Evaluation of the Strength and Creep–Fatigue Behavior of Hot Isostatically Pressed Silicon Nitride

The strength of a commericially available hot isostatically pressed silicon nitride was measured as a function of temperature. To evaluate long-term mechanical reliability of this material, the tensile creep and fatigue behavior was measured at 1150°, 1260°, and 1370°C. The stress and temperature sensitivities of the secondary (or minimum) creep strain rate were used to estimate the stress exponent and activation energy associated with the dominant creep mechanism. The fatigue characteristics were evaluated by allowing individual creep tests to continue until specimen failure. The applicability of the four-point load geometry to the study of strength and creep behavior was also determined by conducting a limited number of flexural creep tests. The tensile fatigue data revealed two distinct failure mechanisms. At 1150°C, failure was controlled by a slow crack growth mechanism. At 1260° and 1370°C, the accumulation of creep damage in the form of grain boundary cavities and cracks dominated the fatigue behavior. In this temperature regime, the fatigue life was controlled by the secondary (or minimum) creep strain rate in accordance with the Monkman–Grant relation.     

Hydrothermal Corrosion of Pure, Hot Isostatically Pressed Silicon Nitride

The aqueous corrosion behavior of hot isostatically pressed Si₃N₄ (HIPed-Si₃N₄) without additives was studied under hydrothermal conditions at 300°C and 8.6 MPa (86 atm). The accelerated weight loss in the HIPed-Si₃N₄ was attributed to uniform thinning of the specimen accompanied by dislodgement of Si₃N₄ grains from the substrate due to preferential attack at grain boundaries. Enhanced attack at grain boundaries was due to the presence of amorphous SiO₂ from impurities in the starting powder.     

Effect of Load on the Hardness of Hot Isostatically Pressed Silicon Nitride

The hardness values of five hot isostatic pressed silicon nitride materials, with varying densities, were measured at loads between 1 and 200 N. For the fully dense materials, the calculated hardness decreased from about 30 to 15 GPa as the load increased to about 10 N, and the hardness remained constant at higher loads. For the samples that showed indentation size effect (ISE), cracks formed at the corners of the indentation, starting at the lowest load of 1 N. Materials with lower densities had lower hardness values, displayed a very small or no ISE, and formed corner cracks only at high loads. For the samples that displayed an ISE at low loads, the formation of cracks was analyzed using the Niihara et al . criterion for Palmqvist cracks.     

Evolution of Stress Failure Resulting from High-Temperature Stress-Corrosion Cracking in a Hot Isostatically Pressed Silicon Nitride

Stress-corrosion cracking in a commercially available, hot isostatically pressed (HIPed), yttria-fluxed, silicon nitride was the prevalent mode of failure in specimens creepruptured at 1370°C. High-temperature diffusional processes associated with oxygen were responsible for the creation of an advancing stress-corrosion front that had formed at the specimen surface and advanced radially inward. The volume of material in the wake of the stress-corrosion front possessed a high concentration of lenticular cavities at two-grain boundaries, a high concentration of multigrain junction cavities, and large amorphous "pockets" in other multigrain junctions that were abnormally rich in oxygen and yttrium. The combination of tensile stress and the high concentration of cavities in the near-surface volume of the material resulted in microcrack coalescence or the formation of a planar, stress-corrosion crack . The concurrent growth of the stress-corrosion front and crack during the tensile creep-rupture tests ultimately led to stress-induced failure.     

Effect of Wear Damage on the Strength of Hot Isostatically Pressed Silicon Nitride

Bending tests have been used to characterize the effect of wear damage of hot isostatically pressed silicon nitride in contact with waspaloy at 600°C. The problem arises at the junction between turbine blades and disks where wear may result in premature fatigue cracking of the blade root. The tests show that wear always results in a reduction of strength, whereas the Weibull modulus may decrease or remain unchanged, depending on the amount of surface damage.     

