Silicon carbide fibre reinforced glass-ceramic matrix composites exhibiting high strength and toughness

Silicon carbide fibre reinforced glass-ceramic matrix composites have been investigated as a structural material for use in oxidizing environments to temperatures of 1000° C or greater. In particular, the composite system consisting of SiC yarn reinforced lithium aluminosilicate (LAS) glass-ceramic, containing ZrO₂ as the nucleation catalyst, has been found to be reproducibly fabricated into composites that exhibit exceptional mechanical and thermal properties to temperatures of approximately 1000° C. Bend strengths of over 700 MPa and fracture toughness values of greater than 17 MN m^–3/2 from room temperature to 1000° C have been achieved for unidirectionally reinforced composites of 50 vol% SiC fibre loading. High temperature creep rates of 10^–5 h^–1 at a temperature of 1000° C and stress of 350 MPa have been measured. The exceptional toughness of this ceramic composite material is evident in its impact strength, which, as measured by the notched Charpy method, has been found to be over 50 times greater than hot-pressed Si₃N₄.     

Thermal properties of MoSi2 and SiC whisker-reinforced MoSi2

The heat capacity, thermal conductivity and coefficient of thermal expansion of MoSi₂ and 18 vol % SiC whisker-reinforced MoSi₂ were investigated as a function of temperature. The materials were prepared by hot isostatic pressing between 1650 and 1700 °C, the hold time at temperature being 4 h. The heat capacity of MoSi₂ showed an increase from about 0.44 Wsg^–11K^–1 at room temperature to 0.53 at 700 °C. Whisker reinforcement increased heat capacity by about 10%. Thermal conductivity exhibited a decreasing trend from 0.63 Wcm^–1 K^–1 at room temperature to 0.28 Wem^–1 K^–1 at 1400°C. Whiskers reduced conductivity by about 10%. The thermal expansion coefficient increased from 7.42 °C^–1 between room temperature and 200 °C to 9.13 °C^–1 between room temperature and 1200 °C. There was a 10% decrease resulting from the whiskers. The measured data are compared with literature values. The trends in the data and their potential implications for high-temperature aerospace applications of MoSi₂ are discussed.     

Thermal expansion of the cubic (3C) polytype of SiC

Thermal expansion of the cubic beta or (3C) polytype of SiC was measured from 20 to 1000° C by the X-ray diffraction technique. Over that temperature range, the coefficient of thermal expansion can be expressed as the second order polynominal: ₁₁=3.19×10^–6+ 3.60×10^–9 T–1.68×10^–12 T ² (1/° C). It increases continuously from about 3.2×10^–6/° C at room temperature to 5.1×10^–6/° C at 1000° C, with an average value of 4.45 × 10^–6/° C between room temperature and 1000° C. This trend is compared with other published results and is discussed in terms of structural contributions to the thermal expansion.     

Whisker reinforcement of glass-ceramics

Silicon carbide whisker reinforcement of anorthite and cordierite glass ceramics has been studied. At 25 vol% whisker loading the flexural strengths increased from 65–103 MPa to 380–410 MPa, the fracture toughnesses increased from 1.0–1.5 MPa m^1/2 to 5.2–5.5 MPa m^1/2. The strengths decline to 240–276 MPa at 1200 °C. The reasons for the decrease in strength with temperature are discussed. Whiskers from two different sources with differences in diameters and aspect ratios were evaluated and the effect of the whisker morphology on the composite properties was studied. It was found that larger diameter, higher aspect ratio whiskers result in improved composite performance. The composites were also characterized in terms of their thermal properties, i.e. thermal expansions and thermal conductivities. The thermal expansion coefficient from 25–1000 °C for anorthite-based composite was 4.6×10^–6 °C^–1 and that for the cordierite-based composite was 3.62×10^–6 °C^–1. The thermal conductivities at 1000 °C were 3.75 and 4.1 Wm^–1 K^–1 for cordierite and anorthite composites, respectively.     

High thermal expansion KAlSiO4 ceramic

Orthorhombic kalsilite (KAlSiO₄) was prepared by solid-state reaction from K₂CO₃, Al₂O₃, and SiO₂. The axial thermal expansion coefficients of the orthorhombic kalsilite were 1.6×10^–5°C^–1 for the a-axis, 1.6×10^–5°C^–1 for the b-axis, 2.8×10^–5°C^–1 for the c-axis, and 2.0×10^–5°C^–1 for the average from room temperature to 1000°C. A high thermal expansion ceramic consisting of the orthorhombic kalsilite was prepared by sintering. The densification was promoted by adding Li₂CO₃. The KAlSiO₄ ceramic sintered at 1200°C for 2 h with 5 wt% Li₂CO₃ had a bending strength of 65 MPa and linear thermal expansion coefficient of 2.2×10^–5 °C^–1 from room temperature to 600°C.     

