High-Thermal-Conductivity Aluminum Nitride Ceramics: The Effect of Thermodynamic, Kinetic, and Microstructural Factors

Improvement in the thermal conductivity of aluminum nitride (AlN) can be realized by additives that have a high thermodynamic affinity toward alumina (Al₂O₃), as is clearly demonstrated in the aluminum nitride-yttria (AlN-Y₂O₃) system. A wide variety of lanthanide dopants are compared at equimolar lanthanide oxide:alumina (Ln₂O₃: Al₂O₃, where Ln is a lanthanide element) ratios, with samaria (Sm₂O₃) and lutetia (Lu₂O₃) being the dopants that give the highest- and lowest-thermal-conductivity AlN composites, respectively. The choice of the sintering aid and the dopant level is much more important than the microstructure that evolves during sintering. A contiguous AlN phase provides rapid heat conduction paths, even at short sintering times. AlN contiguity decreases slightly as the annealing times increase in the range of 1–1000 min at 1850°C. However, a substantial increase in thermal conductivity results, because of purification of AlN grains by dissolution-reprecipitation and bulk diffusion. Removal of grain-boundary phases, with a concurrent increase in AlN contiguity, occurs at high annealing temperatures or at long times and is a natural consequence of high dihedral angles (poor wetting) in liquidphase-sintered AlN ceramics.     

On some aspects of breakdown of β″-alumina solid electrolyte

A theoretical expression is derived for the pressure generated in the sodium-filled cracks of -alumina under electrolytic conditions by treating the flux of sodium ions to the cracks in terms of the Laplace equation for the appropriate boundary conditions. It is demonstrated that the pressure generated decreases with increasing crack length for a given current density in contrast to the predictions of some investigators. It is suggested that some other factors must be considered if the microfracture model via Poiseuille pressure is to be a viable mechanism for electrolyte degradation.     

Fabrication, Microstructural Characterization, and Mechanical Properties of Polycrystalline t'-Zirconia

Large-grained (100- to 200-μm), yttria-doped, polycrystalline t '-zirconia ceramics were fabricated by heat-treating presintered samples at temperatures 2100°C. Polarized light microscopy revealed the ferroelastic domain structure in the t ' samples. XRD showed that no monoclinic phase was detected on as-polished, ground and fracture surfaces, or on surfaces while under a tensile stress as high as 400 MPa. By contrast, relative changes occurred in the tetragonal peak intensities, which were attributed to ferroelasatic domain switching. The higher toughness of 3-mol%-Y₂O₃-doped t ' samples (7.7 MPa · m^1/2) compared to that of 8 mol% Y₂O₃ cubic samples (2.4 MPa · m^1/2) was explained in part by ferroelastic domain switching.     

Fabrication and characterization of SiC-AIN alloys

SiC-AIN alloys were prepared by the carbothermal reduction of silica and alumina, derived from an intimate mixture of silica, aluminium chloride and starch. The resulting single-phase SiC-AIN powder was hot-pressed without additives to a high density. The dense bodies had a fine-grained uniform microstructure. The Young's elastic modulus, microhardness, fracture toughness, thermal expansion and thermal conductivity were measured as functions of composition. The creep behaviour of the SiC-AIN alloy was compared with that of silicon carbide.     

Organic Semiconductor Growth and Morphology Considerations for Organic Thin‐Film Transistors

Analogous to conventional inorganic semiconductors, the performance of organic semiconductors is directly related to their molecular packing, crystallinity, growth mode, and purity. In order to achieve the best possible performance, it is critical to understand how organic semiconductors nucleate and grow. Clever use of surface and dielectric modification chemistry can allow one to control the growth and morphology, which greatly influence the electrical properties of the organic transistor. In this Review, the nucleation and growth of organic semiconductors on dielectric surfaces is addressed. The first part of the Review concentrates on small‐molecule organic semiconductors. The role of deposition conditions on film formation is described. The modification of the dielectric interface using polymers or self‐assembled mono­layers and their effect on organic‐semiconductor growth and performance is also discussed. The goal of this Review is primarily to discuss the thin‐film formation of organic semiconducting species. The patterning of single crystals is discussed, while their nucleation and growth has been described elsewhere (see the Review by Liu et. al). 1 The second part of the Review focuses on polymeric semiconductors. The dependence of physico‐chemical properties, such as chain length (i.e., molecular weight) of the constituting macromolecule, and the influence of small molecular species on, e.g., melting temperature, as well as routes to induce order in such macromolecules, are described.     

