentionally grown to 8.8 μm in order to elucidate the effect of grain size on the ionic conductivity. Impedance spectroscopy was used to determine the grain and grain boundary conductivities of the above specimens in the temperature range of RT to 800 °C. Highest conductivity of 0.134 S/cm was exhibited by SPS sample having an average grain size of 1.16 μm and a decrease in conductivity to 0.104 S/cm was observed for SPS sample with a grain size of 8.8 μm. Ionic conductivity of all other samples sintered vide the techniques of TSS, CRH and MWS samples was found to be ∼0.09 S/cm. Highest conductivity irrespective of the grain size of SPS sintered samples, can be attributed to the low densification temperature of 1325 °C as compared to other sintering techniques which necessitated high temperatures of ∼1500 °C. The exposure to high temperatures while sintering with TSS, CRH and MWS resulted into yttria segregation leading to the depletion of yttria content in fully stabilized zirconia stoichiometry as evidenced by Energy Dispersive Spectroscopy (EDS) studies.     

Densification and grain growth of 8YSZ containing NiO

The effects of NiO addition on sintering yttria-stabilized zirconia were systematically studied to understand the role of the additive in the sintering process of the solid electrolyte. Specimens of 8 mol% yttria-stabilized zirconia with NiO contents up to 5.0 mol% were prepared using different Ni precursors and sintered at several dwell temperatures and holding times. Densification and microstructural features were studied by apparent density measurements and scanning electron microscopy observations, respectively. The sintering dynamic study was carried out by following the linear shrinkage of powder compacts containing 0-0.75 mol% NiO. Small (up to 1.0 mol%) NiO addition was found to improve the sinterability of yttria-stabilized zirconia. The activation energy for volume diffusion decreases with increasing NiO content, whereas the grain boundary diffusion seems to be independent on this additive. The grain growth of yttria-stabilized zirconia is found to be enhanced even for small NiO contents.     

Electro‐Sintering of Yttria‐Stabilized Cubic Zirconia

Electro‐sintering, i.e., electrically enhanced densification without the assistance of Joule heating, has been observed in 70% dense 8 mol% Y₂O₃‐stabilized ZrO₂ ceramics at temperatures well below those for conventional sintering. Remarkably, full density can be obtained without grain growth under a wide range of conditions, including those standard for solid oxide fuel cell (SOFS) and solid oxide electrolysis cell (SOEC), such as 840°C with 0.15 A/cm². Microstructure evidence and scaling analysis suggest that electro‐sintering is aided by electro‐migration of pores, made possible by surface flow of cations across the pore meeting lattice/grain‐boundary counter flow of O^2?. This allows pore removal from the anode/air interface and densification at unprecedentedly low temperatures. Shrinkage cracking caused by electro‐sintering of residual pores is envisioned as a potential damage mechanism in SOFC/SOEC 8YSZ membranes.