Grain-Boundary Microstructure and Chemistry of a Hot Isostatically Pressed High-Purity Silicon Nitride

Two high-purity Si₃N₄ materials were fabricated by hot isostatic pressing without the presence of sintering additives, using an amorphous laser-derived Si₃N₄ powder with different oxygen contents. High-resolution transmission electron microscopy and electron energy-loss spectroscopy (EELS) analysis of the Si₃N₄ materials showed the presence of an amorphous SiO₂ grain-boundary phase in the three-grain junctions. Spatially resolved EELS analysis indicated the presence of a chemistry similar to silicon oxynitride at the two-grain junctions, which may be due to partial dissolution of nitrogen in the grain-boundary film. The chemical composition of the grain-boundary film was SiN_xO_y, (x ∼ 0.53 and y ∼ 1.23), and the triple pocket corresponded to the amorphous SiO₂ containing ∼2 wt% nitrogen. The equilibrium grain-boundary-film thickness was measured and found to be smaller for the material with the lower oxygen content. This difference in thickness has been explained by the presence of the relatively larger calcium concentration in the material with the lower amount of SiO₂ grain-boundary phase, because the concentration of foreign ions has been shown to affect the grain-boundary thickness.     

Transmission Electron Microscopy Investigation of the Oxidation of Hot Isostatically Pressed Silicon Nitride with and without Sintering Aids

Analytical transmission electron microscopy of thin-foil cross sections has been used to examine the oxidation behavior of hot isostatically pressed silicon nitride (Si₃N₄) materials. The transmission electron microscopy (TEM) cross sections are prepared by a special technique that provides electron transparency through the entire oxide, interfacial, subscalar, and matrix regions simultaneously. The materials are oxidized in an alumina furnace at 1250°C for 100 h. TEM investigation indicates that oxidation of Si₃N₄ occurs in an oxidation reaction zone that is comprised of the scale, oxide/matrix interface, and subscalar regions; therefore, the silica (SiO₂)/Si₃N₄ interfacial surface area that is available for oxidation is very large. The oxidative attack on the Si₃N₄ grains is not uniform or sequential, and oxygen diffuses into the matrix before the surface grains are consumed. Gas bubbles, probably nitrogen gas, accumulate at all levels of the scale, and no evidence is found for the existence of an "oxynitride" layer. Disintegration of the secondary phase, Y₂Si₂O₇, in the subscalar region is observed to occur, indicating that secondary, oxidation-related phenomena are occurring.     

Oxidation Behavior of Chemically-Vapor-Deposited Silicon Carbide and Silicon Nitride from 1200° to 1600°C

The isothermal oxidation of pure CVD SiC and Si₃N₄ has been studied for 100 h in dry, flowing oxygen from 1200° to 1600°C in an alumina tube furnace. Adherent oxide formed at temperatures to 1550°C. The major crystalline phase in the resulting silica scales was alpha-cristobalite. Parabolic rate constants for SiC were within an order of magnitude of literature values. The oxidation kinetics of Si₃N₄ in this study were not statistically different from that of SiC. Measured activation energies were 190 kJ/mol for SiC and 186 kJ/mol for Si₃N₄. Silicon oxynitride did not appear to play a role in the oxidation of Si₃N₄ under the conditions herein. This is thought to be derived from the presence of ppm levels of sodium impurities in the alumina furnace tube. It is proposed that sodium modifies the silicon oxynitride, rendering it ineffective as a diffusion barrier. Material recession as a function of oxide thickness was calculated and found to be low. Oxidation behavior at 1600°C differed from the lower temperatures in that silica spallation occurred after exposure.     

