Deformation of Hyperstoichiometric UO2 Single Crystals

Hyperstoichiometric UO₂ single crystals having O/M ratios from 2.06 to 2.10 were deformed in compression. The active slip plane for deformation, as evaluated from slip traces, has an orientation between (112) and (111). The critical resolved shear stresses for hyperstoichiometric specimens are approximately the same as those for stoichiometric specimens; the dislocation structures, as revealed by transmission electron microscopy, however, are very different and suggest more rapid motion and/or climb of dislocations in the hyperstoichiometric samples. The response to strain rate changes during deformation also reflects the difference in deformation behavior of hyperstoichiometric and stoichiometric crystals.     

Solution-Based Synthesis of Submicrometer ZrB2 and ZrB2–TaB2

Zirconium diboride and a zirconium diboride/tantalum diboride mixture were synthesized by solution-based processing. Zirconium n -propoxide was refluxed with 2,4-pentanedione to form zirconium diketonate. This compound hydrolyzed in a controllable fashion to form a zirconia precursor. Boria and carbon precursors were formed via solution additions of phenol–formaldehyde and boric acid, respectively. Tantalum oxide precursors were formed similarly as zirconia precursors, in which tantalum ethoxide was used. Solutions were concentrated, dried, pyrolyzed (800°–1100°C, 2 h, flowing argon), and exposed to carbothermal reduction heat treatments (1150°–1800°C, 2 h, flowing argon). Spherical particles of 200–600 nm for pure ZrB₂ and ZrB₂–TaB₂ mixtures were formed.     

Compression Test and Plastic Strain of alpha-Al2O3 Single Crystals

Compression tests of single crystals are analyzed with respect to shear due to the friction at the loaded ends. This simple approach permits an explanation of the features associated with prism plane slip in sapphire (α-Al₂O₃), i.e., the shape changes of the specimens and the curvature of the glide planes.     

Thermophysical Properties of ZrB2 and ZrB2–SiC Ceramics

Thermophysical properties were investigated for zirconium diboride (ZrB₂) and ZrB₂–30 vol% silicon carbide (SiC) ceramics. Thermal conductivities were calculated from measured thermal diffusivities, heat capacities, and densities. The thermal conductivity of ZrB₂ increased from 56 W (m K)⁻¹ at room temperature to 67 W (m K)⁻¹ at 1675 K, whereas the thermal conductivity of ZrB₂–SiC decreased from 62 to 56 W (m K)⁻¹ over the same temperature range. Electron and phonon contributions to thermal conductivity were determined using electrical resistivity measurements and were used, along with grain size models, to explain the observed trends. The results are compared with previously reported thermal conductivities for ZrB₂ and ZrB₂–SiC.     

Laser Sintering of ZrB2

Preliminary results about laser sintering of zirconium diboride (ZrB₂), a good ultra high-temperature ceramics candidate, are presented. In order to evaluate a suitable sintering method, single pulsed laser and a concentric dual laser system were carried out. Two different ZrB₂ powders having ∼15 and ∼2 μm particle size were assessed for sintering. Scanning electron microscopy images showed that the concentric dual laser sintered layer using ∼2 μm particle size of ZrB₂ had relatively smooth surface morphology. X-ray diffraction results confirmed that the sintered layer mainly retained the crystalline phases as the starting powder. In addition, the rapid cooling rate of laser sintering enabled the formation of needle-like nanostructures at the sintered surface.     

The ZrB2 Volatility Diagram

A volatility diagram was calculated for temperatures of 1000, 1800, and 2500 K to understand the oxidation of ZrB₂. Applying the diagram, it can be seen that exposure of ZrB₂ to air produces ZrO₂ (cr) and B₂O₃ (l) over the temperature range considered. The pressure of the predominant vapor species was predicted to increase from ∼10⁻⁶ Pa at 1000 K, to 344 Pa at 1800 K, and to ∼10⁵ Pa at 2500 K. Predictions were consistent with experimental observations that ZrB₂ exhibits passive oxidation below 1200 K, but undergoes active oxidation at higher temperatures due to B₂O₃ (l) evaporation.     

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.     

Fabrication and Characterization of ZrB2-Based Ceramic Using Synthesized ZrB2–LaB6 Powder

ZrB₂–LaB₆ powder was obtained by reactive synthesis using ZrO₂, La₂O₃, B₄C, and carbon powders. Then ZrB₂–20 vol% SiC–10 vol% LaB₆ (ZSL) ceramics were prepared from commercially available SiC and the synthesized ZrB₂–LaB₆ powder via hot pressing at 2000°C. The phase composition, microstructure, and mechanical properties were characterized. Results showed that both LaB₆ and SiC were uniformly distributed in the ZrB₂ matrix. The hardness and bending strength of ZSL were 17.06±0.52 GPa and 505.8±17.9 MPa, respectively. Fracture toughness was 5.7±0.39 MPa·m^1/2, which is significantly higher than that reported for ZrB₂–20 vol% SiC ceramics, due to enhanced crack deflection and crack bridging near SiC particles.     

