Microstructural development during crystallization firing of a dental-grade nanostructured lithia-zirconia glass-ceramic

The microstructural development during crystallization firing of a commercially-available dental-grade nanostructured lithia-zirconia glass-ceramic (Vita Suprinity® PC) was unraveled using a wide battery of ex-situ and in-situ characterization techniques. It was found that the milling blocks are slightly crystallized glass-ceramics, with a complex chemical composition and consisting of partially de-polymerized glass plus lithium silicate (Li₂SiO₃) nanocrystals. It was also found that during crystallization firing the glassy matrix first reacts with part of the Li₂SiO₃ to form lithium disilicate (Li₂Si₂O₅) at ～810?820 °C, and then lithium orthophosphate (Li₃PO₄) precipitates from the glass. This results in glass-ceramics with abundant nanocrystals embedded in a sparse zirconosilicate glass matrix (containing many other cations subsumed) that, due to its high viscosity, inhibited crystal growth. Therefore, these dental glass-ceramics are not reinforced with zirconia (ZrO₂) crystals unless over-fired above ～890 °C and at the expense of its singular nanostructure. Finally, this study opens doors for optimizing the clinical performance of these dental glass-ceramics via microstructural tailoring.     

Effect of temperature on the pre-creep mechanical properties of silicon nitride

The elasto-plastic properties and contact damage evolution of a commercial polycrystalline silicon nitride are evaluated as a function of temperature up to 1000 °C, using a recently developed method combining Hertzian indentation and FEM simulation. The results of the study are compared to existing data for other ceramic materials such as alumina and zirconia. Silicon nitride is found to exhibit an excellent combination of elasto-plastic properties in the pre-creep temperature range and good contact damage resistance. These qualities make this material ideal for high temperature applications in general, and in particular to be used in spherical indenters for the evaluation of mechanical properties of other materials at elevated temperature using the procedure applied in this work.     

Effect of the sintering additive content on the protective passive oxidation behaviour of pressureless liquid-phase-sintered SiC

The long-term oxidation behaviour in air of pressureless liquid-phase-sintered SiC was investigated as a function of the sintering-additive content (a mixture of Y₂O₃ and Al₂O₃ in the 3:5 molar ratio) at oxidizing temperatures in the interval 1100–1300 °C. It is shown that oxidation under these mild conditions is always passive, and with formation of protective oxide scales. However, the oxidation kinetics cannot be described appropriately by the parabolic-rate law. Instead, due to the gradual crystallization of the oxide scales during oxidation, it is more complex, exhibiting two different stretches given respectively by the arctan- and parabolic-rate laws. Furthermore, it was found that the rate-limiting mechanism of the initial arctan oxidation is the outward diffusion of metal cations from the secondary intergranular phase into the oxide scale, with the activation energy of the oxidation being very high and decreasing from 545 to 432 kJ/mol with increasing sintering-additive content from 5 to 20 wt%. The rate-limiting mechanism of the subsequent parabolic oxidation is however the inward diffusion of oxygen through the multicomponent oxide scale, with the activation energy being lower than before and also decreasing from 345 to 205 kJ/mol as the sintering-additive content increases from 5 to 20 wt%. It is also shown that the oxidation resistance decreases with increasing sintering-additive content, but that while the decrease is moderate up to 10 wt%, it is very marked for greater contents.     

Effect of the sintering additive content on the non-protective oxidation behaviour of pressureless liquid-phase-sintered α-SiC in air

The long-term oxidation resistance of pressureless liquid-phase-sintered (PLPS) α-SiC was investigated as a function of the content of sintering additive (in particular, YAG) at 1500 °C in air. It is shown that, regardless of the vol.% YAG, the oxidation is passive at that high temperature, with a kinetics given by the paralinear-rate law. This is because the oxide scales grow due to oxidation of the SiC grains, but recede due to the formation of a eutectic phase and to the carbothermal reduction of YAG. It is also shown that the oxidation resistance of PLPS SiC decreases markedly with increasing vol.% YAG, an effect that is especially marked above 7.3 vol.% YAG where a change in oxidation behaviour occurs. Thus, while up to 7.3 vol.% YAG the PLPS SiC ceramics gain mass during the entire oxidation process (500 h) because the oxide scales are at least semi-protective, from 11.1 vol.% YAG onwards the PLPS SiC ceramics first gain mass and then lose mass linearly over oxidizing time because the oxide scales are non-protective. Finally, implications for the design of PLPS SiC ceramics that can tolerate prolonged exposures at high temperatures in air are discussed.     