Cyclic fatigue crack growth behaviour in β-(Si–Al–O–N) at ambient and elevated temperatures

Four-point bending fatigue tests on a hot-pressed sintered Sm–-(Si–Al–O–N) ceramic were conducted at room temperature, 900 °C and 1000 °C in air under different load ratios and cyclic frequencies. The growth of indentation cracks was measured during the fatigue tests. The results indicate that the cyclic fatigue crack growth threshold is lower and crack growth rates are higher, for given values of K_max, at 1000 °C than those at room temperature. The cyclic fatigue crack growth behaviour at 900 °C is similar to that at room temperature. It was found that the crack growth retardation due to cyclic fatigue loading is much more pronounced at higher frequencies. An increase in cyclic frequency from 1 to 10 Hz cause a reduction of up to two orders of magnitude in crack propagation rates. High-temperature cyclic fatigue crack growth rates increased and threshold stress intensity factor ranges decreased with increasing load ratio. Possible mechanisms for cyclic crack growth are discussed.     

Phenomenology of fracture in hot-pressed silicon nitride

Fracture phenomenology in hot-pressed silicon nitride has been studied fractographically as a function of flaw size, temperature and loading rate. Surface cracks of controlled size were introduced using the microhardness indentation technique. At room temperature, the fracture stress was found to depend on initial crack size according to the Griffith relationship and extrapolation of the data indicated that inherent processing flaws of the order of 12 to 24 m are strength-controlling in virgin material. Using a simplified Griffith approach, the fracture surface energy, , at 20° C for hot-pressed Si₃ N₄ is about 22 000 erg cm^–2. Two mechanistic regimes were manifest in the temperature dependence of the fracture stress. A mixed mode of fracture consisting of transcrystalline and intergranular crack propagation occurred up to 1100° C; at 1200° C and above, subcritical crack growth (SCG) occurred intergranularly and the extent of SCG increased with increasing temperature. Similarly, the extent of SCG decreased with increasing loading rate.     

Synthesis and high temperature mechanical properties of Ti3SiC2/SiC composite

A high density Ti₃SiC₂/20 vol % SiC composite was hot pressed under a uniaxial pressure of 45 MPa for 30 min in an Ar atmosphere at 1600 °C. The grain size of the Ti₃SiC₂/SiC composite was finer than that of monolithic Ti₃SiC₂, though the composite was hot pressed at a higher temperature, due to the dispersion of SiC particles in the Ti₃SiC₂ matrix. Room temperature fracture toughness of the composite and Vickers hardness were measured as 5.4 MPa m^1/2 and 1080 kg mm^–2, respectively. A higher flexure strength of the composite compared to that of monolithic Ti₃SiC₂ was measured both at room temperature and up to 1200 °C. At 1000 °C, the composite showed a lower oxidation rate than that of monolithic Ti₃SiC₂.     

Coprecipitation-derived mullite and mullite-zirconia composites

Precursor powders of mullite-zirconia (0–40 wt% ZrO₂) were prepared by a hydroxide coprecipitation method and their behaviour during calcination between room temperature and 1500 °C was studied using thermal analysis, X-ray diffraction and electron microscopy. The only crystalline phases present in the precalcined powders were bayerite and gibbsite, and these were stable up to 250 °C. Powders containing ZrO₂ were initially amorphous, but on calcination between 250 and 850 °C produced different crystalline phases at temperatures which depended on the amount of zirconia present. Thus in the case of mullite-40 wt% ZrO₂, zirconia crystallized at about 850 °C and was stable up to 1200 °C, when it reacted with free silica to form zircon (ZrSiO₄). Mullite formed above 1250 °C at the expense of zircon and remained stable at higher temperatures. The oxide powders were very homogeneous, and on sintering produced ceramics with a fine-grained uniform microstructure. The powders were very reactive and could be sintered conventionally to near-theoretical density at 1600–1700 °C without sintering aids. The fracture strength of mullite was about 275 MPa, and this could be improved to 350 MPa by hot isostatic pressing the presintered bodies. Addition of zirconia enhanced the sintering kinetics as well as the fracture strength of mullite.     

Sliding wear of self-mated Al2O3-SiC whiskerreinforced composites at 23–1200°C

Microstructural changes occurring during sliding wear of self-mated Al₂O₃-SiC whiskerreinforced composites were studied using optical, scanning electron microscopy and transmission electron microscopy. Pin-on-disc specimens were slid in air at 2.7 m s^–1 sliding velocity under a 26.5 N load for 1 h. Wear tests were conducted at 23, 600, 800 and 1200°C. Mild wear with a wear factor of 2.4 x 10^–7–1.5 x 10^–6 mm³ N^–1 m^–1 was experienced at all test temperatures. The composite showed evidence of wear by fatigue mechanisms at 800°C and below. Tribochemical reaction (SiC oxidation and reaction of SiO₂ and Al₂O₃) leads to intergranular failure at 1200°C. Distinct microstructural differences existing at each test temperature are reported.Resident Research Associate at NASA Lewis Research Center.     

