Thickness Alteration of Grain-Boundary Amorphous Films during Creep of a Multiphase Silicon Nitride Ceramic

Experimental observations of the creep response of a commercial sintered silicon nitride ceramic are presented. The stable microstructure of this material at high temperature contains secondary crystalline phases which result from partial devitrification of the intergranular phase. The widths of amorphous films along grain boundaries (between silicon nitride grains) and phase boundaries (between silicon nitride and secondary phase grains) are characterized by transmission electron microscopy. The thickness distributions of grain-boundary films before and after creep are analyzed by a statistical method. While the film widths are highly uniform before creep, a bimodal distribution is observed after creep. The results suggest that viscous flow of the boundary amorphous films occurs during creep deformation.     

Grain-Boundary Viscosity of Preoxidized and Nitrogen-Annealed Silicon Carbides

Internal friction experiments were conducted on a model SiC polycrystal prepared from preoxidized (high-purity) SiC powder. This material contained high-purity SiO₂ glass at grain boundaries in addition to a free-carbon phase, which was completely removed upon powder preoxidation. Comparative tests were conducted on a SiC polycrystal, obtained from the as-received SiC powder with the addition of 2.5 vol% of high-purity SiO₂. This latter SiC material was also investigated after annealing at 1900°C for 3 h in a nitrogen atmosphere. Electron microscopy observations revealed a glass-wetted interface structure in SiC polycrystals prepared from both as-received and preoxidized powders. However, the former material also showed a large fraction of interfaces coated by turbostratic graphite. Upon high-temperature annealing in nitrogen, partial glass dewetting occurred, and voids were systematically observed at multigrain junctions. The actual presence of nitrogen could only be detected in a limited number of wetted interfaces. A common feature in the internal friction behavior of the preoxidized, SiO₂-added and nitrogen-annealed SiC was a relaxation peak that resulted from grain-boundary sliding. Frequency-shift analysis revealed markedly different characteristics for this peak: both the magnitude of the intergranular glass viscosity and the activation energy for grain-boundary viscous flow were much higher in the nitrogen-annealed material. Results of torsional creep tests were consistent with these findings, with nitrogen-annealed SiC being the most creep resistant among the tested materials.     

Nucieation and Growth of Cracks in Vitreous-Bonded Aluminum Oxide at Elevated Temperatures

The nucleation and growth of cracks was studied at elevated temperatures on a grade of vitreous-bonded aluminum oxide that contained ∼8 vol% glass at the grain boundaries. Cracks were observed to nucleate within the vitreous phase, close to the tensile surface of the flexural test specimens used in these experiments. Crack nucleation occurred at a strain of ∼0.08% to 0.12% which corresponded to a crack nucleation time of ∼35% of the time to failure by creep rupture. Once nucleated, cracks propagated along grain boundaries, as long as the stress for crack propagation was maintained. The crack velocity for cracks that were nucleated by the creep process was found to be linearly proportional to the apparent stress intensity factor, whereas for cracks that were nucleated by indentation, the crack velocity was proportional to the fourth power of the apparent stress intensity factor.     

Redistribution of a Grain-Boundary Glass Phase during Creep of Silicon Nitride Ceramics

The compressive creep behavior of a high-purity silicon nitride ceramic with and without the addition of Ba was studied at 1400°C. Two distinct creep stages were observed during high-temperature deformation of both materials. Transmission electron microscopy (TEM) has been used to characterize the intergranular glass film thickness. Statistical analysis of a number of grain-boundary films indicates that the film thickness is confined to a narrow range in the as-sintered materials. However, the mean thickness is greater in the Ba-doped ceramic than in the undoped material. The standard deviation of the film thickness of a given material is considerably larger after creep than before. We conclude that the grain-boundary glass phase is redistributed during creep, suggesting that viscous flow of the glass phase is responsible for the first stage of the creep process.     

