Effect of cation doping on lattice and grain boundary diffusion in superplastic yttria-stabilized tetragonal zirconia

Lattice diffusion coefficients D_l and grain boundary diffusion D_gb coefficients of hafnium were studied for 0.5 and 1 mol% cation-doped yttria-stabilized tetragonal zirconia at the temperature range from 1283 to 1510 °C. The diffusion profiles were determined by two experimental techniques: secondary ion mass spectroscopy and electron microprobe analysis. Additionally the first principle calculations of the electronic states of Zr⁴⁺, dopant cations and O^2? anions and elastic properties in 3Y-TZP were performed. Superplastic strain rate versus stress and inverse temperature was also measured. For 1 mol% doped samples the significant increase of the grain boundary diffusion and superplastic strain rate was observed. Correlations between the calculated ionic net charges and D_gb indicate that enhancement of D_gb was caused by the reduction of ionic bonding strength between metal cation and oxygen anion in zirconia. The new constitutive equation for superplastic flow of yttria-stabilized tetragonal zirconia ceramics was obtained.     

Grain-Size Dependence of Thermal-Shock Resistance of Yttria-Doped Tetragonal Zirconia Polycrystals

Thermal-shock fracture behavior of yttria-doped tetragonal zirconia polycrystals (Y-TZP) of various grain sizes was evaluated by the quenching method using water as the quenching solvent. The tetragonal-to-monoclinic phase transformation behavior of Y-TZP around cracks introduced by thermal stress was investigated by using Raman microprobe spectroscopy. The critical quenching temperature difference (Δ T _c ) of Y-TZP ceramics increased from 250° to 425°C with increasing grain size of zirconia from 0.4 to 3.0 μm, while the fracture strength decreased from 900 to 680 MPa. The improvement of Δ T _c of Y-TZP with increasing grain size of zirconia corresponded with the quantity of tetragonal-to-monoclinic phase transformation around cracks introduced by thermal stress.     

Revealing crack profiles in polycrystalline tetragonal zirconia by ageing

Exposure to hot water vapour is shown to be useful for staining indentation crack profiles in doped zirconia polycrystals. This is illustrated here in 3Y-TZP with two different grain sizes, for which Vickers indentation cracks are of Palmqvist type, as well as in 3Y-TZP with 2.5 wt.% cerium oxide, for which indentation cracks are half-penny. The crack profile is clearly revealed on the fracture surface after biaxial flexural testing in all the specimens previously exposed to hot water vapour. The contrast in 3Y-TZP is induced by t–m transformation caused by hydrothermal degradation, which induces an intergranular fracture zone in front of the initial position of the indentation crack tip. The biaxial strength and apparent fracture toughness of 3Y-TZP increase substantially with the time of exposure at a rate that depends on the grain size. On the contrary, in 3Y-TZP doped with ceria no signal of t–m transformation is found and the flexure biaxial stress remains practically constant, but the initial position of the indentation crack is also clearly revealed by an intergranular fracture zone in front of the initial position of the crack tip. In this case, this is associated to environmentally assisted slow crack growth under the indentation residual stress during exposure to hot water vapour in autoclave.     

Grain Growth of Silica-Added Zirconia Annealed in the Cubic/Tetragonal Two-Phase Region

The grain growth in silica-doped 3-mol%-yttria-stabilized tetragonal zirconia polycrystals (SiO₂-doped 3Y-TZP) and undoped 3Y-TZP has been examined in the temperature range of 1400°-1800°C. The presence of a SiO₂ phase inhibits rather than promotes the grain growth in 3Y-TZP, particularly at high temperatures. During the grain growth in 3Y-TZP, yttrium ions are partitioned between grains, and the grain growth mechanism can be understood from Ostwald ripening dominated by lattice diffusion of cations. In SiO₂-doped 3Y-TZP, an amorphous SiO₂-rich phase exists only in the grain-boundary corners or junctions, not in the grain-boundary faces. The grain growth in SiO₂-doped 3Y-TZP is controlled by using different mechanisms below and above the eutectic temperature of the zirconia-silica (ZrO₂-SiO₂) system. The glass phase does not have a major role in grain growth below the eutectic temperature, and the grain growth is dominated by a similar mechanism in undoped 3Y-TZP. The grain growth is more effectively retarded by the presence of a SiO₂ phase above the eutectic temperature and is likely to be controlled by a solution-reprecipitation process in the amorphous phase at the grain-boundary corners or junctions.     