Sliding-wear resistance of pure near fully-dense B4C under lubrication with water,diesel fuel,and paraffin oil

The sliding-wear resistance of pure near fully-dense B₄C is investigated, and the wear mode/mechanisms identified, under lubrication with water, diesel fuel, and paraffin oil. It is found that the wear is mild in the three cases, with specific wear rates (SWRs) of 10^?16–10^?17 m³/N m. Nonetheless, the wear resistance of the B₄C ceramic is one order of magnitude greater under oil lubrication (10¹⁶ N m/m³) than under water lubrication (10¹⁵ N m/m³), and twice as great for the specific case of paraffin oil than diesel fuel, attributable to the lubricant’s viscosity. It is also found that the wear mode is always abrasion, and that the wear mechanisms are plastic deformation and localized fracture with grain pullout. However, in agreement with the macro-wear data, the severity of the wear damage is lower under lubrication with paraffin oil, followed by diesel fuel, and lastly water. Finally, microstructural considerations are discussed with a view to enhancing the sliding-wear resistance of B₄C triboceramics.     

Microhardness and Fracture Toughness Anisotropy in Cubic Zirconium Oxide Single Crystals

Vickers and Knoop indentation tests have been used to study the fracture and deformation characteristics of 9.4-mol%-Y₂O₃-stabilized ZrO₂ single crystals. K_c is anisotropic, with values of 1.9 and 1.1 MPa·m^1/2 for radial cracks propagating along (100) and (110), respectively. The toughness for these two orientations was also determined using the single-edge notched-beam geometry, and yielded values of 1.9 and 1.5 MPa·m^1/2.     

Transient liquid-phase assisted spark-plasma sintering and dry sliding wear of B4C ceramics fabricated from B4C nanopowders

With the motivation of developing B₄C composites with superior wear resistance for tribological applications, an ultrafine-grained (～200?300 nm) B₄C composite was fabricated, characterized microstructurally, and tested mechanically and tribologically. First, a well-dispersed powder mixture of B₄C nanopowders (～40 nm) with coarse Ti-Al powders (～38 μm) as transient liquid-phase sintering additives was environmentally-friendly prepared by aqueous colloidal processing, optimized by measurements of the zeta potential of dilute suspensions and rheological studies of concentrated suspensions. Second, the powder mixture obtained by freeze-drying was densified by spark-plasma sintering (SPS), identifying the optimal SPS temperature (1850°C) by measurements of density, hardness, and toughness. Third, the dry sliding-wear behaviour of the optimal superhard B₄C composite (～31.5 GPa) was investigated by pin-on-disk tests and observations of the worn surface, determining its specific wear rate (～4.4·10^?8 mm³/(N·m)) as well as wear mode (two-body abrasion) and mechanism (plastic deformation). And lastly, the wear behaviour of the ultrafine-grained B₄C composite was compared with that of a reference fine-grained (～0.7?0.9 μm) B₄C composite, finding that both have the same mode and mechanism of wear but with the former being more resistant than the latter (～2.3·10⁷ vs 1.9·10⁷ (N·m)/mm³). Implications for the fabrication of B₄C tribocomponents with greater superior wear resistance are discussed.     

Differentiation between Pseudocubic and Cubic Phases in Y–ZrO2 Using Rietveld Analysis

The precise microstructural characterization of the yttriapartially stabilized zirconia (Y-PSZ) system by means of X-ray diffractometry (XRD) experiments faces a serious challenge: the discrimination beween the cubic, c , and pseudocubic, t', phases. We show how the confusion between the two phases goes beyond a simple qualitative problem, because the relative abundances for all the present polymorphs can be substantially modified. This is particularly true for the amount of transformable tetragonal phase, which is of paramount importance for the design of zirconia-based tough ceramics. Similarly, we show that a conclusive discrimination between c and I' phases is possible on the basis of XRD experiments by a careful application of the Rietveld method and by emphasizing some subtle details around the angular domain close to the {200} planes. The procedure is applied to samples of Y-PSZ (4.7 mol%).     

Sliding-Wear-Resistant Liquid-Phase-Sintered SiC Processed Using α-SiC Starting Powders

Low-cost α-silicon carbide (SiC) starting powder, instead of the more expensive β-SiC starting powder, has been used to process liquid-phase-sintered (LPS) SiC ceramics with different microstructures: (i) elongated SiC grains ( in situ toughened LPS SiC), (ii) fine equiaxed SiC grains, and (iii) coarse equiaxed SiC grains. The effects of microstructure on the sliding-wear properties of these LPS SiC ceramics have been studied. The sliding-wear resistance of the in situ toughened LPS SiC ceramic is found to be significantly better than that of two equiaxed-grain LPS SiC ceramics. This has been attributed to the existence of a hard, interlocking network of elongated SiC grains and the isolated nature of the yttrium aluminum garnet (YAG) second phase in the in situ toughened LPS SiC ceramic. This is in contrast to the equiaxed-grain LPS SiC ceramics, where the equiaxed grains are embedded within a continuous YAG phase matrix. The use of the α-SiC starting powder allows the processing of low-cost LPS SiC ceramics that are both sliding-wear resistant and tough.