Cation Tracer Diffusion in Cr2O3 and Cr2O3-0.09 wt% Y2O3

The cation diffusivities in the lattice and along dislocations and grain boundaries have been measured on sintered polycrysals of Cr₂O₃; and Cr₂Cr₂O₃-0.09 wt% Y₂O₃ at1100°C and at the pO₂ corresponding to that of Cr/Cr₂O₃ equilibrium at that temperature. Results for lattice and dislocation diffusivities in pure Cr₂O₃ are in good agreement with previous work. The present results indicate that yttrium additions have negligible effect on lattice and dislocation diffusion. However, grain-boundary diffusion in pure Cr₂O₃ is significantly slower than grain-boundary diffusion in Cr₂O₃-0.09 wt% Y₂O₃. The results are discussed in terms of their implications for the reactive-element effect in high-temperature oxidation of chromium-containing alloys.     

Microstructural Analysis of Sintered High-Conductivity Zirconia with Al203 Additions

Transmission electron microscopy (at 100 and 1000 kV potential) and analytical scanning transmission electron microscopy were used to study α-Al₂0₃ second-phase particles and their interactions with grain boundaries in two high-conductivity Y₂0₃/Yb₂0₃ stabilized zirconia ceramics containing deliberate additions of the alumina as a sintering aid. Most of the Al₂0₃ particles were intragranular and microanalysis showed that they contained inclusions rich in Zr or Si plus Zr. Al₂O₃ particles at grain boundaries were frequently associated with amorphous cusp areas rich in Si and Al. The results suggest that the Al₂0₃ acts as a scavenger for SiO₂, removing it from grain-boundary localities. A model is proposed whereby this process occurs as the boundaries meet the second-phase particles, assisted by rapid grain-boundary diffusion. Such an ZrO₂-Al₂O₃-SiO₂ interaction and partitioning is predicted thermodynamically and offers a possible explanation for the improvements in ionic conductivity brought about by Al₂O₃ additions, as reported in the literature.     

Exaggerated Grain Growth in ZrO2-Toughened Al2O3

Annealing of ZrO₂-toughened Al₂O₃ (ZTA) at elevated temperatures causes growth of both the intergranular ZrO₂ particles and the Al₂O₃"matrix" grains. Exaggerated ("breakaway") grain growth occurs in some, but not all, specimens. Analytical electron microscopy of two ZTA's, both of which contained a continuous amorphous (glassy) grain-boundary phase, but only one of which showed breakaway grain growth, revealed that the occurrence of breakaway grain growth could be correlated with the chemistry of the ubiquitous glassy grain-boundary phase.     

Diffusion-Induced Grain-Boundary Migration in Ceria-Stabilized Tetragonal Zirconia Polycrystals

The microstructure and microchemistry of grain-boundary regions in (CeO₂+ La₂O₃)-stabilized tetragonal ZrO₂ polycrystals (Ce(La)-TZP) were studied by means of transmission electron microscopy (TEM). Evidence was found for the existence of crystalline and vitreous intergranular phases situated in small pockets at multiple grain junctions and in thin films along grain boundaries. In this ceramic system grain-boundary migration was observed in situ in the TEM in sample areas subjected to electron irradiation. Interfaces migrated away from their centers of curvature. Evidence was found for Ce de-alloying in the volume swept by the advancing boundaries. It is suggested that the coherency lattice strain brought about by a partial reduction of Ce, resulting in the diffusion of Ce³⁺ along grain boundaries to free surfaces, is the driving force for this phenomenon.     

Analysis of Grain-Boundary Impurities and Fluoride Additives in Hot-Pressed Oxides by Auger Electron Spectroscopy

Auger electron spectroscopy was used to characterize grain-boundary chemistry in MgO, Al₂O₃, and MgAl₂O₄ (spinel) hot-pressed with LiF or NaF. The presence of additives (F, Na) at the grain boundaries was confirmed; observation of grain-boundary impurities in MgO extends previous studies.     