Thermodynamic and Kinetic Effects of Oxygen Removal on the Thermal Conductivity of Aluminum Nitride

High thermal conductivity, low dielectric constant, high electrical resistivity, low density, and a thermal expansion coefficient that matches well with that of silicon are the principal attributes of AIN that have attracted much attention over the past decade. It is also now well established that oxygen as an impurity lowers the thermal conductivity of AIN. Processing techniques have been developed which not only facilitate pressureless densification of AIN but also enhance its thermal conductivity. The present work explores the thermodynamics and the kinetics of oxygen removal and the resultant enhancement of thermal conductivity. Polycrystalline AIN ceramics were fabricated with Y₂O₃, Dy₂O₃, Yb₂O₃, CaO, BaO, or MgO as additives. Samples were sinter/annealed at 1850°C for up to 1000 min. The AIN grain size of sintered samples ranged between 2 and 9 μm. The samples typically contained two or three phases with the predominant phase being AIN. Secondary phases in Y₂O₃-doped AIN consisted of yttrium aluminates which were along three grain junctions and along grain facets. The presence of Y₃Al₅O₁₂, YAIO₃, and Y₄Al₂O₉, as well as Y₂O₃, depending upon the Y₂O₃/Al₂O₃ ratio, was revealed by X-ray diffraction. Thermal conductivity increased with the amount of additive and annealing time. Thermal conductivity also depended on the type of additive. Samples with thermal conductivity up to 200 W/(m · K) were fabricated. The variation in thermal conductivity with the type and the amount of the additive is explained on the basis of the thermodynamics of oxygen removal. In particular, the higher thermal conductivity of CaO-doped, in comparison with MgO-doped, samples is rationalized on the basis that the free energy of formation, ΔG°, of CaAl₂O₄ is less than that of MgAl₂O₄. It is proposed that the higher the |ΔG°|, with ΔG° < 0, the higher is the resultant thermal conductivity. An increase in the thermal conductivity with annealing time is attributed to the kinetics of oxygen removal from AIN grains.     

High temperature creep in polycrystalline AIN-SiC ceramics

Polycrystalline dense ceramic specimens containing 75 mol % AIN-25 mol % SiC and 60 mol % AIN-40 mol % SiC were subjected to creep deformation in bending at elevated temperatures. Over the range of temperatures and stresses investigated, the creep rate was found to vary linearly with stress indicative of diffusional creep. Creep was found to be thermally activated with activation energy in the range from 175 kcal mol⁻¹ to 219 kcal mol⁻¹. Electron microscopic observation indicated that crack like cavities formed near the tensile surfaces during creep.     

The Tetragonal-Monoclinic Transformation in Zirconia: Lessons Learned and Future Trends

Zirconia ceramics have found broad applications in a variety of energy and biomedical applications because of their unusual combination of strength, fracture toughness, ionic conductivity, and low thermal conductivity. These attractive characteristics are largely associated with the stabilization of the tetragonal and cubic phases through alloying with aliovalent ions. The large concentration of vacancies introduced to charge compensate of the aliovalent alloying is responsible for both the exceptionally high ionic conductivity and the unusually low, and temperature independent, thermal conductivity. The high fracture toughness exhibited by many of zirconia ceramics is attributed to the constraint of the tetragonal-to-monoclinic phase transformation and its release during crack propagation. In other zirconia ceramics containing the tetragonal phase, the high fracture toughness is associated with ferroelastic domain switching. However, many of these attractive features of zirconia, especially fracture toughness and strength, are compromised after prolonged exposure to water vapor at intermediate temperatures (∼30°–300°C) in a process referred to as low-temperature degradation (LTD), and initially identified over two decades ago. This is particularly so for zirconia in biomedical applications, such as hip implants and dental restorations. Less well substantiated is the possibility that the same process can also occur in zirconia used in other applications, for instance, zirconia thermal barrier coatings after long exposure at high temperature. Based on experience with the failure of zirconia femoral heads, as well as studies of LTD, it is shown that many of the problems of LTD can be mitigated by the appropriate choice of alloying and/or process control.