Mixed-mode high temperature toughness of silicon nitride

Both opening-mode and mixed-mode fracture toughness tests were carried out at 1200 and 1300 °C on a sinter/HIP grade of silicon nitride. Data for pure opening loading (K _Ic) agree well with other experiments on the same material, which showed that the toughness was lower at 1000 °C than at room temperature, but increased as temperature increased above 1000 °C. The ratio of K _IIc/K _Ic was sufficiently insensitive to temperature that it can be considered to be constant. Results are discussed in the context of mechanisms that have been proposed to explain fracture toughness in silicon nitride.     

Structure and properties of highly crystallized graphite films based on polyimide Kapton

Highly crystallized graphite films were prepared by heat treatment of carbonized polyimide films (Kapton) at temperatures of 2700 and 3050° C. Interlayer spacing d ₀₀₂ at room temperature, and electrical resistivity, magnetoresistance and Hall coefficient at room and liquid nitrogen temperatures were measured. All of these data indicate high crystallinity of the graphitized Kapton films obtained. For the graphite films heat treated at 3050° C mean-square mobilities were estimated from the magnetoresistance data at 1 T to be 0.91 m² V^–1 sec^–1 at room temperature and 2.3 m² V^–1 sec^–1 at liquid nitrogen temperature; the value at liquid nitrogen temperature corresponds to that for a pyrolytic graphite heat treated at 3200° C for 1 h (PG 3200). Magnetic field dependence of Hall coefficient at liquid nitrogen temperature for this sample also agrees well with that for PG 3200. Scanning electron micrographs on the surfaces show that the present graphite films consist of grains of large crystallites, and grain size increases as the crystallinity of the material improves.     

Deposition and microhardness of SiC from the Si2Cl6-C3H8-H2-Ar system

We obtained SiC coating layers on a graphite substrate using hexachlorodisilane (Si₂Cl₆, boiling point 144° C) as a silicon source and propane as a carbon source. We examined the deposition conditions, contents of carbon, silicon and chlorine in the deposits, and the microhardness. Mirror-like amorphous silicon layers were deposited in the reaction temperature range 500 to 630° C. well-formed silicon carbide layers with good adherency to the substrate were obtained above 850° C. The lowest deposition temperature of SiC was estimated to be 750 to 800° C. The Vickers microhardness of the SiC layer was about 3800 kg mm^–2 at room temperature and 2150 kg mm^–2 at 1000° C.     

Thermal and dielectric properties of zirconyl phosphate compact

Experimental results are presented on the measurements of thermal expansion (up to 1500°C), thermal conductivity (up to 1000°C), dielectric constant (up to 450 °C) and tan (up to 800 °C) of zirconyl phosphate compacts obtained by sintering at 1600°C. The thermal expansion coefficient of the samples at the temperature below 1100°C was less than 1.7 × 10^–6°C^–1. The samples showed a definite shrinkage at temperatures of 1110 and 1470°C due to the phase transformations. The expansion at 1500°C was less than that at 1100°C probably because of the phase transformation. The thermal conductivity at room temperature was a very small value (0.0046 to 0.0065 cal s^–1 cm°C^–1 cm^–2). The dielectric constant was close to 9. The value of tan° (–0.0001) measured is one of the lowest values for ceramic materials.     

Thermomechanically induced embrittlement in hot isostatically pressed Si3N4/SiC composites

The macroscopic fracture properties of an Si₃N₄/SiC-platelet composite fabricated by hot isostatic pressing (HIP) without sintering aids were measured by the chevron-notch technique in bending and related to micromechanisms of fracture by means of a quantitative profilometric analysis of the fracture surfaces. Compositional and processing parameters were varied systematically in order to maximize both the fracture toughness and the work of fracture of the composite. Data were compared with those of monolithic Si₃N₄ fabricated by the same process. Cooling-rate from the HI Ping temperature was indicated as a critical parameter especially when cooling was performed under high pressure. A marked embrittlement of the composite body was found by cooling at around 650 °C h^–1 and it could not be completely recovered by successive annealing even up to temperatures above 1700 °C. The highest fracture toughness and work of fracture in the composite (obtained at a cooling rate of about 100 °C h^–1), were measured as 4.6 MPa m^1/2 and 58.6 J m^–2, respectively. In agreement with fractal analysis results, they were estimated to be about 60%–70% of the maximum values, respectively, obtainable in the present composite system, provided that a complete debonding at the platelet/matrix interface can occur.     

