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.     

Effects of Grain Size and Humidity on Fretting Wear in Fine-Grained Alumina, Al2O3/TiC, and Zirconia

Friction and wear of sintered alumina with grain sizes between 0.4 and 3 μm were measured in comparison with Al₂O₃/TiC composites and with tetragonal ZrO₂(3 mol% Y₂O₃). The dependence on the grain boundary toughness and residual microstresses is investigated, and a hierarchical order of influencing parameters is observed. In air, reduced alumina grain sizes improve the micromechanical stability of the grain boundaries and the hardness, and reduced wear is governed by microplastic deformation, with few pullout events. Humidity and water slightly reduce the friction of all of the investigated ceramics. In water, this effect reduces the wear of coarser alumina microstructures. The wear of aluminas and of the Al₂O₃/TiC composite is similar; it is lower than observed in zirconia, where extended surface cracking occurs at grain sizes as small as 0.3 μm.     

Processing of Homogeneous Zirconia-Toughened Alumina Ceramics with High Dry-Sliding Wear Resistance

The preparation of dense homogeneous zirconia-toughened alumina (ZTA) with high dry-sliding wear resistance is described. These ZTA ceramics are obtained by sintering green compacts, made by colloidal filtration of well-defined ZrO₂-Al₂O₃ particle suspensions, for 2 h at 1400°C. The optimum solid and stabilizer concentrations for the filtration process were determined. The sintered ZTA microstructure consists of a homogeneous distribution of zirconia grains in an alumina matrix with grain sizes of 0.2 and 0.5 µm, respectively. In pin-on-disk tribological measurements at relatively high initial contact pressures (1130 MPa) and sliding speeds (0.5 m/s) a very low specific wear rate (about 5 × 10^-8 mm³/(N·m)) and a coefficient of friction of 0.45–0.55 were found. It is shown that, in this case, wear is dominated by abrasion and polishing.     

Load Dependence of Hardness in Sintered Submicrometer Al2O3 and ZrO2

Monolithic alumina bodies with a grain size of 0.5 μm and submicrometer tetragonal ZrO₂ (3 mol% Y₂O₃) polycrystals were produced and investigated. With decreasing indentation load, the hardness increases but may again decrease below about 5 N; relevant measurements require the application of fairly high loads. Decreasing grain sizes increase the hardness of alumina and zirconia ceramics even for very small grain sizes in the submicrometer range.     

Effect of Microstructure on the Tribological and Mechanical Properties of CuO-Doped 3Y-TZP Ceramics

Dense 8 mol% CuO-doped 3Y-TZP ceramics were prepared by pressureless sintering for 8 h at 1500° and 1550°C, respectively. Transmission electron spectroscopy revealed that the ceramic sintered at 1500°C exhibits grain boundaries free of any amorphous phase, while crystalline copper-oxide grains were found in the zirconia matrix, whereas the sample sintered at 1550°C contains a Cu-rich amorphous grain boundary layer. The tribological behavior of these materials was tested under dry-sliding conditions using a pin-on-disk tribometer. The material sintered at 1500°C showed self-lubrication resulting in a low coefficient of friction ( f ) of 0.2–0.3 and a low specific wear rate ( k ) ≪ 10⁻⁶ mm³·(N·m)⁻¹. In contrast, the material sintered at 1550°C showed poor tribological behavior ( f =0.8–0.9; k ≫ 10⁻⁶ mm³·(N·m)⁻¹ under the same conditions. The difference in the tribological behavior of these two materials was interpreted on the basis of mechanical properties and microstructural characteristics.     

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).     

