Microstructure, Strength, and Oxidation of a 10 wt% Zyttrite-Si3N4 Ceramic

Hot-pressed Si₃N₄ doped with 10 wt% zvttrite as a sinterine aid was studied. An equiaxed, fine-grainid microstructure was predominant, with no apparent porosity. Bend strengths were determined at room temperature and high temperatures (up to 1370°C/2500°F). Oxidation was measured by weight gain at 1370°C in air. The resulting material exhibited very good room-temperature strength (755 MPa/110 ksi). The work showed that room-temperature strength can be improved significantly by using controlled Si₃N₄ powder with 10 wt% zyttrite. High-temperature strength (514 MPd75 ksi) at 1370°C was nearly double that of hot-pressed Si₃N₄ (NC-132). The oxidation resistance at 1370°C was also higher than that of NC-132.     

Effects of Heat Treatment in a Wet Hydrogen Atmosphere on the Reliability of Sintered α-Silicon Carbide

Sintered α-SiC was exposed, for times up to 2 h, to a flowing wet H₂ atmosphere ( P _H2O= 1 × 10^-4 MPa) at temperatures of 1300°, 1400°, and 1500°C. The effect of such conditions on the reliability of the ceramic was estimated by comparing the Weibull modulus of the groups of specimens, tested in four-point flexure, before and after exposure. The Weibull modulus of as-polished specimens was 6.7, indicating a wide variation in room-temperature flexural strength. The Weibull modulus was increased to 14.2 by the heat treatment for 2 h in wet H₂ at 1400°C. The average strength was also improved from 347 to 446 MPa by such exposure. Heat treatment at 1300° and 1500°C also improved the reliability of the material, as indicated by increases in the Weibull modulus, but to less a degree than did exposure at 1400°C. The increases in reliability and average strength were attributed to the blunting of surface flaws by the formation of a thin SiO₂ layer on the sample surface.     

Potential of SiC as a heat exchanger material in combined cycle plant

The short and long term mechanical properties of a sintered silicon carbide intended as a heat exchanger material have been investigated. The short term strength shows an acceptable scatter characterised by a Weibull modulus of seven from room temperature up to 1400°C. In the time-dependent regime failure occurs by subcritical crack growth from surface located inherent defects at high stresses. Below a threshold stress oxidation blunting of these surface defects occurs and causes a transition from subritical crack growth to diffusion creep as life-limiting mechanism. Unlike other ceramics, the threshold stress for subcritical crack growth falls within the low probability range of fast fracture. Failure mechanism maps presenting the life-limiting mechanisms of the investigated sintered silicon carbide over a range of stresses and temperatures are presented.     

Time-Dependent Strength Degradation of a Siliconized Silicon Carbide Determined by Dynamic Fatigue

Both fast-fracture strength and strength as a function of stressing rate at room temperature, 1100°, and 1400°C were measured for a siliconized SiC. The fast-fracture strength increased slightly from 386 MPa at room temperature to 424 MPa at 1100°C and then dropped to 308 MPa at 1400°C. The Weibull moduli at room temperature and 1100°C were 10.8 and 7.8, respectively, whereas, at 1400°C, the Weibull modulus was 2.8. The very low Weibull modulus at 1400°C was due to the existence of two exclusive flaw populations with very different characteristic strengths. The data were reanalyzed using two exclusive flaw populations. The ceramic showed no slow crack growth (SCG), as measured by dynamic fatigue at 1100°C, but, at 1400°C, an SCG parameter, n , of 15.5 was measured. Fractography showed SCG zones consisting of cracks grown out from silicon-rich areas. Time-to-failure predictions at given levels of failure probabilities were performed.     

Pressure-Sintered Silicon Carbide

Silicon carbide was hot-pressed to uniform densities of the order of 98% of the theoretical density, with slight additions of aluminum and iron aiding in this densification. Other elements having some effect were lithium, calcium, chromium, zirconium, and boron. This dense silicon carbide had very high strength at high temperatures; for example, it had a modulus of rupture of 70,000 1b. per sq. in. at 2500°F.     

