High-pressure sintered yttria stabilized zirconia ceramics

Fast densification of 8YSZ ceramics under a high pressure of 4.5 GPa was carried out at different temperatures (800, 1000, 1450 °C), by which a high relative density above 92% could be obtained. FT-Raman spectra indicate that the 8YSZ underwent a phase transition from partially tetragonal to partially cubic phase as temperatures increase from 1000 to 1450 °C when sintering under high pressure. The electrical properties of the samples under different high-pressure sintering conditions were measured by complex impedance method. The total conductivity of 0.92 × 10⁻² S cm⁻¹ at 800 °C has been obtained for 8YSZ under high pressure at 1450 °C, which is about 200 °C lower than that of the samples prepared by conventional pressureless sintering.     

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 manganese oxide addition and reductive atmosphere annealing on the phase stability and microstructure of yttria stabilized zirconia

The effects of Mn₃O₄ addition and reductive atmosphere (N₂:H₂ = 97:3) annealing on the microstructure and phase stability of yttria stabilized zirconia (YSZ) ceramics during sintering at 1500 °C for 3 h in air and subsequent annealing in a reductive atmosphere were investigated. Mn₃O₄ added 6 mol% YSZ (6YSZ) and 10 mol% YSZ (10YSZ) ceramics were prepared via the conventional solid-state reaction processes. The X-ray diffraction results showed that a single cubic phase of ZrO₂ was obtained in 1 mol% Mn₃O₄ added 6YSZ ceramic at a sintering temperature of 1500 °C for 3 h. A trace amount of monoclinic ZrO₂ phases were observed for 1 mol% Mn₃O₄ added 6YSZ ceramics after annealing at 1300 °C for 60 cycles in a reductive atmosphere by transmission electron microscopy. Furthermore, a single cubic ZrO₂ phase existed stably as Mn₃O₄ added 10YSZ ceramics was annealed at 1300 °C for 60 cycles in reductive atmosphere.     

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.     

Microstructure and mechanical properties of yttria stabilized zirconia coatings prepared by plasma spray physical vapor deposition

Plasma spray physical vapor deposition (PS-PVD) was used to deposit yttria stabilized zirconia (YSZ) coatings with different columnar morphologies by varying the spray distance. Although similar quasi-columnar structures were formed at the spray distances of 600 mm and 1400 mm, the formation mechanisms of particles in the coatings were different. Besides, an electron beam physical vapor deposition (EB-PVD) like columnar coating out of pure vapor was deposited at a spray distance of 1000 mm and the columnar consisted of elongated nano-sized secondary columns. The hardness and Young׳s modulus of the coatings were investigated. Compared to the other two quasi-columnar structures, the EB-PVD like columnar coating exhibited higher hardness (~9.0 GPa ) and Young׳s modulus (~110.9 GPa), mainly due to its low porosity and defect.     

Thermophysical behavior of thermal sprayed yttria stabilized zirconia based composite coatings

The effective thermal conductivity of a composite coating depends on intrinsic thermal conductivity of the constituent phases, its characteristics (size, shape) and volume fraction of porosities. The present study concerns studying the effect of CoNiCrAlY and Al₂O₃ content on the coefficient of thermal expansion and thermal conductivity of the YSZ (YSZ-CoNiCrAlY and YSZ-Al₂O₃) based composite coatings developed by thermal spray deposition technique. The coefficient of thermal expansion and thermal conductivity of the composite coatings were measured by push rod dilatometer and laser flash techniques, respectively, from room temperature to 1000 °C. Variation in density, porosity, coefficient of thermal expansion, and thermal conductivity was observed in the composite coatings with the addition of different volume fraction of CoNiCrAlY and Al₂O₃ powders in YSZ-CoNiCrAlY and YSZ-Al₂O₃ composites, respectively. Comparison between the theoretical and experimental thermal conductivities showed a mismatch varying from 4% to 58% for YSZ-CoNiCrAlY composite coatings and from 58% to 80% for YSZ-Al₂O₃ composite coatings. Model based analyses were used to understand the mechanism of thermal conductivity reduction in the composite coatings. It was concluded that the morphology of porosities varied with composition.     