The effect of DO3 ordering on the parent ⇄ martensitic transformation in the CuZnAl shape-memory alloy

The character of D03 ordering resulting from different quenching rates and its effect on the characteristic martensitic transformation temperatures and shape-memory effect in the Cu-21.5 at % Zn-12.5 at % Al alloy has been analysed. ln room temperature water-quenched samples with a cooling rate 1000° C sec^–1 showing B2 long-range order and DO₃ Short-range order, e significant stabilization of martensite in the reverse transformation was observed. This stabilization was eliminated in the air-cooled samples with a cooling rate 20° C sec^–1 showing DO₃ long-range order. Mechanical tests revealed a more complete shape recovery in the air-cooled samples, when compared to room temperature waterquenched ones.     

A study of the evolution of the constituent phases and magnetic properties of hydrogen-treated Sr-hexaferrite during calcination

A hydrogen treatment followed by calcination, has been developed in order to enhance the intrinsic coercivity of Sr-hexaferrite (SrFe₁₂O₁₉). Fully hydrogen-treated Sr-hexaferrite consists of a mixture of 73%, by weight, of Fe and 27% of Sr₇Fe₁₀O₂₂ phases. Calcination of this material to reform the SrFe₁₂O₁₉ phase occurs in two stages. Between room temperature and 600°C, oxygen was absorbed resulting in a large increase in weight with the formation of a mixture of SrFeO_3–x and Fe₂O₃( and ). During the second stage, the intermediate phases reacted to form SrFe₁₂O₁₉ at a temperature of between 700 and 800°C. A partial desorption of oxygen occurred until calcination reached completion at 1000°C. The magnetization at 1100 kA m^–1 and the remanence were similar to those of the untreated material, but, because of a much refined grain size, the intrinsic coercivity was considerably larger, with values around 400 kA m^–1. Grain growth occurs at temperatures > 1000°C, resulting in a decrease in the intrinsic coercivity.     

Oxidation behaviour of a pressureless sintered AlN-SiC composite

The present study aims to investigate the oxidation behaviour of an AlN-SiC composite, pressureless sintered with the addition of Y₂O₃. Two main aspects are considered: (1) the evaluation of the oxidation kinetics in the temperature range 1300–1450°C for short term tests (30 h) and (2) the degradation of the flexural strength after oxidation at temperatures from 1000 to 1400°C for 100 h, in relationship with the microstructure of the exposed surfaces.The material starts to oxidize notably at temperatures higher than 1300°C. The oxidation kinetics is parabolic in the temperature range 1350–1450°C, the oxidation products are dependent on temperature and exposure time and are mainly constituted by crystalline mullite and alumina.The surface modification induced by long term oxidation does not affect mechanical strength until 1200°C, while after oxidation at 1400°C, the residual strength is about 25% of the starting one. These results are discussed in terms of the microstructure modifications induced by oxidation.     

Oxidation kinetics of SiC deposited from CH3SiCl3/H2 under CVI conditions

Oxidation tests were performed on SiC deposits prepared from CH₃SiCl₃/H₂ under chemical vapour infiltration conditions, at temperatures ranging from 900–1500 °C under a flow of pure oxygen at 100 kPa (passive oxidation regime). The kinetics of growth of the silica layer were established from thickness measurements performed by spectroreflectometry. They obey classical parabolic laws from which rate constants are calculated. Within 1000–1400 °C, the oxidation process is thermally activated with an apparent activation energy of 128 kJ mol^–1. Above 1400 °C and below 1000 °C, an increase in the activation energy is observed which is thought to be related to a change in the mechanism of the oxygen transport across the silica layer forT>1400 °C and tentatively to stress effects forT<1000 °C. The kinetics data are compared to those measured on silicon single crystals (used as a standard) and to other reported data on SiC.     

Rate-dependent fracture toughness of pure polycrystalline ice

A series of three-point bend tests using single edge notched testpieces of pure polycrystalline ice have been performed at three different temperatures (–20°C, –30°C and –40°C). The displacement rate was varied from 1 mm/min to 100 mm/min, producing the crack tip strain rates from about 10^–3 to 10^–1 s^–1. The results show that (a) the fracture toughness of pure polycrystalline ice given by the critical stress intensity factor (K _IC) is much lower than that measured from the J—integral under identical conditions; (b) from the determination of K _IC, the fracture toughness of pure polycrystalline ice decreases with increasing strain rate and there is good power law relationship between them; (c) from the measurement of the J—integral, a different tendency was appeared: when the crack tip strain rate exceeds a critical value of 6 × 10^–3 s^–1, the fracture toughness is almost constant but when the crack tip strain rate is less than this value, the fracture toughness increases with decreasing crack tip strain rate. Re-examination of the mechanisms of rate-dependent fracture toughness of pure polycrystalline ice shows that the effect of strain rate is related not only to the blunting of crack tips due to plasticity, creep and stress relaxation but also to the nucleation and growth of microcracks in the specimen.