Effect of Yttrium and Lanthanum on the Final-Stage Sintering Behavior of Ultrahigh-Purity Alumina

Final-stage sintering has been investigated in ultrahigh-purity Al₂O₃ and Al₂O₃that has been doped individually with 1000 ppm of yttrium and 1000 ppm of lanthanum. In the undoped and doped materials, the dominant densification mechanism is consistent with grain-boundary diffusion. Doping with yttrium and lanthanum decreases the densification rate by a factor of ˜11 and 21, respectively. It is postulated that these large rare-earth cations, which segregate strongly to the grain boundaries in Al₂O₃, block the diffusion of ions along grain boundaries, leading to reduced grain-boundary diffusivity and decreased densification rate. In addition, doping with yttrium and lanthanum decreases grain growth during sintering. In the undoped Al₂O₃, surface-diffusion-controlled pore drag governs grain growth; in the doped materials, no grain-growth mechanism could be unambiguously identified. Overall, yttrium and lanthanum decreases the coarsening rate, relative to the densification rate, and, hence, shifted the grain-size-density trajectory to higher density for a given grain size. It is believed that the effect of the additives is linked strongly to their segregation to the Al₂O₃grain boundaries.     

Investigation of Grain-Boundary Segregation in Ceramic Oxides by Analytical Scanning Transmission Electron Microscopy

Analytical scanning transmission electron microscopy (AEM) was used to study grain-boundary solute segregation in the systems MgO-NiO, A1₂O₃-Y, O₃, NiO-Cr₂O₃, and NiO-Al₂O₃. Electron beam spreading within the specimen was incorporated into a model to quantitatively measure solute segregation. Grain-boundary segregation occurred in A1₂O₃-Y₂O₃ and NiO-Cr₂O₃ but was not detected in MgO-NiO and NiO-Al₂O₃ specimens. These results and the quantitative measurements agree with equilibrium solute segregation theories. Microhard-ness measurements indicate no difference in hardness between the grain boundary and the matrix for Cr-doped NiO, a system in which segregation was detected.     

Densification and Grain Growth of Al2O3 Nanoceramics During Pressureless Sintering

α - Al₂O₃ nanopowders with mean particle sizes of 10, 15, 48, and 80 nm synthesized by the doped α-Al₂O₃ seed polyacrylamide gel method were used to sinter bulk Al₂O₃ nanoceramics. The relative density of the Al₂O₃ nanoceramics increases with increasing compaction pressure on the green compacts and decreasing mean particle size of the starting α-Al₂O₃ nanopowders. The densification and fast grain growth of the Al₂O₃ nanoceramics occur in different temperature ranges. The Al₂O₃ nanoceramics with an average grain size of 70 nm and a relative density of 95% were obtained by a two-step sintering method. The densification and the suppression of the grain growth are achieved by exploiting the difference in kinetics between grain-boundary diffusion and grain-boundary migration. The densification was realized by the slower grain-boundary diffusion without promoting grain growth in second-step sintering.     

Grain-Growth Kinetics for Alumina in the Absence of a Liquid Phase

The kinetics of grain growth in fully dense Al₂O₃ with and without MgO solute additions were measured for high-purity samples containing no liquid phases. The MgO was found to suppress the grain-boundary migration rate by a factor of 50. Compensating lattice defects are suggested to play a role in grain-growth inhibition. Implications of these results to the sintering of Al₂O₃ are discussed.     

Thermal Conductivity of β-Si3N4: II, Effect of Lattice Oxygen

Dense β-Si₃N₄ with various Y₂O₃/SiO₂ additive ratios were fabricated by hot pressing and subsequent annealing. The thermal conductivity of the sintered bodies increased as the Y₂O₃/SiO₂ ratio increased. The oxygen contents in the β-Si₃N₄ crystal lattice of these samples were determined using hot-gas extraction and electron spin resonance techniques. A good correlation between the lattice oxygen content and the thermal resistivity was observed. The relationship between the microstructure, grain-boundary phase, lattice oxygen content, and thermal conductivity of β-Si₃N₄ that was sintered at various Y₂O₃/SiO₂ additive ratios has been clarified.     

Imaging Secondary-Ion Mass Spectroscopy Observation of the Scavenging of Siliceous Film from 8-mol%-Yttria-Stabilized Zirconia by the Addition of Alumina

The scavenging of a resistive siliceous phase via the addition of Al₂O₃ was studied, using imaging secondary-ion mass spectroscopy (SIMS), given the improved grain-boundary conductivity in 8-mol%-yttria-stabilized zirconia (8YSZ). The grain-boundary resistivity in 8YSZ decreased noticeably with the addition of 1 mol% of Al₂O₃. Strong SiO₂ segregation at the grain boundaries was observed in a SIMS map of pure 8YSZ that contained 120 ppm of SiO₂ (by weight). The addition of 1 mol% of Al₂O₃ caused the SiO₂ to gather around the Al₂O₃ particles. The present observations provided direct and visual evidence of SiO₂ segregation at the grain boundaries (which had a deleterious effect on grain-boundary conductivity) and the scavenging of SiO₂ via Al₂O₃ addition.     