Tensile Creep of Alumina-Silicon Carbide "Nanocomposites"

The tensile creep behavior of an (Al₂O₃-SiC) nanocomposite that contains 5 vol% of 0.15 μm SiC particles is examined in air under constant-load conditions. For a stress level of 100 MPa and in the temperature range of 1200°–1300°C, the SiC reduces the creep rate of Al2O3 by 2–3 orders of magnitude. In contrast to Al₂O₃, the nanocomposite exhibits no primary or secondary stages, with only tertiary creep being observed. Microstructural examination reveals extensive cavitation that is associated with SiC particles that are located at the Al₂O₃ grain boundaries. Failure of the nanocomposite occurs via growth of subcritical cracks that are nucleated preferentially at the gauge corners. A modified test procedure enables creep lifetimes to be estimated and compared with creep rupture data. Several possible roles of the SiC particles are considered, including (i) chemical alteration of the Al₂O₃ grain boundaries, (ii) retarded diffusion along the Al₂O₃-SiC interface, and (iii) inhibition of the accommodation process (either grain-boundary sliding or grain-boundary migration).     

Flexural Creep of an in Situ-Toughened Silicon Carbide

Flexural creep behavior is reported for an in situ -toughened SiC between 1100° and 1500°C in four-point bending. The flexural creep rate of this SiC, sintered with aluminum, boron, and carbon (ABC-SiC), exhibits linear stress dependence, low apparent activation energy, and low incidence of cavitation and dislocation production. Most grain boundaries in this ceramic contain 1–5 nm intergranular films. The creep rate is consistent with a grain-boundary transport mechanism involving diffusion along the grain-boundary film-SiC interfaces. The microstructure and grain boundaries have been examined using transmission electron microscopy to assess possible changes during creep, particularly in relation to the applied stress direction.     

Intergranular Fracture of Lithium Fluoride–22% Calcium Fluoride Hypereutectic Salt at 800 K

Constant-velocity compression tests were conducted at 800 K on as-cast LiF-22 mol% CaF₂ hypereutectic salt with engineering strain rates varying between 1.8 × 10⁻⁶ and 2.3 × 10⁻¹ s⁻¹. Considerable stain hardening was observed during the initial stages of deformation, and the true stress-strain curves exhibited maxima. Plots of the true strain rate against the flow stress at the proportional limit and the peak stress exhibited a power-law relation with stress exponents of 7.7. Microstructural examination of the deformed specimens showed extensive grain-boundary cracking and cavitation. These results suggest that grain-boundary cracking and interfacial sliding is important for cavity nucleation at the grain boundaries and at the LiF-CaF₂ interfaces, and cavity growth and interlinkage, which appear to depend on the morphological differences between different grain boundaries, occur through the preferential failure of the weaker LiF phase.     

Structure and Viscosity of Grain Boundary in High-Purity SiAlON Ceramics

Three high-purity SiAlON materials (Si_{6− z} Al _z O _z N_{8− z} , z = 1, 2, 3) were characterized with respect to both structure and viscous behavior of internal grain boundaries. Internal friction experiments provided a direct measure of the intrinsic viscosity of grain boundaries and concurrently revealed the occurrence of a grain-boundary interlocking mechanism that suppressed sliding. A residual glass phase (consisting of aluminum-rich SiO₂) and nanometer-sized mullite residues were found at glassy triple-grain junctions of the z = 1 SiAlON. A low-melting intergranular phase dominated the high-temperature behavior of this material and caused grain-boundary sliding at temperatures as low as 1100°C. A quantitative analysis of the grain-boundary internal friction peak as a function of oscillation frequency indicated an intergranular film viscosity of log η∼ 7.5 Pa · s at 1100°C. Glass-free grain boundaries were a characteristic of SiAlON materials with z ≥ 2, which yielded a significant improvement in refractoriness as compared to the z = 1 SiAlON material. In these materials, relaxation resulting from grain-boundary sliding was suppressed, and the internal friction curve simply experienced an exponential-like increase.     