Some Physical Properties of Eight Refractory Oxides and Carbides

An investigation of eight hot-pressed refractory oxides and carbides for possible gas-turbine application was undertaken. The properties, short-time tensile strength at elevated temperatures, thermal-shock resistance, coefficient of linear expansion, and density, were determined. The compositions of the ceramics included beryllium oxide, magnesium oxide, stabilized zirconia, zircon, boron carbide, 85% silicon carbide plus 15% boron carbide, titanium carbide, and zirconium carbide. The short-time tensile strengths of these ceramics were determined at 1800° and 2200°F. Resistance to thermal shock was determined by rapid cooling in air to room temperature from 1800°, 2000°, 2200°, and 2400°F. The thermal-expansion characteristics of these materials were studied from room temperature to 1100°F.
Zirconium carbide was the strongest material at 2200°F. with a maximum short-time tensile strength of 15,850 lb. per sq. in.; however, it exhibited extremely poor resistance to oxidation. Boron carbide had a short-time tensile strength of 22,550 lb. per sq. in. at 1800°F., and was the strongest material at this temperature. Boron carbide also had very poor resistance to oxidation and was among the worst compositions investigated in its ability to resist fracture by thermal shock. The evaluation of strength of boron carbide at 2200°F. was unsuccessful because it fluxed with the grips. Titanium carbide had the best resistance to thermal shock, and had strengths of 15,850 lb. per sq. in. at 1800°F. and 9400 lb. per sq. in. at 2200°F. It was the most promising of the eight compositions investigated. Hot-pressing of these eight highly refractory bodies indicated that a density of at least 93% of theoretical density could be obtained by this fabrication method.     

Thermomechanical Fatigue Behavior of a Silicon Carbide Fiber-Reinforced Calcium Aluminosilicate Composite

Isothermal fatigue and in-phase thermomechanical fatigue (TMF) tests were performed on a unidirectional, continuous-fiber, Nicalon®-reinforced calcium aluminosilicate glass-ceramic composite ([O]_16, SiC/CAS-II). Monotonic tensile tests were performed at 1100°C (2012°F) and 100 MPa/s (14.5 ksi/s) to determine the material's ultimate strength (σ_ult) and proportional limit (σ_pl). Isothermal fatigue tests at 1100°C employed two loading profiles, a triangular waveform with ramp times of 60 s and a similar profile with a superimposed 60-s hold time at σ_max. All fatigue tests used a σ_max of 100 MPa (40% of σ_pl), R = 0.1. TMF loading profiles were identical to the isothermal loading profiles, but the temperature was cycled between 500° and 1100°C (932° and 2012°F). All fatigued specimens reached run-out (1000 cycles) and were tested in tension at 1100°C immediately following the fatigue tests. Residual modulus, residual strength, cyclic stress-strain modulus, and strain accumulation were all examined as possible damage indicators. Strain accumulation allowed for the greatest distinction to be made among the types of tests performed. Fiber and matrix stress analyses and creep data for this material suggest that matrix creep is the primary source of damage for the fatigue loading histories investigated.     

Densification and Mechanical Behavior of HfC and HfB2 Fabricated by Spark Plasma Sintering

Hafnium diboride (HfB₂)- and hafnium carbide (HfC)-based materials containing MoSi₂ as sintering aid in the volumetric range 1%–9% were densified by spark plasma sintering at temperatures between 1750° and 1950°C. Fully dense samples were obtained with an initial MoSi₂ content of 3 and 9 vol% at 1750°–1800°C. When the doping level was reduced, it was necessary to raise the sintering temperature in order to obtain samples with densities higher than 97%. Undoped powders had to be sintered at 2100°–2200°C. For doped materials, fine microstructures were obtained when the thermal treatment was lower than 1850°C. Silicon carbide formation was observed in both carbide- and boride-based materials. Nanoindentation hardness values were in the range of 25–28 GPa and were independent of the starting composition. The nanoindentation Young's modulus and the fracture toughness of the HfB₂-based materials were higher than those of the HfC-based materials. The flexural strength of the HfB₂-based material with 9 vol% of MoSi₂ was higher at 1500°C than at room temperature.     

Mechanical strength and defect distributions in flash sintered 3YSZ

The influence of preexisting defects and the generation of new ones during flash sintering was studied in 3YSZ. Weibull statistics was used to analyse mechanical testing data from flash and conventionally sintered specimens with equal densification. The obtained values for Weibull modulus and characteristic strength are 6.09 and 371 MPa for the conventionally sintered samples, respectively, and 5.92 and 506 MPa for the flash sintered samples. It can be inferred that flash sintering does not alter significantly the defect distribution on the studied material. Preexisting defects were manufactured with rice starch as a pore forming agent, in 5, 10 and 15 vol%. Those samples were flash sintered in isothermal and constant heating rate experiments. The experiments show that there is no noticeable difference on the incubation time and the onset temperature for flash sintering.     