Mechanistic Analysis of Time-Dependent Failure of Oxynitride Glass-Joined Silicon Nitride below 1000°C

Time-dependent failure at elevated temperatures currently governs the service life of oxynitride glass-joined silicon nitride. Creep, devitrification, stress-aided oxidation-controlled slow crack growth, and viscous cavitation-controlled failure are examined as possible controlling mechanisms. Creep deformation failure is observed above 1000°C. Fractographic evidence indicates cavity formation and growth below 1000°C. Auger electron spectroscopy verified that the oxidation rate. Time-to-failure is independent of oxygen concentration. Reasonable agreement is found between the observed time-to-failure data and those predicted using the Tsai and Raj, and Raj and Dang viscous cavitation models. It is concluded that viscous relaxation and isolated cavity growth control the rate of failure in oxynitride glassfilled silicon nitride joints below 1000°C. Several possible methods are also proposed for increasing the service lives of these joints.     

Silicon Nitride/Molybdenum Disilicide Composite with Superior Long-Term Oxidation Resistance at 1500°C

The long-term high-temperature cyclic oxidation (100 cycles, 10⁴ h, 1500°C) of a Si₃N₄ material and a Si₃N₄/MoSi₂ composite, both fabricated with Y₂O₃ as a sintering additive, was studied. Both materials exhibited similar oxidation rates because of surface SiO₂ formation described by an almost parabolic law and a total weight gain of 3–4 mg/cm² after 10⁴ h. As a consequence of oxidation processes in the bulk, microstructural damage was found in the Si₃N₄ material. These effects were not observed in the composite. The remarkable microstructural stability observed offers the high potential of Si₃N₄/MoSi₂ composites for long-term structural applications at elevated temperatures up to 1500°C.     

Time-Dependent Strength of Siliconized Silicon Carbide under Stress at 1000° and 1100°C

The time-dependent strength of a fine-grained siliconized silicon carbide under stress at 1000° and 1100°C was investigated. Both macroscopic stress redistribution and localized flaw blunting were found to contribute to the strengthening of siliconized silicon carbide in bending tests. Strengthening through macroscopic stress redistribution involved nonlinear creep behavior which decreased the maximum outer fiber stress in the bending beam. Localized flaw blunting processes were determined to be operative in this material through artificial flaw tests using a prestress to prevent flaw healing. The sharp artificial cracks were blunted during static load tests by localized deformation processes at the crack tip.     

Fracture Toughness of a Silicon Nitride/Silicon Carbide Nanocomposite at 1350°C

The fracture toughness of a hot-pressed silicon nitride/silicon carbide (Si₃N₄/SiC) nanocomposite and reference monolithic Si₃N₄ has been investigated in four-point bending at 1350°C in air, using different loading rates (0.01-1 mm/min). Single-edge V-notched bend specimens that were prepared by polishing the notch tip to a radius of <10 µm, using 1 µm diamond paste, were used for the fracture toughness measurement. Slow crack growth (SCG) prior to catastrophic failure was detected at all applied loading rates at 1350°C. The fracture toughness at 1350°C, as calculated using the actual crack size measured on the fracture surface after the bend test, increased in both ceramics with decreasing loading rate and increasing area of the SCG region.     

Oxidation of Silicon Carbide-Reinforced Oxide-Matrix Composites at 1375° to 1575°C

Oxidation studies were conducted on Al₂O₃-SiC and mullite-SiC composites at 1375° to 1575°C in O₂ and in Ar-1% O₂. The composites were prepared by hot-pressing mixtures of Al₂O₃ or mullite and SiC powders. The reaction products contained alumina, mullite, an aluminosilicate liquid, and gas bubbles. The parabolic rate constants were about 3 orders of magnitude higher than those expected for the oxidation of SiC. Higher rates are caused by higher oxygen permeabilities through the reaction products than through pure silica. Our results suggest that oxygen permeabilities are comparable in the three condensed phases observed in the reaction products.     