Rheological Behavior of Dilute SiAlON with or without Intergranular X-Phase

Dense nearly single-phase β'-SiAlON materials (with substitutional level z ∼ 1) have been prepared by hot isostatic pressing and their high-temperature deformation behavior has been investigated using low-frequency damping and torsional creep experiments. Addition of a small fraction of AlN (∼0.5 wt%) to the starting (nominally z = 1) SiAlON powder enabled us to "balance" the excess SiO₂ which likely arises from surface contamination of the starting SiAlON powder upon exposure to atmosphere. As a result, a fine-grained β'-SiAlON polycrystal free of residual (glassy) X-phase segregated to grain boundaries could be prepared. This microstructure is in contrast with that found for an "unbalanced" composition prepared from the same raw β'-SiAlON powder but without the corrective AlN addition. In this latter case, residual glass (X-phase), consisting of Al-rich SiO₂, was entrapped at multiple grain junctions. The presence of such a low-melting intergranular glass dominates the high-temperature deformation behavior of the dilute SiAlON material, involving marked degradation of creep resistance and significant damping relaxation due to grain-boundary sliding. "Balancing" the SiAlON microstructure with a small addition of AlN enabled us to suppress anelastic relaxation by grain-boundary sliding and to increase the creep resistance of the material by more than 1 order of magnitude.     

Role of Oxidation in the Time-Dependent Failure Behavior of Hot Isostatically Pressed Silicon Nitride at 1370°C

Dynamic fatigue studies were conducted on a hot isostatically pressed silicon nitride in ambient air and inert (argon or nitrogen) environments using four-point flexure at 1370°C. Specimens tested in ambient air exhibited a stressing rate dependence with decreased flexure strength with decreased stressing rates. All fracture surfaces of specimens tested in ambient air possessed a sweeping stress-oxidation damage zone that originated at the tensile side of each bend bar. In addition to this stress-oxidation damage, creep damage (e.g., cavitation) was concurrently observed in the specimens tested at the slower stressing rates, which appeared to further weaken the material. However, tests conducted in argon or nitrogen revealed flexure strength to be independent of the stressing rate. Creep damage was present at the slower stressing rates, but no stress-oxidation damage was evident similar to that observed on the specimens tested in ambient air. By decoupling the effects of oxidation and creep, it was evident that the former contributed to the formation of a detrimental stress-oxidation damage zone which significantly reduced the strength of this material at 1370°C.     

Grain-Boundary Viscosity of Polycrystalline Silicon Carbides

Internal friction experiments were conducted on three SiC polycrystalline materials with different microstructural characteristics. Characterizations of grain-boundary structures were performed by high-resolution electron microscopy (HREM). Observations revealed a common glass-film structure at grain boundaries of two SiC materials, which contained different amounts of SiO₂ glass. Additional segregation of residual graphite and SiO₂ glass was found at triple pockets, whose size was strongly dependent on the amount of SiO₂ in the material. The grain boundaries of a third material, processed with B and C addition, were typically directly bonded without any residual glass phase. Internal friction data of the three SiC materials were collected up to similar/congruent2200°C. The damping curves as a function of temperature of the SiO₂-bonded materials revealed the presence of a relaxation peak, arising from grain-boundary sliding, superimposed on an exponential-like background. In the directly bonded SiC material, only the exponential background could be detected. The absence of a relaxation peak was related to the glass-free grain-boundary structure of this polycrystal, which inhibited sliding. Frequency-shift analysis of the internal friction peak in the SiO₂-containing materials enabled the determination of the intergranular film viscosity as a function of temperature.     

Creep Behavior and Grain-Boundary Sliding in Polycrystalline A12O3

The creep properties of polycrystalline A1₂O₃ (grain size 14 to 65 μm) were examined under compressive stresses of between 4,000 and 18,000 psi (27.6 and 124 MPa) in the range 1600° to 1700°C. Two distinct types of behavior were observed. The creep rate of medium-grained specimens (14 to 30 μm) could be described by ασ^1.2 / d² where σ is the applied stress and d is the grain size. These results are consistent with the Nabarro-Herring creep mechanism. For the coarse-grained (65 μm) specimens, the creep rate was related to the stress by ασ^2.6. This behavior was not related to cracking; instead, a dislocation mechanism was thought to be rate-controlling. Considerable evidence for grain-boundary sliding was seen, and measurements showed that grain-boundary sliding contributed between 46 and 77% of the total strain in the 3 medium-grained specimens examined and between 38 and 50% in the 3 coarsegrained specimens examined.     