FTIR Spectra, Lattice Shrinkage, and Magnetic Properties of CoTi-Substituted M-Type Barium Hexaferrite Nanoparticles

Single-phase BaCoTiFe₁₀O₁₉ (BaCoTi-M) nanoparticles were prepared by a modified sol–gel process, using metallic chlorides as starting materials. The physical chemistry process of BaCoTi-M formation, the interdependences between composition, technological conditions, microstructure, and magnetic properties were studied by X-ray diffraction (XRD), Fourier transform-infrared (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM). XRD and FTIR results show that BaCoTi-M nanoparticles formed directly from γ-Fe₂O₃, spinel ferrite, and barium salts without the formation of α-Fe₂O₃ and BaFe₂O₄. The lattice shrinkage of BaCoTi-M nanoparticles that occurred on increasing the calcining temperature from 973 to 1173 K under holding for 2 h or on increasing the holding time in the range 0–2 h at 1173 K was discovered by analyzing the dependences of lattice parameters on the heat-treatment conditions. The shrinkage led to a relatively higher concentration of magnetic Fe³⁺ cations in the unit cell, and resulted in an increase of specific saturation magnetization under the corresponding conditions. Microstructural characterization shows that the evolutions of coercivity, remnant magnetization, and squareness ratio depended on the crystal growth and the reduction of structural defect as well as a decrease of grain boundary.     

Grain Growth in Fe3O4

Sintering and microstructural evolution were studied in Fe₃O₄ as a model system for spinel ferrites. Fe₃O₄ powder, purified by the salt-crystallization method, was sintered to ∼99.5% density in a CO-CO₂ atmosphere. The p _O2 Of the sintering atmosphere drastically affects the microstructure (grain size) of sintered Fe₃O₄ without significantly affecting density. The measured grain-boundary mobilities, M , of Fe₃O₄ fit the equation M=M ₀( T ) p _O2^−1/2 with M ₀( T ) = 2.5×10⁵ exp[-(609kJ·mol-¹/ RT ](m/s)(N/m²)^−l. The grain-boundary migration process appeared to be pore-drag controlled, with lattice diffusion of oxygen as the most likely rate-limiting step.     

Microstructural Characterization of Superplastic SiO2-doped TZP with a Small Amount of Oxide Addition

The microstructures of 5 wt% SiO₂-doped TZP, 5 wt% (SiO₂+ 2 wt% MgO)-doped TZP, and 5 wt% (SiO₂+ 2 wt% Al₂O₃)-doped TZP are characterized by high-resolution electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy loss spectroscopy. An amorphous phase is formed at multiple grain junctions but not along the grain-boundary faces in these three materials. A small addition of MgO and Al₂O₃ into the SiO₂ phase results in a marked reduction in tensile ductility of SiO₂-doped TZP. This reduction seems to correlate with segregation of magnesium or aluminum ions at grain boundaries and a resultant change in the chemical bonding state.     

Faceting Behavior of Alumina in the Presence of a Glass

The faceting of alumina interfaces in the presence of a glass affects both grain growth and grain-boundary mobility during liquid-phase sintering. The geometry and movement of facets that form during this sintering process are expected to play an essential role in the development of the final microstructure, in particular, by their influence on the topology of the grain boundaries which ultimately control the properties of Al₂O₃ compacts. A new method for studying the interaction between Al₂O₃ and a glass has been developed. A thin sample of Al₂O₃ suitable for examination in a transmission electron microscope is prepared and examined and then reacted with SiO₂ and CaO via the vapor phase. This experimental approach allows the faceting behavior of glass/Al₂O₃ interfaces to be studied systematically without introducing unnecessary complications during subsequent sample preparation. Faceting occurs almost exclusively on the (0001) and {1 1 02} planes. The interaction between glass and certain structured grain boundaries in alumina has been studied using polycrystalline thin films.     

A Diffusion-Compensation Relation for Normal Grain Growth and Grain-Boundary Diffusion of Oxygen in Oxides

Values of D₀/δ and Q for grain-boundary diffusion, derived from published studies of normal grain growth in Al₂O₃, BeO, CaO, MgO, SiO₂, and CaSiO₃, are fit by the linear compensation equation log D₀/δ=0.03170Q -7.6792 (r²=0.9384). Comparison of grain-boundary diffusion coefficients derived from grain growth in oxides with those obtained by direct experimental measurement suggests that the kinetics of normal grain growth are controlled by grain-boundary diffusion of oxygen.     