Compressive Creep of Al2O3 Single Crystals

Aluminum oxide single crystals deformed by dislocation glide and deformation twinning during compressive creep at 1400° to 1700°C. The activation energy for basal slip was a function of the applied stress and agreed with activation energies previously measured by observation of yielding phenomena. The overcoming of a large Peierls-Nabarro stress is the most probable rate-controlling mechanism. Rhombohedral twinning, a significant deformation mode in creep, depends on surface damage for nucleation. The activation energy for rhombohedral twin growth, a function of the applied stress, is substantially lower than that for basal slip. When basal slip and rhombohedral twinning occur concurrently, creep by basal slip results, but the presence of twins can substantially reduce the creep rate.     

Plastic Deformation of Al2O3 During Abrasion

X-ray diffraction line broadening examination of the debris produced by abrasion of polycrystalline Al₂O₃ on a 320-grade diamond-impregnated lap showed that heavy plastic deformation is associated with the abrasive process. Annealing of the debris resulted in an increase in crystallite size at temperatures >800°C but only minor changes in microstrain. This behavior contrasts with the large reduction in microstrain reported for ball-milled Al₂O₃ with similar initial crystallite size. The results are consistent with recovery during formation of the debris particles. A transient temperature of 900° to 1200°C was estimated from the plastic work done, assuming that material is removed by a mechanism similar to that observed in the abrasion of metals.     

Thermal Expansion of Y2SiO5 Single Crystals

The thermal expansion of Y₂SiO₅ crystals has been measured for the principal crystallographic directions and two orthogonal directions in the (010) plane in the temperature range 25° to 200°C. This monoclinic crystal has strongly anisotropic expansions with coefficients which range from 0.6 × 10⁻⁶/°C for [100] to 11.4 × 10⁻⁶/°C for [001]. Third-order polynomials have been calculated from the expansion curves. Data for the β angle and cell volume as a function of temperature are also given. The thermal expansion of Y₂SiO₅ crystals is not affected by doping with 5% Tb.     

Substructure and Perfection in UO2 Single Crystals

The quality of UO₂ single crystals grown by arc-melting, by a modified floating-zone technique (ICZG), and by vapor deposition was studied using etch-pit patterns, electron microscopy, and X-ray topography. These techniques complemented each other and indicated significant variations between the crystals grown by the different techniques. Both types of melt-grown crystals contained extensive substructure and approximately 10⁶ etch pits/cm²; finely dispersed inhomogeneities were found in the vapor-grown crystals. Stoichiometry control during growth permitted a major improvement in the perfection of the ICZG crystals.     

Transmission Electron Microscopy Characterization of Hot-Pressed ZrB2 with MoSi2 Additive

Microstructure of the hot-pressed ZrB₂ with MoSi₂ additive was investigated by transmission electron microscopy (TEM). The effect of MoSi₂ addition on the microstructure of the ceramic was assessed. For the pure ZrB₂, the microstructure consisted of the equiaxed ZrB₂ grains and a few elongated ZrB₂ grains. For the ZrB₂ with MoSi₂ additive, the microstructure consisted almost entirely of equiaxed ZrB₂ grains. A few dislocations were present in the ZrB₂ grains. In addition, high-resolution TEM observations showed that the intergranular amorphous phase was absent at two ZrB₂ grain boundaries in the ZrB₂ with MoSi₂ additive.     

Room-Temperature Strength and Fracture of ZrO2-Y2O3 Single Crystals

Strength and fracture toughness results are presented for ZrO₂ single crystals stabilized with Y₂O₃. The crystals (2 cm in diameter by 5 cm long) were prepared by skull melting. The partially stabilized compositions with 4 to 6 wt% Y₂O₃ showed a dramatic improvement in mechanical properties over the fully stabilized samples containing 20 wt% Y₂O₃, i.e. a strength exceeding 1000 MPa and a fracture toughness of 8 Mpa,.m ^1/2 were achieved compared to 200 MPa and 2 Mpa.m^1/2, respectively, for fully stabilized ZrO₂ single crystals.     

High-Temperature Tensile Strength of Er2O3-Doped ZrO2 Single Crystals

The deformation and fracture mechanisms in tension were studied in single-crystal Er₂O₃-doped ZrO₂ monofilaments processed by the laser-heated floating zone method. Tensile tests were carried out between 25° and 1400°C at different loading rates and the dominant deformation and fracture mechanisms were determined from the shape of the stress–strain curves, the morphology of the fracture surfaces, and the evidence provided by monofilaments deformed at high temperature and broken at ambient temperature. The tensile strength presented a minimum at 600°–800°C and it was controlled by the slow growth of a crack from the surface. This mechanism was also dominant in some monofilaments tested at 1000°C and above, while others showed extensive plastic deformation before fracture at these temperatures. The strength of plastically deformed monofilaments was significantly higher than those which failed by slow crack growth due to the marked strain hardening capacity of this material.