Flexural Creep Deformation of ZrB2/SiC Ceramics in Oxidizing Atmosphere

Flexural creep of ZrB₂/0–50 vol% SiC ceramics was characterized in oxidizing atmosphere as a function of temperature (1200°–1500°C), stress (30–180 MPa), and SiC particle size (2 and 10 μm). Creep behavior showed strong dependence on SiC content and particle size, temperature and stress. The rate of creep increased with increasing SiC content, temperature, and stress and with decreasing SiC particle size, especially, at temperatures above 1300°C. The activation energy of creep showed linear dependence on the SiC content increasing from about 130 to 511 kJ/mol for ceramics containing 0 and 50 vol% 2-μm SiC, respectively. The stress exponent was about 2 for ZrB₂ containing 50 vol% SiC regardless of SiC particle size, which is an indication that the leading mechanism of creep for this composition is sliding of grain boundaries. Compared with that, the stress exponent is about 1 for ZrB₂ containing 0–25vol% SiC, which is an indication that diffusional creep has a significant contribution to the mechanism of creep for these compositions. Cracking and grain shifting were observed on the tensile side of the samples containing 25 and 50 vol% SiC. Cracks propagate through the SiC phase confirming the assumption that grain-boundary sliding of the SiC grains is the controlling creep mechanism in the ceramics containing 50 vol% SiC. The presence of stress, both compressive and tensile, in the samples enhanced oxidation.     

Creep of CaO-Stabilized ZrO2

The compressive creep of 18 mol% CaO-stabilized ZrO₂ was studied at 1200° to 1400°C and 500 to 4000 psi. The specimens were polycrystalline with grain diameters from 7 to 29 μm. The activation energy for creep is 94 kcal/mol, and the creep rates are linearly proportional to the stress and to the inverse of the grain size. These results lead to the conclusion that creep in 18 mol% CaO-stabilized ZrO₂ may be controlled by cation diffusion associated with grain-boundary sliding.     

Creep of Doped Polycrystalline Al2O3

Creep behavior of polycrystalline A1₂O₃ doped with MgO + NiO, both as-hot-pressed in graphite dies and additionally annealed, was determined for 1300° to 1470°C and for 1000 to 15,000 psi in compression. The deformed specimens contained intergranular separations. Creep rates were proportional to stress to the 1.1 and 1.3 powers and were independent of grain size changes occurring during creep. The suggested creep mechanism is localized plastic deformation at stress concentration points accommodated by grain-boundary separations initiated by grain-boundary sliding.     

Plastic Deformation of Fine-Grained Alumina (Al2O3): I, Interface-Controlled Diffusional Creep

Plastic deformation in fine-grained alumina polycrystals (grain size 1 to 15 μm) was studied. At least three distinct deformation mechanisms are important: diffusional creep, basal slip, and unaccommodated grain-boundary sliding. The first and most important of these processes is addressed in this paper. Analysis of the deformation dynamics suggests that both lattice and grain-boundary diffusion are important in the diffusional creep. Aluminum, rather than oxygen, lattice and grain-boundary diffusion are rate-controlling because oxygen diffusion is very slow in the lattice but very rapid in grain boundaries. Significantly, the diffusional creep can become interfacecontrolled at low stresses, causing the often-reported non-Newtonian creep behavior of fine-grained alumina.     