Influence of ZrO2 Grain Size and Content on the Transformation Response in the Al2O3─ZrO2 (12 mol% CeO2) System

Based on experimental and modeling studies, the rate of increase in the martensite start temperature M _s for the tetragonal-to-monoclinic transformation with increase in zirconia grain size is found to rise with decrease in ZrO₂ content in the zirconia-toughened alumina ZTA system. The observed grain size dependence of M _s can be related to the thermal expansion mismatch tensile (internal) stresses which increase with decrease in zirconia content. The result is that finer zirconia grain sizes are required to retain the tetragonal phase as less zirconia is incorporated into the alumina, in agreement with the experimental observations. At the same time, both the predicted and observed applied stress required to induce the transformation are reduced with increase in the ZrO₂ grain size. In addition, the transformation-toughening contribution at temperature T increases with increase in the M _s temperature brought about by the increase in the ZrO₂ grain size, when T > M _s. In alumina containing 20 vol% ZrO₂ (12 mol% CeO₂), a toughness of ∼10 MPa. √m can be achieved for a ZrO₂ grain size of ∼2 μm ( M _s∼ 225 K). However, at a grain size of ∼2 μm, the alumina–40 vol% ZrO₂ (12 mol% CeO₂) has a toughness of only 8.5 MPa. √m ( M _s∼ 150 K) but reaches 12.3 MPa. ∼m ( M _s∼ 260 K) at a grain size of ∼3 μm. These findings show that composition (and matrix properties) play critical roles in determining the ZrO₂ grain size to optimize the transformation toughening in ZrO₂-toughened ceramics.     

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.     

Measurement of the Crystallographically Transformed Zone Produced by Fracture in Ceramics Containing Tetragonal Zirconia

During fracture of ceramics containing tetragonal zirconia particles, a volume of zirconia material on either side of the crack irreversibly transforms to the monoclinic crystal structure. Transformation zone sizes, measured using Raman microprobe spectroscopy, are presented for three sintered ceramics. In a single-phase ZrO₂−3.5 mol% Y₂O₃ material, an upper bound measurement of 5 μm is obtained for the zone size. In the Al₂O₃/ZrO₂ composites studied, the zone size is deduced to correspond to ∼1 grain in diameter. On the basis of the monoclinic concentrations derived from the Raman spectra it is further concluded that only a fraction of the ZrO₂ grains within the transformation zone transform, providing indirect evidence for the effect of particle size on the propensity for transformation.     

Influence of Grain Size and Humidity on the Nanotribological Properties of Wear-Resistant Nanostructured ZrO2 Coatings: An Atomic Force Microscopy Study

The nanotribological properties of nanostructured thin films of tetragonal ZrO₂ on oxidized Si (100) were studied as a function of grain size and relative humidity (RH) by atomic force microscopy. The nanostructured ZrO₂ showed a 50% decrease in friction coefficient μ compared with oxidized Si (100) in dry nitrogen atmosphere and 40% RH. A maximum of μ was observed at ca. 40% RH for both samples, while there were insignificant differences in μ for ZrO₂ samples with grain sizes between 12 and 30 nm. The good tribological properties open the possibility for nanostructured zirconia to be applied as wear-resistant, low friction coatings on various materials.     

Development of Nanocrystalline Wear-Resistant Y-TZP Ceramics

The present contribution reports some interesting and new results obtained while developing yttria-stabilized tetragonal zirconia (Y-TZP) using spark plasma sintering (SPS). The experimental results clearly showed that ZrO₂-nanoceramics with high hardness(∼14.5 GPa) can be processed at a lower sintering temperature of 1200°C in a short time (5 min). Another important result is that the newly developed Y-TZP nanoceramics, compared with the conventional sintered TZP, exhibit better fretting wear resistance against bearing steel. The intergranular fracture and the grain pullout were observed as the major wear mechanisms of the zirconia nanoceramics.     

High Electrical Conductivity and High Fracture Strength of Sc2O3-Doped Zirconia Ceramics with Submicrometer Grains

The microstructure, crystal phase, electrical conductivity, and mechanical strength of less than 7-mol%-Sc₂O₃-doped zirconia ceramics fabricated by comparatively low-temperature sintering at 1200–1300°C for 1 h were investigated. Zirconia ceramics having a uniform microstructure (grain size < 0.5 μm) stabilized with 6 mol% Sc₂O₃ showed high electrical conductivity (0.15 S/cm at 1000°C) and high fracture strength (660 MPa). With the increase of Sc₂O₃ content from 3.5 to 7 mol%, the grain size, fracture strength, and electrical conductivity at 1000°C changed from 0.2 to 0.5 μm, 970 to 440 MPa, and 0.07 to >0.2 S/cm, respectively. Sc₂O₃-doped zirconia polycrystals with high fracture strength and high electrical conductivity are promising candidates for the electrolyte material of solid oxide fuel cells.     