Microstructure and thermal properties of nanostructured gadolinia doped yttria-stabilized zirconia thermal barrier coatings produced by air plasma spraying

In this article, the nanostructured 2 mol% Gd₂O₃-4.5 mol% Y₂O₃-ZrO₂(2GdYSZ) coating was developed by the atmospheric plasma spraying technique. And the microstructure and thermal properties of plasma-sprayed 2GdYSZ coating were investigated. The result from the investigation indicates that the as-sprayed coating is characterized by typical microstructure consisting of melted zones, nano-zones, splats, nano-pores, high-volume spheroidal pores and micro-cracks. The 2GdYSZ coating shows a lower resistance to destabilization of the metastable tetragonal (t′) phase compared to the yttria stabilized zirconia(YSZ). The thermal diffusivity and thermal conductivity of the nano-2GdYSZ coating at room temperature are 0.431 mm² s⁻¹ and 1.042 W/m K, respectively. Addition of gadolinia to the nano-YSZ can significantly reduce the thermal conductivity compared to the nano-YSZ and the conventional YSZ. The reduction is mainly attributed to the synergetic effect of gadolinia doping along with nanostructure.     

Synthesis of nanocrystalline 8 mol% yttria stabilized zirconia by the oleate complex route

Nanocrystalline 8 mol% yttria stabilized zirconia (YSZ) powder has been synthesized by the oleate complex route. Oleate complexes of zirconium and yttrium were formed in the hexane rich layer by the reaction of sodium oleate with zirconyl chloride and yttrium chloride at the interface of the two ternary solutions in water–ethanol–hexane system. The zirconyl oletae and yttrium oleate complexes on heating decomposed to oxide through the formation of carbonate intermediates. The powder obtained by calcination at 600 °C for 2 h was cubic YSZ with surface area of 42 m²/g. The YSZ powder contained primary particles of ∼300 nm size and the primary particles were aggregate of crystallites of 5–10 nm. The compacts prepared from the YSZ powder were sintered to ∼99% TD (theoretical density) at 1400 °C. The sintered YSZ had a low average grain size of 0.73 μm.     

X-ray absorption spectroscopy based investigation of local structure in yttria stabilized zirconia nanoparticles generated by laser evaporation method: Effect of pulsed vs CW mode of laser operation

Two order higher ionic conductivity was reported by us (J. Khare et al., Ceram. Int. 40 (2014) 14677) in pellet made from yttria stabilized zirconia nanoparticles grown under pulsed mode in comparison with pellets made from yttria stabilized zirconia nanoparticles grown under CW mode of CO₂ laser based vaporization method. To understand possible cause of difference in conductivity, the local structure around Zr⁺⁴ ion and Y⁺³ ion has been investigated using X-ray absorption fine structure spectroscopy. The local structure around Zr has been found to depend on the mode of laser vaporization for nanoparticles generation. In case of pulsed mode of vaporization method the charge compensating oxygen vacancies created by the substitution of Y are preferentially forming dipole type defect configuration leading to high ionic conductivity. While formation of immobile tripole type defects are responsible for low ionic conductivity in pellets made from nanoparticles generated under CW mode of laser vaporization.     

Mechanical properties and thermal conductivities of 3YSZ-toughened fully stabilized HfO2 ceramics

In this work, the 3 mol% yttria stabilized zirconia (3YSZ) composed of tetragonal phase has been introduced into the 10 mol% Er₂O₃ stabilized cubic hafnia (10ErSH) matrix to improve its fracture toughness. The effects of the addition of 3YSZ on the phase composition, microstructure, mechanical properties and thermal conductivities of the 10ErSH have been investigated. The results showed that all the 3YSZ-toughened 10ErSH samples were composed of cubic phase and a little (<10 mol%) monoclinic phase. The introduced tetragonal phase of 3YSZ fully disappeared even when the volume fraction of 3YSZ reached 50%, indicating that the phase transformation occurred during 1500 °C. The fracture toughness for the sample with 50% 3YSZ was improved by 60% compared with the pure 10ErSH ceramics owing to the sub-mico/micro hybrid structure, which changed the crack propagation mode and consumed part of the crack extension energy. Additionally, the thermal conductivity slightly decreased due to the mass and radius misfits induced by substitution atoms (Zr⁴⁺, Er³⁺ and Y³⁺). Considering the improved mechanical and thermal properties, the 3YSZ-toughened 10ErSH ceramics may be alternative TBC materials.     

New insights into the thermal aging mechanism of yttria stabilized zirconia: A phase field study

In this paper, a novel phase-field (PF) model is proposed to study the thermal aging mechanism of single crystalline t'-YSZ. The influences of the initial compositional content of yttria and the initial twin structure of the t' phase on the aging process are systematically discussed. The PF model can recover the modulated structure and nano/micro hybrid structure observed in experiments. The PF simulation results indicate that the initial compositional content of yttria is the most important influential factor of the thermal aging process. Besides that, the transformation strain, the initial twin structure and the anti-phase boundaries (APBs) of the t' phase can also have significant influences on the thermal aging kinetics. The typical spinodal region is more suitable to predict the thermal aging behavior of single domain YSZ. For multi-domain YSZ with initial twin structures and APBs, the spinodal region should be further divided into the kernel region and marginal region. In the kernel region, the thermal aging occurs by spinodal decomposition with the formation of a modulated structure, which is followed by merging and coarsening. In the marginal region and outside the spinodal region, the phase decomposition leads to a hybrid structure with coarse grained cubic phase and fine grained tetragonal phase, which exhibits the characteristics of nucleation and growth. The hybrid structure is consistent with previous experimental observations. It is revealed that the boundaries of the nano sized tetragonal grains evolve from the twin boundaries and APBs. The nucleation-growth mechanism should be properly understood when it is applied to illustrate the evolution process of the hybrid structure. The PF model and the new insights obtained in this study are helpful to understand the thermal aging mechanisms of t'-YSZ.     