Isothermal Oxidation Behavior of Mo-Si-B Intermetallics at 1450°C

Five Mo-Si-B multiphase intermetallic compositions were synthesized and oxidized isothermally at 1450°C in flowing air. Average mass change rates were strongly dependent on sample composition, particularly boron content. An Mo₅Si₃ matrix material containing 1.6 wt% boron exhibited parabolic mass gain with a rate of 5.3 × 10^-4 mg²(cm⁴.h), while a similar material with 0.14 wt% boron oxidized rapidly in a linear manner at a rate of -3.3 mg/(cm².h). Oxidation rates of the Mo-Si-B intermetallics were compared to that of MoSi₂ oxidized at 1450°C under identical conditions.     

Displacement Rate and Temperature Effects in Fracture of a Hot-Pressed Silicon Nitride at 1100° to 1325°C

An MgO-fluxed hot-pressed silicon nitride was fractured in four-point flexure between 1100° and 1325°C at three crosshead speeds. Above 1200°C, a temperature and strain-rate dependence of fracture stress and KIc was seen. Scanning and transmission electron microscopy were used to analyze as received and fractured material. A map of temperature vs crosshead speed was drawn showing regions where subcritical cracking was or was not observed and a transition region where microcracks and voids were detected.     

Passive and Active Oxidation of Hot–Pressed Silicon Nitride Materials with Two Magnesia Contents

Hot-pressed Si₃N₄ materials containing 1 and 5 wt% MgO were oxidized for 1000 h at 1000°, 1100°, and 1200°C in helium at 0.4 to 0.8 Pa total oxidants. Transition from passive to active oxidation occurred between 1000° and 1100° C, in agreement with published theoretical calculations for pure Si₃N₄. The amounts of both passive and active oxidation were greater for the material containing 5 wt% MgO. Specimen surfaces were porous and oxide–free under active oxidation conditions but contained porous oxide at transition.     

Oxidation Behavior of NBD 200 Silicon Nitride Ceramics

The oxidation behavior of NBD 200 Si₃N₄ containing 1 wt% MgO sintering aid was investigated in oxygen at 900°-1300°C. The oxide growth followed a parabolic rate law with an apparent activation energy of 260 kJ/mol. The oxide layers were enriched with sodium and magnesium because of outward diffusion of intergranular Na⁺ and Mg²⁺ cations in the ceramics. The 2-4 orders of magnitude higher oxidation rate for NBD 200 Si₃N₄ than for other Si₃N₄ ceramics with a similar amount of MgO could be attributed to the presence of sodium. The oxidation process was most likely rate limited by grain-boundary diffusion of Mg²⁺.     

Phase Analysis and Thermal Stability of Hot Isostatically Pressed Zirconia–Hydroxyapatite Composites

Composites of zirconia and hydroxyapatite (OHAp) have been processed via hot isostatic pressing (HIP) or sintering in air. When the composites were sintered in air at a temperature of 950°C, decomposition of the OHAp to tricalcium phosphate occurred. Using the HIP technique, composites without any detectable degradation of the OHAp phase were produced at 1200°C. The reactivity between zirconia and OHAp was dependent on both the amount of water lost from OHAp and the geometry of the interaction. The phase composition of the materials prepared was evaluated from their powder X-ray diffraction patterns, and their microstructures were studied via electron microscopy.     

Hot Corrosion Behavior of Barium Aluminosilicate-Coated C/SiC Composites at 900°C

Barium aluminosilicates (BAS) were coated on the carbon fiber-reinforced silicon carbide composites (C/SiC) as environmental barriers. The hot corrosion behavior of the coated composites was studied at 900°C in dry air and water vapor, respectively. The molten Na₂SO₄ was used as the corrosion reactant. The results indicate that the BAS coatings can effectively block the attack of molten Na₂SO₄ to C/SiC composites in dry air. However, the coated composites degrade rapidly when exposed to molten Na₂SO₄ coupled with water vapor. It is found that the BAS is corroded by Na₂SO₄ melt with the formation of BaSO₄, resulting in the destruction of BAS structure, which makes the coating lose its protection to the C/SiC composites in water vapor.