Energy Variations in Diffusive Cavity Growth

The assignment of boundary values for the chemical potential and the calculation of energy-release rates for the growth of creep cavities along grain boundaries by self-diffusion are discussed. For simplicity, it is assumed that the boundaries are flat and that surface and grain-boundary diffusion are the dominant transport mechanisms. As matter diffuses from the void surface into and along the grain boundary, misfit residual stresses are induced to alleviate the high stress concentration ahead of the cavity apex. As a result, the contribution of strain-energy terms to the chemical potential can be neglected in typical cases. Also, contrary to the Griffith crack-extension model, the energy dissipation incurred by diffusive removal of material from the cavity surface and deposition in the grain boundary is a major term in the energy transfers associated with cavity growth. The primary energy "sink" in diffusive cavity growth is shown to arise from the work done by the grain-boundary normal stress when matter is inserted in the near-tip region by diffusion, not from the loss of strain energy of matter that is removed from the cavity at its tip or from the work of bond separation. Thermodynamic restrictions on the angle formed by the void surfaces at their apex, where they join the grain boundary, are considered. Boundary values for the chemical potential are derived in a manner appropriate for arbitrarily large but elastic distortions of material near the cavity tip and, in contrast to most previous work in the area, the effects of surface tension (i.e. of "surface stress," as distinct from surface energy) are included.     

High-Temperature Stress-Strain Behavior of MgO in Compression

Compressive stress-strain curves for several types of polycrystalline MgO specimens were correlated with those for single crystals and analyzed as a function of grain size and grain-boundary character at 1200° and 1400°C for several strain rates. The results for fully dense specimens were explained in terms of grain-boundary sliding and intergranular separation in addition to slip. The modification of grain-boundary nature concurrent with heat treatment for grain growth, caused by residual LUF, was associated with enhanced grain-boundary sliding and intergranular separation. For grain sizes <30 μm, it was concluded that the von Miss criteria for ductility could be relaxed by the Occurrence of dislocation climb and, to a limited extent, by intergranular separation. Yield drop corresponding to dislocation multiplication occurred when grain-boundary sliding was initially promoted. Specimens with a liquid phase of adequate viscosity also indicated plasticity accompanied by high strength. Specimens with clean grain boundaries exhibited ductility and normal strain hardening with no intergranular separation.     

Grain-Boundary Wetting-Dewetting in z= 1 SiAlON Ceramic

The grain-boundary structure of a model SiAlON polycrystal with nominal composition Si₅AlON₇ was characterized by transmission electron microscopy (TEM) both in an equilibrium (as-processed) state at room temperature and after quenching from elevated temperature. In addition, low-frequency (1–13 Hz) internal friction data were recorded as a function of temperature, showing a pronounced grain-boundary sliding peak positioned at 1030°C. High-resolution transmission electron microscopy (HRTEM) of the equilibrated low-temperature microstructure revealed residual glass only at multigrain junctions, but no amorphous intergranular films were observed. The detection of clean interfaces in the as-processed sample contradicts the internal friction data, which instead suggests the presence of a low-viscosity grain boundary phase, sliding at elevated temperatures. Therefore, a thin section of the as-sintered material was heated to 1380°C and rapidly quenched. HRTEM analysis of this sample showed, apart from residual glass pockets, wetted grain boundaries, which is in line with the internal friction experiment. This wetting-dewetting phenomenon observed in z = 1 SiAlON is expected to have a strong impact not only on high-temperature engineering ceramics but also on geological, temperature-activated processes such as volcanic eruptions.     

Electrical Conductivities of (CeO2)1−x(Y2O3)x Thin Films

Electrical properties of CeO₂ thin films of different Y₂O₃ dopant concentration as prepared earlier were studied using impedance spectroscopy. The ionic conductivities of the films were found to be dominated by grain boundaries of high conductivity as compared with that of the bulk ceramic of the same dopant concentration sintered at 1500°C. The film grain-boundary conductivities were investigated with regard to grain size, grain-boundary impurity segregation, space charge at grain boundaries, and grain-boundary microstructures. Because of the large grain boundary and surface area in thin films, the impurity concentration is insufficient to form a continuous highly resistive Si-rich glassy phase at grain boundaries, such that the resistivity associated with space-charge layers becomes important. The grain-boundary resistance may originate from oxygen-vacancy-trapping near grain boundaries from space-charge layers. High-resolution transmission electron microscopy coupled with a trans-boundary profile of electron energy loss spectroscopy gives strong credence to the space-charged layers. Since the conductivities of the films were observed to be independent of crystallographic texture, the interface misorientation contribution to the grain-boundary resistance is considered to be negligible with respect to those of the impurity layer and space-charge layers.