Enhanced bioactivity and low temperature degradation resistance of yttria stabilized zirconia/clay composites for dental applications

Yttria stabilized zirconia (YSZ)/clay composites were produced to improve osseointegration and undesired tetragonal-to-monoclinic phase transformation (low temperature degradation, LTD) of YSZ ceramics so that long-term clinical success of YSZ implants is achieved. Various amounts (0.5,1,2, and 4 wt%) of clay was incorporated to YSZ. Predetermined amounts of clay and YSZ were mixed and pressed uniaxially at 15 MPa into compacts that were subsequently pressureless sintered at 1450 °C. Density, compressive strength, hardness and indentation crack resistance of 4 wt% clay incorporated YSZ/clay composite were 5.77 ± 0.01 g/cm³, 1188 ± 121 MPa, 1223 ± 9 HV, and 4.4 ± 0.1 MPa√m, respectively. Additionally, biological properties of YSZ/clay composites were assessed in vitro using bone cells. Incorporation of 4 wt% clay significantly enhanced bone cell proliferation, spreading, and functions. Moreover, a significant increase in the LTD resistance of YSZ was achieved upon 4 wt% clay incorporation. The findings collectively suggest that YSZ/clay composites have a potential to be used as an alternative material for dental applications.     

Comparison of thermal shock resistances of plasma-sprayed nanostructured and conventional yttria stabilized zirconia thermal barrier coatings

The main goal of the current study is evaluation and comparison of thermal shock behavior of plasma-sprayed nanostructured and conventional yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs). To this end, the nanostructured and conventional YSZ coatings were deposited by atmospheric plasma spraying (APS) on NiCoCrAlY-coated Inconel 738LC substrates. The thermal shock test was administered by quenching the samples in cold water of temperature 20–25 °C from 950 °C. In order to characterize elastic modulus of plasma-sprayed coatings, the Knoop indentation method was employed. Microstructural evaluation, elemental analysis, and phase analysis were performed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffractometry (XRD) respectively. The results revealed that failures of both nanostructured and conventional TBCs were due to the spallation of ceramic top coat. Thermal stresses caused by mismatch of thermal expansion coefficients between the ceramic top coat and the underlying metallic components were recognized as the major factor of TBC failure. However, the nanostructured TBC, due to bimodal unique microstructure, presented an average thermal cycling lifetime that was approximately 1.5 times higher than that of the conventional TBC.     

Synthesis of nanocrystalline 8 mol% yttria stabilized zirconia powder from sucrose derived organic precursors

An organic precursor synthesis of 8 mol% yttria stabilized zirconia (YSZ) powder from Zr–Y composite nitrate solution and sucrose has been studied. Oxidation of sucrose in Zr–Y composite nitrate solution containing excess nitric acid in situ generates hydroxy carboxylic acids that forms a white sol which showed peaks at 1640 cm⁻¹ and 1363 cm⁻¹ in IR spectrum corresponding to hydroxy carboxylic acid complexes of Zr and Y. Precursor mass obtained by drying the sol on calcinations at 600 °C produced loosely agglomerated particles of cubic YSZ. Deagglomerated YSZ contain submicron particles with D₅₀ value of 0.5 μm and the particles are aggregates of nanocrystallites of nearly 10 nm size. Compacts prepared by pressing the YSZ powder sintered to 96.7% TD at 1450 °C. The sintered YSZ ceramic showed an average grain size of 2.2 μm.     

Stability of yttria stabilized zirconia in molten oxy-fluorite flux for the production of silicon with the solid oxide membrane process

Solar grade silicon can be formed using a YSZ solid oxide membrane (SOM). The SOM membrane is exposed to a complex fluoride flux with dissolved silica at high temperature and electrochemically separated into silicon and oxygen. A failure mode of the SOM membrane by the formation of ‘inner cracks’ was studied, and attributed to yttria depletion in the YSZ, leading to phase transformation from cubic to tetragonal phase. The roles of silica and YF₃ in the flux were studied, and it was shown that silica attacks the SOM membrane, while YF₃ retards the attack. A detailed mechanism of the yttrium depleted layer (YDL) formation, and its role in the formation of inner cracks is proposed. Based on this study, a new flux composition was designed and tested. The flux composition did not attack the SOM membrane, and Si crystals were produced, demonstrated long-term viability of the Si–SOM process.     