Synthesis,sintering and microstructure of 3Y-TZP/CuO nano-powder composites

Nanocrystalline 3Y-TZP and copper-oxide powders were prepared by co-precipitation of metal chlorides and copper oxalate precipitation respectively. CuO (0.8 mol%) doped 3Y-TZP powder compacts were prepared from the nanocrystalline powders. Dilatometer measurements on these compacts were performed to investigate the sintering behaviour. Microstructure investigations of the sintered compacts were conducted. It is found that additions of the copper-oxide powders in the nanocrystalline 3Y-TZP leads to an enhancement of densification, formation of monoclinic zirconia phase and significant zirconia grain growth during sintering.     

Manipulating microstructure and mechanical properties of CuO doped 3Y-TZP nano-ceramics using spark-plasma sintering

Nano-powder composites of 3Y-TZP doped with 8 mol% CuO were processed by spark-plasma sintering (SPS). A 96% dense composite ceramic with an average grain size of 70 nm was obtained by applying the SPS process at 1100 °C and 100 MPa for 1 min. In contrast to normal, pressureless, sintering during SPS reactions between CuO and 3Y-TZP were suppressed, the CuO phase was reduced to metallic Cu, while the 3Y-TZP phase remained almost purely tetragonal. Annealing after SPS results in grain growth and tetragonal to monoclinic zirconia phase transformation. The grain size and monoclinic zirconia phase content are strongly dependent on the annealing temperature. By combining the processing techniques studied in this work, including traditional pressureless sintering, properties of the composite ceramic can be tuned via manipulation of microstructure. Tuning the mechanical properties of dense 8 mol% CuO doped 3Y-TZP composite ceramic by utilising different processing techniques is given as an example.     

Deformation of Monoclinic ZrO2 Polycrystals and Y2O3-Stabilized Tetragonal ZrO2 Polycrystals below the Monoclinic–Tetragonal Transition Temperature

Ultrafine-grained monoclinic ZrO₂ polycrystals (MZP) and 3-mol%-Y₂O₃-stabilized tetragonal ZrO₂ polycrystals (3Y-TZP) were obtained by hot isostatic pressing (HIP). Both MZP and TZP were "high-purity" materials with impurities less than 0.1 wt%. The deformation behavior was studied at 1373 K, which was lower than the monoclinic ↔ tetragonal transition temperature. The stress exponent of 3Y-TZP with grain size of 63 nm was 3 in the higher stress region, and increased from 3 to 4 with decreasing stress. The deformation of MZP was characterized by a stress exponent of 2.5 over a wide stress range. The strain rate of 3Y-TZP was slower than that of MZP by 1 order of magnitude. It was suggested that either the doped yttrium or the difference in the crystal structure affected the diffusion coefficients of ZrO₂.     

Optimization of particle size,dispersity, and conductivity of 8 mol% Y2O3 doped tetragonal zirconia polycrystalline nanopowder prepared by modified sol-gel method via activated carbon absorption

8 mol% Y₂O₃ doped tetragonal zirconia polycrystalline (8Y-TZP) ceramic nanopowders were synthesized via a novel modified sol-gel method employing zirconium carbonate basic as zirconium resources. The activated carbon as a dispersant was added to the precursor solution during the formation of the sol. The phase behavior, thermal decomposition, microstructure morphology, and electrochemical performance of nanopowders with the addition of activated carbons were investigated by X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron microscopy (SEM), particles size distribution, and electrochemical impedance spectroscopy analysis (EIS). After adding the activated carbon, the average crystallite size of 8Y-TZP nanopowders decreased from about 53.16–33.51 nm when calcined at 900 ℃, and the 8Y-TZP nanopowders were produced loosely agglomerated. Meanwhile, compacts prepared by pressing the as-obtained 8Y-TZP nanopowders sintered to 98.8% relative density at 1600 ℃ and exhibited an average grain size of 0.89 µm, which brought a positive effect on ionic conductivity (0.079 S·cm^?1).     