Influence of Microstructure on the Electrical Properties of Iron-Substituted Calcium Titanate Ceramics

CaTi_0.8Fe_0.2O_3–δ ceramics with grain sizes that varied from 2 to 10 μm were obtained and studied using SEM, TEM, Mössbauer spectroscopy, impedance spectroscopy, and electrochemical oxygen permeability measurements. Smaller grains developed a core–shell microstructure that consisted of a pure CaTiO₃ core and an iron-rich microdomain structure at the shell. The effect of grain size on electronic conductivity was negligible. The ionic conductivity was higher for the ceramics with core–shell grains, which suggested that fast oxygen transport along microdomain walls may have occurred. For the homogeneous ceramics, the ionic conductivity decreased with decreased grain size, in which case the grain boundary represented an additional resistance, probably because of the depletion of oxygen vacancies.     

Alumina/Zirconia Micro/Nanocomposites: A New Material for Biomedical Applications With Superior Sliding Wear Resistance

In the present investigation, the sliding wear behavior is described for Al₂O₃/ZrO₂ micro/nanocomposites and monolithic alumina of similar grain size under defined conditions of a constant sliding speed and different loads (20–150 N). Nano ZrO₂ particles (1.7 vol%) were observed uniformly distributing throughout the composites, and most of them were located within the matrix alumina grains. The wear rate of the alumina and the micro/nanocomposites increased as the contact load increased and a clear transition in friction and wear behavior was observed in both materials. However, the nanocomposite wear resistance at low contact loads was one order of magnitude higher than that of the alumina. In the severe regime, no difference was observed among the materials. The low wear rate (10⁻⁷ mm³·(N·m)⁻¹) along with low pullout indicates higher wear resistance of micro/nanocomposites in the mild regime compared with monolithic alumina. Based on the morphological observation of worn surfaces by scanning electron microscope and on residual stress analysis performed by neutron diffraction, some wear mechanisms of Al₂O₃–ZrO₂ micro/nanocomposites are proposed. The high wear resistance of the nanocomposites is discussed in terms of fracture resistance properties and residual stress. Improvements in mechanical and tribological properties of these composites make them promising candidates for biomedical applications.     

Cubic-Formation and Grain-Growth Mechanisms in Tetragonal Zirconia Polycrystal

The microstructure in Y₂O₃-stabilized tetragonal zirconia polycrystal (Y-TZP) sintered at 1300°–1500°C was examined to clarify the role of Y³⁺ ions on grain growth and the formation of cubic phase. The grain size and the fraction of the cubic phase in Y-TZP increased as the sintering temperature increased. Both the fraction of the tetragonal phase and the Y₂O₃ concentration within the tetragonal phase decreased with increasing fraction of the cubic phase. Scanning transmission electron microscopy (SEM) and X-ray energy dispersive spectroscopy (EDS) measurements revealed that cubic phase regions in grain interiors in Y-TZP generated as the sintering temperature increased. High-resolution electron microscopy and nanoprobe EDS measurements revealed that no amorphous layer or second phase existed along the grain-boundary faces in Y-TZP and Y³⁺ ions segregated at their grain boundaries over a width of ∼10 nm. Taking into account these results, it was clarified that cubic phase regions in grain interiors started to form from grain boundaries and the triple junctions in which Y³⁺ ions segregated. The cubic-formation and grain-growth mechanisms in Y-TZP can be explained using the grain boundary segregation-induced phase transformation model and the solute drag effect of Y³⁺ ions segregating along the grain boundary, respectively.     