The influence of laser treatment on hot corrosion behavior of plasma-sprayed nanostructured yttria stabilized zirconia thermal barrier coatings

In this study, the effect of laser glazing on the hot corrosion behavior of nanostructured thermal barrier coatings (TBCs) was investigated. To this end, the hot corrosion test of plasma-sprayed and laser-glazed thermal barrier coatings conducted against 45 wt.% Na₂SO₄ + 55 wt.% V₂O₅ molten salt at 910 °C for 30 h in open air atmosphere. The results obtained from hot corrosion test showed that the reaction between Y₂O₃ and the corrosive salt produced YVO₄, leached Y₂O₃ from YSZ and led to the progressive destabilization transformation of YSZ from tetragonal to the monoclinic phase. The lifetimes of the plasma-sprayed TBCs were enhanced approximately twofold by laser glazing. Reducing the reactive specific surface area of the dense glazed layer with the molten salts and improving the stress accommodation through network cracks produced by laser glazing were the main enhancement mechanisms accounting for TBC life extension.     

A new and simple way to prepare monolithic solid oxide fuel cell stack by stereolithography 3D printing technology using 8 mol% yttria stabilized zirconia photocurable slurry

Yttria (8 mol%) stabilized zirconia (8YSZ) photocurable slurry is the basis for stereolithography-based 3D (SLA) printed structured electrolyte support for monolithic solid oxide fuel cell (SOFC) stack. The curing resin with trifunctional trimethylolpropane triacrylate and 1,6-hexanediol diacrylate (TMPTA/HDDA) mass ratio of 1.5:8.5 and 1 wt% of photoinitiator provided excellent curing performance and low viscosity of 2.1 mPa·s. Stable 8YSZ photocurable slurry possessing high solid content of 43 vol% and low viscosity of 3.6 Pa·s at 30 s^?1 shear rate were obtained, without particle sedimentation after 180-day stability test. The activation energy of 8YSZ fabricated by 3D printing method was 0.87 eV, similar to that by dry-pressing method. The 3D printed monolithic 3-tube SOFC stack exhibited a peak power density of 230 mW·cm^?2 at 850 °C. This research proves the great potential of 3D printing technology to prepare monolithic SOFC stack, paving the way to develop SOFCs for practical applications.     

Effect of Y doping on microstructure and thermophysical properties of yttria stabilized hafnia ceramics

A series of Y₂O₃-doped HfO₂ ceramics (Hf_1-xY_xO_2-0.5×, x?=?0, 0.04, 0.08, 0.12, 0.16 and 0.2) were synthesized by solid-state reaction at 1600?°C. The microstructure, thermophysical properties and phase stability were investigated. Hf_1-xY_xO_2–0.5x ceramics were comprised of monoclinic (M) phase and cubic (C) phase when Y³⁺ ion concentration ranged from 0.04 to 0.16. The thermal conductivity of Hf_1-xY_xO_2–0.5x ceramic decreased as Y³⁺ ion concentration increased and Hf_0.8Y_0.2O_1.9 ceramic revealed the lowest thermal conductivity of ~?1.8?W/m*K at 1200?°C. The average thermal expansion coefficient (TEC) of Hf_1-xY_xO_2–0.5x between 200?°C and 1300?°C increased with the Y³⁺ ion concentration. Hf_0.8Y_0.2O_1.9 yielded the highest TEC of ~?10.4?×?10^?6 K^?1 while keeping good phase stability between room temperature and 1600?°C.     

Anti-CMAS corrosion mechanism of Al2O3 pore sealing and laser remelting on thermal barrier coatings

The sol-dip-coating method and surface laser remelting technology are applied to form an Al₂O₃ layer on a YSZ coating surface to effectively block the environmental sediment CMAS. The behaviour and mechanism for CMAS corrosion of the coating are investigated, and the interfacial reliability of the coating and matrix is calculated by using the Monte Carlo method. The bonding force between the Al₂O₃ sol and YSZ coating can be effectively improved by laser surface treatment. Samples subjected to a laser pretreatment and posttreatment (YL-AL) of the YSZ coating are found to show the best interfacial bonding strength between Al₂O₃ and YSZ. Furthermore, the YL-AL sample shows a higher CMAS resistance than the laser posttreatment (Y-AL) samples, which effectively combines the chemical resistance of Al₂O₃ to CMAS and the physical resistance of the laser re-melted densification layer against CMAS penetration.