Plasticity of nanocrystalline yttria-stabilized tetragonalzirconia polycrystals

The high-temperature behavior of nanocrystalline yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) with an initial grain size of 120 nm has been studied in uniaxial compression as a function of stress (5–200 MPa) and temperature (1150–1250 °C). The creep parameters, n=2 and Q=630 kJ/mol, were obtained for all experimental conditions. Evaluation of the strain rates showed that the material was more creep resistant than expected for very fine-grained materials. An interface-controlled mechanism is proposed to account for the experimental results.     

High-Temperature Tensile Deformation of Glass-Doped 3Y-TZP

Amorphous grain boundary phases in 3-mol%-yttria-stabilized zirconia ceramics (3Y-TZP) were studied to determine the influence of intergranular amorphous silicate phases on tensile superplasticity at temperatures of 1300–1500°C. Controlled additions (1 wt%) of compositionally distinct barium silicate and borosilicate phases were used. The initial grain sizes of the pure, barium silicate added, and borosilicate-added samples were 0.45, 0.55, and 0.55 μm, respectively. Systems with added barium silicate and borosilicate glass both exhibited a 60% reduction in flow stress as compared with pure 3Y-TZP, with the lower-viscosity barium silicate system exhibiting a slightly greater reduction in flow stress. The higher-viscosity borosilicate glass/3Y-TZP materials exhibited the greatest elongation to failure, while the barium silicate/3Y-TZP materials had the least elongation. Yttrium was found to segregate to grain boundaries in the pure and borosilicate-containing samples, and both yttrium and barium were found to segregate to grain boundaries in the barium silicate containing samples. No silicon was observed along two-grain boundaries in any of the samples, even those containing pockets of glass. The difference in deformation behavior may be due to a combination of viscosity of the glass addition, grain boundary segregation, and grain boundary bond character.     

Adsorption as a Method of Doping 3-mol%-Yttria-Stabilized Zirconia Powder with Copper Oxide

The adsorption behavior of Cu²⁺ on 3-mol%-yttria-stabilized tetragonal zirconia polycrystalline (3Y-TZP) powder was studied. There is a window of ph values (10 < pH < 11) where adsorption may be used as a method of doping 3Y-TZP with Cu²⁺. The maximum mole percent of the CuO additions is determined by the specific surface area of the 3Y-TZP powder; a powder with a specific surface area of 16.1 m²/g is limited to about 1 mol% CuO. Compacts made from powders doped with CuO using this method exhibited an enhancement in superplasticity comparable to that observed in other studies using samples doped with CuO by attrition milling.     

Sintering Behavior of 0.8 mol%-CuO-Doped 3Y-TZP Ceramics

In recent years, 3 mol% yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) doped with copper oxide has obtained increasing interest due to its enhanced superplastisity and good potential in tribological applications. In this work, the effect of addition of small amounts (0.8 mol%) of copper oxide on the sintering behavior of 3Y-TZP was studied using a dilatometer and high-temperature X-ray diffraction (XRD). A qualitative sintering model was established based on several reactions during sintering as indicated by thermal analysis and XRD. Some of these reactions remarkably retard densification and consequently result in low final density (86%) of the sample sintered at 1400°C in air. The reaction between molten Cu₂O and yttria as segregated to the Y-TZP grain boundaries at around 1180°C leads to the depletion of yttria from Y-TZP grains, which results in the formation of monoclinic phase during cooling. A relatively higher oxygen partial pressure can inhibit the dissociation of CuO to Cu₂O. This inhibition in dissociation is one of the reasons why a dense (>96%) 0.8 mol% CuO-doped 3Y-TZP ceramic can be obtained after sintering at 1400°C in flowing oxygen.     

Influence of Amorphous Grain Boundary Phases on the Superplastic Behavior of 3-mol%-Yttria-Stabilized Tetragonal Zirconia Polycrystals (3Y-TZP)

Amorphous silicate grain boundary phases of varying chemistry and amounts were added to 3Y-TZP in order to determine their influence on the superplastic behavior between 1200° and 1300°C and on the room-temperature mechanical properties. Strain rate enhancement at high temperatures was observed in 3Y-TZP containing a glassy grain boundary phase, even with as little as 0.1 wt% glass. Strain rate enhancement was greatest in 3Y-TZP with 5 wt% glass, but the room-temperature hardness, elastic modulus, and fracture toughness were degraded. The addition of glassy grain boundary phases did not significantly affect the stress exponent of 3Y-TZP, but did lower the activation energy for superplastic flow. Strain rate enhancement was highest in samples containing the grain boundary phase with the highest solubility for Y₂O₃ and ZrO₂, but the strain rate did not scale inversely with the viscosity of the silicate phases. Grain boundary sliding accommodated by diffusional creep controlled by an interface reaction is proposed as the mechanism for superplastic deformation in 3Y-TZP with and without glassy grain boundary phases.     