Effect of the ac Field Level on the Aging of the Dielectric Response in Polycrystalline BaTiO3

BaTiO₃ ceramics with grain sizes from 0.6 to 60 μm and relative densities of 89% to 92% were prepared by hot forging and conventional sintering from very pure-oxalate-derived powder. The aging of both the dielectric constant and the dielectric loss was examined at weak and strong fields with respect to grain size and frequency. It was concluded that the main aging mechanism is the aging of hysteretic domain wall motion for coarse-grained ceramics. At grain size of less than 1 μm, the lack of frequency and E _AC dependence, along with a lower aging rate, suggests that domain motions or hysteretic domain wall motions are restricted in finegrained ceramic BaTiO₃ and contribute little to the aging.     

Low Friction in CuO-Doped Yttria-Stabilized Tetragonal Zirconia Ceramics: A Complementary Macro- and Nanotribology Study

The tribological behavior of CuO-doped yttria-stabilized tetragonal zirconia (3Y-TZP) ceramics in the absence of additional lubricants was characterized by macroscale pin-on-disk measurements and nanoscale atomic force microscopy (AFM) for a broad range of velocities. The previously observed low shear strength interfacial layers generated in pin-on-disk tracks by Al₂O₃ ball counter surfaces on CuO-doped 3Y-TZP, as well as virgin surfaces, were probed quantitatively by AFM with Si₃N₄ tips as the counter surface. The observed trends in nanoscale coefficient of friction determined by AFM were found to be in agreement with data acquired using a pin-on-disk tribometer. The combined data support the notion that a layer of surface contaminations is removed during the initial sliding, and wear of high asperities occurs. Subsequently, an interfacial layer with low shear strength is generated during sliding. While these results do not provide an exhaustive explanation for the process of layer formation, they represent the first report of bridged nano- and macrotribological analysis of a compositionally heterogeneous low-friction, low-wear ceramic material and further confirm some of the key assumptions for the deterministic model reported previously by Pasaribu and Schipper.     

Creep in Yttria- and Scandia-Stabilized Zirconia

Compression creep measurements at constant load on ZrO₂-6 mol% Sc₂O₃ (grain size ∼1 μm), ZrO₂-6 mol% Y₂O₃ (grain size ∼17 μm), and heat-treated ZrO₂-6 mol% Sc₂O₃ (grain size ∼2 μm) yield activation energies of 89, 86, and 74 kcal/mol, respectively. The creep rates are linearly proportional to the inverse square of the grain size of the material. A stress exponent, n , of 1.5 was found for the scandia-doped zirconia and two regimes, with n =1 and 6, were found for the yttria-doped zirconia. These data, supported by metallographic evidence, are interpreted as showing that n =1 is associated with cation diffusion control of creep, n =6 with local propagation of inter-crystalline cracks, and n =1.5 with a transition region.     

Sintering and Properties of Monazite-Type CePO4

Monazite-type CePO₄ powder (average grain size 0.3 μm) was dry-pressed to disks or bars. The green compacts began to sinter above 950°C. Relative density ≧ 99% and apparent porosity <1% were achieved when the specimens were sintered at 1500°C for 1 h in air. The linear thermal expansion coefficient and thermal conductivity of the CePO₄ ceramics were 9 × 10⁻⁶/°C to 11 × 10⁻⁶/°C (200° to 1300°C) and 1.81 W/(m · K) (500°C), respectively. Bending strength of the ceramics (average grain size 4 μm) was 174 ± 28 MPa (room temperature). The CePO₄ ceramics were cracked or decomposed by acidic or alkaline aqueous solutions at high temperatures.     

Dry Sliding Wear Behavior of Al2O3–SiC Submicro- and Nano-Composites

The wear behavior of a pure alumina matrix and two Al₂O₃-based composites, one with 5 vol% SiC nanosized particles (mean size 52 nm) and the other with 5 vol% SiC sub-microsized particles (mean size 230 nm), was studied in two different experimental conditions corresponding to mild and severe wear regime, respectively. Whether considering the friction or the wear resistance, in the mild regime no difference was observed among the materials. In the severe regime, the composites performed much better than the matrix alone due to stronger grain boundaries. The SiC particle size had no influence on the mean wear resistance.