Characteristics of Si3N4-SiO2-Ce2O3 Compositions Sintered in High-pressure Nitrogen

Full-density Si₃N₄-SiO₂-Ce₂O₃ compositions were prepared by sintering with 2.5 MPa nitrogen pressure at temperatures of 1900° and 2090°C. Room-temperature flexural strengths near 700 MPa for sintered material compared favorably with the strength of hot-pressed material. At 1370°C, where flexural strengths as high as 363 MPa were obtained, it was observed that the coarsest structure was the strongest and the finest structure was the weakest. One of the compositions tested, Si₃N₄-8.7 wt% SiO₂-8.3 wt%-Ce₂O₃, was found to have excellent 200-h oxidation resistance at 700°, 1000°, and 1370°C, without incidence of 700° to 1000°C phase instability and cracking.     

Thermophysical and Mechanical Properties of a Three-Dimensional Hi–Nicalon/SiC Composite

Key thermophysical and mechanical properties of a three-dimensional Hi-Nicalon™/silicon carbide (SiC) composite were tested. The relationship between the thermal expansion coefficient and temperature of the composite from room temperature (RT) to 1400°C was similar to that of chemical vapor deposition SiC. The thermal diffusivity of the composite could be well fitted by a logarithmic function. The composite exhibited excellent mechanical properties at RT and high temperature in vacuum. At RT, the flexural strength and flexural modulus were 1193 MPa and 255.6 GPa, respectively. Above 1200°C, the value of the flexural strength and flexural modulus at high temperature in vacuum decreased as the temperature increased, while the fracture toughness increased as the temperature increased.     

Tensile Rupture Strength and Fracture Defects of Sintered Silicon Carbide

The tensile strength distribution of sintered silicon carbide was measured at room temperature and 1300°C in air and fracture defects were characterized. The measured strength was compared with strength obtained from flaw characteristics and fracture toughness assuming a peripherally cracked spherical void model.     

Pressureless Sintering of ZrB2–SiC Ceramics

A pressureless sintering process was developed for the densification of zirconium diboride ceramics containing 10–30 vol% silicon carbide particles. Initially, boron carbide was evaluated as a sintering aid. However, the formation of a borosilicate glass led to significant coarsening, which inhibited densification. Based on thermodynamic calculations, a combination of carbon and boron carbide was added, which enabled densification (relative density >98%) by solid-state sintering at temperatures as low as 1950°C. Varying the size of the starting silicon carbide particles allowed the final silicon carbide particle morphology to be controlled from equiaxed to whisker-like. The mechanical properties of sintered ceramics were comparable with hot-pressed materials with Vickers hardness of 22 GPa, elastic modulus of 460 GPa, and fracture toughness of ∼4 MPa·m^1/2. Flexure strength was ∼460 MPa, which is at the low end of the range reported for similar materials, due to the relatively large size (∼13 μm long) of the silicon carbide inclusions.     

Effect of Heat Treatments on the Crack-Healing and Static Fatigue Behavior of Silicon Carbide Sintered with Sc2O3 and AlN

Crack-healing behavior of silicon carbide ceramics sintered with AlN and Sc₂O₃ has been studied as a function of heat-treatment temperature and applied stress. Results showed that heat treatment in air could significantly increase the indentation strength whether a stress is applied or not. After heat treatment with no applied stress at 1300°C for 1 h in air, the indentation strength of the specimen with an indentation crack of ∼100 μm (≈2c) recovered its strength fully at room temperature. In addition, a simple heat treatment at 1200°C for 5 h under an applied stress of 200 MPa in air resulted in a complete recovery of the unindented strength at the healing temperature. However, higher applied stress led to fracture of the specimens during heat treatment. The static fatigue limit of the specimens crack healed at 1200°C for 5 h under 200 MPa was ∼450 MPa at the healing temperature. The ratio of the static fatigue limit of the crack-healed specimen to the unindented strength was ∼80%.     

Joining SiC ceramics with silicon resin YR3184

Joints between reaction-bonded silicon carbide (RBSiC) and joints between pressureless sintered silicon carbide (SSiC) were produced respectively using a polysiloxane silicon resin (YR3184, GE Toshiba Silicones) as joining material. Samples were heat treated in a nitrogen flux at temperatures around 1200 °C. The maximum three point bending strength of the joints between reaction-bonded silicon carbide is 197 MPa. The maximum three point bending strength of the joints between sintered silicon carbide is 163 MPa. The join layers are continuous, homogeneous and densified and have thickness of 2–5 μm. The joining mechanism is that the amorphous silicon oxycarbide ceramic pyrolyzed from YR3184 acts as an inorganic adhesive.     