Grain-Size Dependence of Sliding Wear in Tetragonal Zirconia Polycrystals

Using a pin-on-plate tribometer with the reciprocating motion of SiC against yttria-doped tetragonal zirconia polycrystal (Y-TZP) plates, the friction and wear of Y-TZP ceramics were investigated as a function of grain size in dry N₂ at room temperature. The results showed that the overall wear resistance increased as the grain size of Y-TZP ceramics decreased. For grain sizes ≤0.7 μm, the wear results revealed a Hall-Petch type of relationship ( d ^−1/2) between wear resistance and grain size. In this case, the main wear mechanisms were plastic deformation and microcracking. For grain sizes ≥0.9 μm, the wear resistance was proportional to the reciprocal of the grain diameter. In this regime, delamination and accompanying grain pullout were the main mechanisms. In this case, the phase transformation to monoclinic zirconia had a negative effect on the wear resistance of TZP ceramics. The coefficient of friction tended to be higher for fine-grained TZP-SiC couples than for coarse-grained TZP-SiC couples, whereas, for a specific regime of grain size, the coefficient of friction was almost independent of the grain size.     

Low-Temperature Processing and Mechanical Properties of Zirconia and Zirconia–Alumina Nanoceramics

The 1.5- to 3-mol%-Y₂O₃-stabilized tetragonal ZrO₂ (Y-TZP) and Al₂O₃/Y-TZP nanocomposite ceramics with 1 to 5 wt% of alumina were produced by a colloidal technique and low-temperature sintering. The influence of the ceramic processing conditions, resulting density, microstructure, and the alumina content on the hardness and toughness were determined. The densification of the zirconia (Y-TZP) ceramic at low temperatures was possible only when a highly uniform packing of the nanoaggregates was achieved in the green compacts. The bulk nanostructured 3-mol%-yttria-stabilized zirconia ceramic with an average grain size of 112 nm was shown to reach a hardness of 12.2 GPa and a fracture toughness of 9.3 MPa·m^1/2. The addition of alumina allowed the sintering process to be intensified. A nanograined bulk alumina/zirconia composite ceramic with an average grain size of 94 nm was obtained, and the hardness increased to 16.2 GPa. Nanograined tetragonal zirconia ceramics with a reduced yttria-stabilizer content were shown to reach fracture toughnesses between 12.6–14.8 MPa·m^1/2 (2Y-TZP) and 11.9–13.9 MPa·m^1/2 (1.5Y-TZP).     

Grain-boundary cation diffusion in ceria tetragonal zirconia determined by constant-strain-rate deformation tests

Ceria tetragonal zirconia polycrystals with a content of 12 mol% ceria (CeTZP) have been tested in compression at constant strain rate between 1150 °C and 1300 °C. An accurate analysis of the stress–strain curves has permitted to determine the value of the grain boundary cation diffusion. The results are compared with those reported in literature for this alloy and yttria tetragonal zirconia polycrystals (YTZP). An isotopic effect is found to correlate both grain boundary diffusion coefficients.     