Roles of Alumina in Zirconia for Functional Applications

The Al₂O₃ addition to stabilized ZrO₂ has been studied for more than 20 years. In this article, literature and new results on the positive and negative effects of Al₂O₃ additions on the electrical properties of ZrO₂ are summarized and analyzed. In particular, a comprehensive grain-boundary conduction model is proposed. The Al₂O₃ addition always increases the bulk resistivity, mainly because of the formations of defect associates and insulating Al₂O₃ second-phase particles. The Al₂O₃ addition within the solubility limit increases the grain-boundary resistivity, as a result of increased grain-boundary space-charge potential; the Al₂O₃ addition above the solubility limit, however, scavenges the silicon-rich second phase from the grain boundaries, thereby decreasing the grain-boundary resistivity.     

Influence of Dopant Concentration on Creep Properties of Nd2O3-Doped Alumina

The microstructural features and tensile creep behavior of Al₂O₃ doped with Nd₂O₃ at levels ranging from 100 to 1000 ppm (Nd:Al atomic ratio) were systematically investigated. Compositional mapping, using both high-resolution scanning transmission electron microscopy and secondary ion mass spectroscopy revealed that, for all of the compositions studied, the Nd³⁺ ions were strongly segregated to the Al₂O₃ grain boundaries. Microstructural observations revealed that the solubility of Nd₂O₃ was between 100 and 350 ppm. Tensile creep tests were conducted over a range of temperatures (1200°–1350°C) and stresses (20–75 MPa). Both the stress and grain-size exponents were analyzed. In selected experiments, controlled grain-growth anneals were used to enable creep testing of samples of the same average grain size but different neodymium concentrations. Independent of dopant level, the neodymium additions decreased the creep rate by 2–3 orders of magnitude, compared with that of undoped Al₂O₃. The value of the apparent creep activation energy increased with increased dopant concentration and then saturated at dopant levels exceeding the solubility limit. Overall, the results of the present study were consistent with a creep-inhibition mechanism whereby oversized segregant ions reduce grain-boundary diffusivity by a site-blocking mechanism.     

Atomic Structures and Energies of Σ7 Symmetrical Tilt Grain Boundaries in Alumina Bicrystals

Symmetrical Σ7 tilt grain boundaries of alumina (Al₂O₃) were studied using bicrystals. Three types of Σ7 boundaries were successfully fabricated, that is, rhombohedral twin (Σ7{1[Onemacr]02}) and two types of [0001] symmetrical tilt grain boundaries with grain-boundary planes {4[Fivemacr]10} and {2[Threemacr]10} (Σ7{4[Fivemacr]10} and Σ7{2[Threemacr]10}). Their atomic structures and grain-boundary energies were investigated using high-resolution transmission electron microscopy (HRTEM) and a thermal grooving technique, respectively. HRTEM observations showed that the Σ7{1[Onemacr]02} boundary had a completely symmetrical atomic arrangement with respect to the grain-boundary plane. In contrast, Σ7{2[Threemacr]10} and Σ7{4[Fivemacr]10} boundaries exhibited asymmetrical atomic structures, which were confirmed by analyzing the atomic configurations using static lattice calculations. Thermal grooving experiments showed that the grain-boundary energies strongly depended on the properties of the grain-boundary planes.     

Superior Perovskite Oxide-Ion Conductor; Strontium- and Magnesium-Doped LaGaO3: II, ac Impedance Spectroscopy

Alternating current impedance spectroscopy and electron microscopy were used to investigate the effect of grain boundaries in LSGM-based materials. The impurity LaSrGa₃O₇ existing in the samples La_0.8Sr_0.2Ga_{1- y} Mg _y -O_{3–0.5(0.2+ y )} ( y = 0.05–0.10) gives a contribution to a perfect or depressed grain-boundary semicircle in the impedance spectroscopy. The depressed semicircle represents a constant phase element (CPE) indicating LaSrGa₃O₇ is an oxide-ion insulator. The grain-boundary semicircle vanishes if a hydrogen-containing atmosphere is applied. This fact may reflect proton conduction in LaSrGa₃O₇. In contrast, the impurity LaSrGaO₄ existing, for example, in the samples x = 0.20, y = 0.25–0.30 gives no grain-boundary contribution to the impedance.