Silicon nitride has been researched intensively, largely in response to the challenge to develop internal combustion engines with hot-zone components made entirely from ceramics. The ceramic engine programs have had only partial success, but this research effort has succeeded in generating a degree of understanding of silicon nitride and of its processing and properties, which in many respects is more advanced than of more widely used technical ceramics. This review examines from the historical standpoint the development of silicon nitride and of its processing into a range of high-grade ceramic materials. The development of understanding of microstructure–property relationships in the silicon nitride materials is also surveyed. Because silicon nitride has close relationships with the SiAlON group of materials, it is impossible to discuss the one without some reference to the other, and a brief mention of the development of the SiAlONs is included for completeness.

Silicon Nitride and Related Materials

The use of self-reinforcement by larger elongated grains in silicon nitride ceramics requires judicious control of the microstructure to achieve high steady-state toughness and high fracture strength. With a distinct bimodal distribution of grain diameters, such as that achieved by the addition of 2% rodlike seeds, the fracture resistance rapidly rises with crack extension to steady-state values of up to 10 MPa{center_dot}m{sup 1/2} and is accompanied by fracture strengths in excess of 1 GPa. When the generation of elongated reinforcing grains is not regulated, a broad grain diameter distribution is typically generated. While some toughening is achieved, both the plateau (steady-state) toughness and the R-curve response suffer, and the fracture strength undergoes a substantial reduction. Unreinforced equiaxed silicon nitride exhibits the least R-curve response with a steady-state toughness of only 3.5 MPa{center_dot}m{sup 1/2} coupled with a reduced fracture strength.

Microstructural Design of Silicon Nitride with Improved Fracture Toughness: I, Effects of Grain Shape and Size

The London dispersion forces, along with the Debye and Keesom forces, constitute the long-range van der Waals forces. London's and Hamaker's work on the point-to-point dispersion interaction and Lifshitz's development of the continuum theory of dispersion are the foundations of our understanding of dispersion forces. Dispersion forces are present for all materials and are intrinsically related to the optical properties and the underlying interband electronic structures of materials. The force law scaling constant of the dispersion force, known as the Hamaker constant, can be determined from spectral or parametric optical properties of materials, combined with knowledge of the configuration of the materials. With recent access to new experimental and ab initio tools for determination of optical properties of materials, dispersion force research has new opportunities for detailed studies. Opportunities include development of improved index approximations and parametric representations of the optical properties for estimation of Hamaker constants. Expanded databases of London dispersion spectra of materials will permit accurate estimation of both nonretarded and retarded dispersion forces in complex configurations. Development of solutions for generalized multilayer configurations of materials are needed for the treatment of more-complex problems, such as graded interfaces. Dispersion forces can play a critical role in materials applications. Typically, they are a component with other forces in a force balance, and it is this balance that dictates the resulting behavior. The ubiquitous nature of the London dispersion forces makes them a factor in a wide spectrum of problems; they have been in evidence since the pioneering work of Young and Laplace on wetting, contact angles, and surface energies. Additional applications include the interparticle forces that can be measured by direct techniques, such as atomic force microscopy. London dispersion forces are important in both adhesion and in sintering, where the detailed shape at the crack tip and at the sintering neck can be controlled by the dispersion forces. Dispersion forces have an important role in the properties of numerous ceramics that contain intergranular films, and here the opportunity exists for the development of an integrated understanding of intergranular films that encompasses dispersion forces, segregation, multilayer adsorption, and structure. The intrinsic length scale at which there is a transition from the continuum perspective (dispersion forces) to the atomistic perspective (encompassing interatomic bonds) is critical in many materials problems, and the relationship of dispersion forces and intergranular films may represent an important opportunity to probe this topic. The London dispersion force is retarded at large separations, where the transit time of the electromagnetic interaction must be considered explicitly. Novel phenomena, such as equilibrium surficial films and bimodal wetting/dewetting, can result in materials systems when the characteristic wavelengths of the interatomic bonds and the physical interlayer thicknesses lead to a change in the sign of the dispersion force. Use of these novel phenomena in future materials applications provides interesting opportunities in materials design.

/pdf/origins-and-applications-of-london-dispersion-forces-and-4mqvsuev1r.pdf

Origins and Applications of London Dispersion Forces and Hamaker Constants in Ceramics

The thickness of the intergranular films in Si{sub 3}N{sub 4} densified with lanthanide oxides has been systematically investigated using high-resolution transmission electron microscopy. Four lanthanide oxides--La{sub 2}O{sub 3}, Nd{sub 2}O{sub 3}, Gd{sub 2}O{sub 3}, and Yb{sub 2}O{sub 3}--as well as Y{sub 2}O{sub 3} are chosen so that the results will reflect the overall trend in the effect of the lanthanide utilized. The film thicknesses increase with increasing ionic radius of the lanthanide. In addition, Si{sub 3}N{sub 4} particles flocculated into isolated clusters in the lanthanide-based glasses are also characteristically separated by an amorphous film whose thickness is similar to that in the comparable polycrystalline ceramics, demonstrating that the film thickness is dictated entirely by the composition and not by the amount of the glass phase present.

Grain Boundary Films in Rare‐Earth‐Glass‐Based Silicon Nitride

It has been shown that pressureless sintering of SiC to theoretical density is possible with sintering additives from the system AlN–Y2O3. While commonly a combination of oxides is used such as Al2O3–Y2O3 (–SiO2), the oxynitride additives offer the advantage that only a nitrogen atmosphere is required instead of a powder bed for thermochemical stabilisation at the sintering temperature. The thermal decomposition of AlN is suppressed quite effectively when a moderate nitrogen overpressure is applied, resulting in very small mass loss during densification which only depends on the oxygen content of the SiC starting powder. By varying the mass ratio of β-SiC to α-SiC and applying dedicated post-densification heat treatments, a platelet-strengthened microstructure is obtained which shows enhanced fracture toughness. The platelet formation is attributed to a solution / precipitation process with simultaneous phase transformation from β-SiC to α-SiC, followed by anisotropic grain growth of α-SiC. In the present work, recent progress in the mechanical properties of these materials is reported. By means of a simple surface treatment-annealing in air — it is possible to obtain four-point bending strengths in excess of 1 GPa in liquid phase sintered SiC. The strength retention at temperatures around 1200°C is significantly improved.

High-temperature effects in the fracture mechanical behaviour of silicon carbide liquid-phase sintered with AlN–Y2O3 additives

The microstructural evolution in Si3N4 ceramics is analysed by studies of the growth of isolated Si3N4 grains dispersed in oxinitride glasses as well as model experiments of sintered materials. The experiments with the supersaturated oxynitride glasses offer the possibility to study the grain growth in the absence of steric hindrance and show the influence of the additive composition on the development of the grain morphology. The differences in grain growth behaviour is discussed with respect to the cation radius of the glass forming rare earth oxides. Investigations of polycrystalline Si3N4 ceramics show that the grain size and morphology are controlled by the properties of the Si3N4 starting powder, the sintering temperature and the additives. Different Si3N4 powders and various additive combinations were used in order to explore the dominant growth mechanisms.

M. J. Hoffmann

Papers

Analysis of Microstructural Development and Mechanical Properties of Si3N4 Ceramics