Crystal Structure–Ionic Conductivity Relationships in Doped Ceria Systems

In the past, it has been suggested that the maximum ionic conductivity is achieved in ceria, when doped with an acceptor cation that causes minimum distortion in the cubic fluorite crystal lattice. In the present work, this hypothesis is tested by measuring both the ionic conductivity and elastic lattice strain of 10 mol% trivalent cation-doped ceria systems at the same temperatures. A consistent set of ionic conductivity data is developed, where the samples are synthesized under similar experimental conditions. On comparing the grain ionic conductivity, Nd_0.10Ce_0.90O_2−δ exhibits the highest ionic conductivity among other doped ceria systems. The grain ionic conductivity is around 17% higher than that of Gd_0.10Ce_0.90O_2−δ at 500°C, in air. X-ray diffraction profiles are collected on the sintered powder of all the compositions, from room temperature to 600°C, in air. From the lattice expansion data at high temperatures, the minimal elastic strain due to the presence of dopant is observed in Dy_0.10Ce_0.90O_2−δ. Nd_0.10Ce_0.90O_2−δ exhibits larger elastic lattice strain than Dy_0.10Ce_0.90O_2−δ with better ionic conductivity at intermediate temperatures. Therefore, it is shown that the previously proposed crystal structure–ionic conductivity relationship based on minimum elastic strain is not sufficient to explain the ionic conductivity behavior in ceria-based system.     

Fracture Toughness, Ionic Conductivity, and Low-Temperature Phase Stability of Tetragonal Zirconia Codoped with Yttria and Niobium Oxide

Tetragonal zirconia (t-ZrO₂) solid solutions were prepared with additions of up to 1.5 mol% of niobium oxide (Nb₂O₅) into 3-mol%-yttria-stabilized t-ZrO₂ (3Y-TZP). The influence of pentavalent cation doping on fracture toughness, ionic conductivity, and the tetragonal-to-monoclinic phase transformation in the temperature range of 120°-210°C was investigated. Fracture toughness and ionic conductivity increased and decreased, respectively, as the Nb₂O₅ content increased, which indicated that the annihilation of oxygen vacancies in 3Y-TZP was responsible for the instability of the t-ZrO₂ lattice. The activation enthalpy related to the conductivity was ~83 kJ/mol, regardless of the dopant content, which was consistent with that for the low-temperature degradation of 3Y-TZP doped with Nb₂O₅. Degradation under an applied electric field occurred only on the specimen surface that was in contact with the anode, which suggests that depletion of the oxygen vacancies led to the degradation. The identical activation enthalpies and the involvement of the vacancy migration in both processes fortified the belief that the low-temperature degradation of yttria-stabilized t-ZrO₂ is attributed to oxygen vacancy diffusion.     

Low-Temperature Aging of t'-Zirconia: The Role of Microstructure on Phase Stability

Polycrystalline, tetragonal ( t ') zirconia samples containing 3 and 4 mol% yttria were fabricated by annealing pressureless-sintered samples in air at ∼ 2100°C for 15 min. The grain size of these fully tetragonal samples was on the order of 100 to 200 μm. Domain structure of the samples and of a 3-mol%-yttria-doped tetragonal zirconia single crystal was examined by transmission optical microscopy under polarized light and by transmission electron microscopy. The orientations of the domain/colony boundaries were in accord with the predictions of group theory. As-polished surfaces of polycrystalline t ' materials showed no monoclinic phase even after 1000 h at 275°C in air. By contrast, conventionally yttria-doped tetragonal zirconia polycrystalline (Y-TZP) ceramics of grain size >0.5 μm showed substantial transformation. Surface grinding enhanced the resistance to degradation of Y-TZP but decreased that of t ' materials. Even then, the t ' materials exhibited better resistance to degradation than the Y-TZP ceramics. Excellent resistance of the t ' materials to low-temperature aging despite a very large grain size and the opposite effect of grinding on phase stability are all explained on the basis of ferroelastic domain structure of these materials.     

Sinter-Forging of Nanocrystalline Zirconia: II, Simulation

A quantitative computer simulation of densification, pore-size evolution, and grain growth during sinter-forging has been developed and applied to the sinter-forging of nanocrystalline yttria (30 mol%)-stabilized zirconia (3Y-TZP) at 1050° and 1100°C. Densification is simulated as a superposition of stress-assisted and plastic-strain-controlled pore-shrinkage mechanisms. Grain growth is simulated as a pore-controlled process during intermediate-stage densification and as a combination of normal (static) grain growth and dynamic grain growth during final-stage densification. The densification portion of the model offers very good agreement with the experiment under a wide variety of imposed forging conditions, despite the absence of adjustable variables. Grain-growth predictions qualitatively illustrate a key feature in the sinter-forging of 3Y-TZP: i.e., the minimization of grain size, as a function of density, under forging conditions that promote high strain rates. This particular effect seems to be due to the quick elimination of large pores by plastic strain while small pores (which shrink by diffusion) are still available to control grain growth.