Strengthening of Soda-Lime Glass Rods by heat Treatment Alone and Heat Treatment plus Silanes

A study with soda-lime glass rods showed that modulus of rupture values can be increased from approximately 124 × 10⁶ Pa (18 ksi) to 276 × 10⁶ Pa (40 ksi) by heat treatment. Dipping the rods into diethyldichlorosilane prior to heating at 593°C (1100°F) or exposing hot glass to the silane vapor following heat treatment increased strength an additional 30% over the average strength obtained by heating only at this temperature. Similar treatment with phenyltrichlorosilane or diethyldichlorosilane did not give strengths statistically higher than those obtained by heating alone.     

Mechanical Behavior of SiC(f)/SiC Composites and Correlation to in situ Fiber Strength at Room and Elevated Temperatures

Mechanical properties of Nicalon-fiber-reinforced silicon carbide matrix composites were evaluated, in flexure, at various temperatures ranging from ambient to 1300°C. First matrix cracking stress ranged from 250 to 280 MPa and was relatively insensitive to test temperature. The measured ultimate strength showed a small increase from a room-temperature value of 370 to 460 MPa at 800°C. Beyond 800°C, however, strength dropped to as low as 280 MPa at 1300°C. This decrease in ultimate strength at elevated temperatures is believed to be partly due to degradation of in situ Nicalon fiber strength. Scanning electron microscopy was employed to evaluate the in situ Nicalon fiber strengths via fracture mirror size measurements. Degradation of Nicalon fiber strength is attributed to thermal damage and to structural changes to the fiber at elevated temperatures. Measured values of ultimate strength of the composites were compared with predictions made on the basis of in situ fiber strength characteristics and an available analytical model.     

Static Fatigue Limit for Sintered Silicon Carbide at Elevated Temperatures

The modified static loading technique for estimating static fatigue limits was used to study the effects of oxidation and temperature on the static fatigue limit, K ₁₀ for crack growth in sintered silicon carbide. For as-machined, unoxidized sintered silicon carbide with a static load time of 4 h, K ₁₀× 2.25 MPa * m^1/2 at 1200° and ∼1.75 at 1400°C. On oxidation for 10 h at 1200°C, K ₁₀ drops to ∼1.75 MPam^1/2 at 1200° and ∼1.25 at 1400°C when tested in a nonoxidizing ambient. Similar results were obtained at 1200°C for tests performed in air. A tendency for strengthening below the static fatigue limit appears to result from plastic relaxation of stress in the crack-tip region by viscous deformation involving an oxide grain-boundary phase for oxidized material and, possibly, diffusive creep deformation in the case of unoxidized material.     

预氧化处理对反应烧结碳化硅微观结构和弯曲强度的影响

本文提出了一种简单有效的预氧化处理方法,用来强化反应烧结碳化硅(RBSC),研究了800~1 300 ℃预氧化处理对其微观结构和力学性能的影响,探究了含不同尺寸压痕裂纹的材料在氧化前后残余弯曲强度的变化规律。结果表明,随着氧化温度的升高,RBSC的室温强度和Weibull模数均存在先下降后上升,然后再下降的趋势,主要原因是不同温度氧化后的RBSC表面形貌不同。在1 200 ℃下预氧化2 h,RBSC的弯曲强度和Weibull模数都明显变大,强度提升了19.9%,Weibull模数由7.3提升到11.8。然而,800 ℃低温氧化不完全和1 300 ℃高温氧化反应过于强烈均会导致弯曲强度和Weibull模数下降。在最优氧化条件(1 200 ℃氧化2 h)下,含压痕裂纹(载荷20 N)的RBSC试样的残余弯曲强度在氧化后由201.1 MPa提高到324.2 MPa,强化机理是高温氧化生成的SiO₂能够消除材料表面缺陷和微裂纹。     

Young's Modulus, Flexural Strength, and Fracture of Yttria-Stabilized Zirconia versus Temperature

The flexural strength and elastic modulus of cubic zirconia that was stabilized with 6.5 mol% yttria was determined in the temperature range of 25°–1500°C in air. Specimens were diamond machined from both hot-pressed and sintered billets that were prepared from alkoxy-derived powders. The flexural strength of the hot-pressed material decreased, from }300 MPa at 25°C to 50 MPa at 1000°C, and then increased slightly as the temperature increased to 1500°C. The flexural strength of the sintered material decreased, from 150 MPa at 25°C to 25 MPa at 750°C, and then appeared to increase slightly to }1500°C. Flexural strengths were comparable to other fully stabilized zirconia materials. The overall fracture mode was transgranular at low temperatures, mixed mode at }500°–1000°C, and intergranular at higher temperatures. Pores or pore agglomerates along grain boundaries and at triple points were fracture origins. The value of the porosity-corrected Youngs moduli was 222 GPa at 25°C, decreased to }180 GPa at 400°C, and then was relatively constant with increasing temperature to 1350°C.