Synthesis of Cerium α-SiAlON with Nuclei Addition

Cerium α-SiAlON ceramics were made from a powder mixture of Si₃N₄-AlN-CeO₂ that contained 1 wt% yttrium α-SiAlON powder. Plasma-activated sintering was used to examine the effect of the cooling rate on the formation of α-SiAlON. The formation of cerium α-SiAlON was suggested to be controlled by the nucleation at the surface of α-SiAlON nuclei, because α-phase formation could not occur without the addition of SiAlON powder. The solubility of cerium in the α-SiAlON was shown to be less than a previously predicted critical value.     

Distribution of Cerium Ions in Cerium-Doped α'-SiAlON and Its Effect on Grain Morphology

Cerium-doped α'-SiAlON material was prepared by spark plasma sintering at 1750°C under 30 MPa pressure for 10 min. Yttrium α'-SiAlON seeds (1 wt%) were added to the starting powder mixture. Recent work showed that up to 45 wt% of α'-SiAlON phases are formed in the present sintered ceramics. The material presented a microstructure, containing rodlike cerium-doped α'-SiAlON crystals. In this paper, transmission electron microscopy and energy dispersive spectroscopy examinations of the α'-SiAlON grains are reported. The structural analyses revealed a high density of domain boundaries, within which larger amounts of cerium ions were segregated than in the matrix. The density of the domain boundaries was proportional to the amount of incorporated cerium ions. These structural defects eventually dominated the growth habits of the α'-SiAlON crystals, by modifying the structure of the interstices at the boundary sites. The role of yttrium α'-SiAlON seeds also is discussed in this paper.     

Synthesis of α-SiAlON Seed Crystals

Single-phase seed crystals of Ca- and Y-α-SiAlONs have been synthesized for tailoring microstructure of α-SiAlON ceramics. The influence of composition, sintering temperature, and nitrogen pressure on the size and morphology of seeds has been explored. Guidelines for α-SiAlON seed preparation and morphology control are provided.     

Control of Microstructures in α-SiAlON Ceramics

The effects of sintering cycles and doping elements on the microstructures of Ln-α-sialon were studied. The results showed that microstructures with an elongated α-sialon morphology could be obtained through high-temperature post-heat treatment (1800–1900°C) or by prolonging soaking times during sintering. Different rare-earth elements had a profound effect on the microstructure of the resulting α-sialon. The Ln-α-sialon doped with low- Z -value elements could easily develop elongated grains with higher aspect ratio.     

Microstructure Control of In-Situ-Toughened α-SiAlON Ceramics

Single-phase α-SiAlON with elongated grains is obtained from α-Si₃N₄ powder for a broad range of compositions of practical interest. Following the concept of nucleation and growth, two-step firing is used for microstructure control. This method takes advantage of the slow transformation reaction from α-Si₃N₄ to α-SiAlON at low temperature when the composition is near the α-SiAlON phase boundary and, hence, is marginally stable. For more-stable compositions, the seeding of α-SiAlON crystals is more effective, because it allows elongated grains to grow onto the seed crystals. The fracture toughness is strongly correlated with the microstructure and is enhanced greatly in the optimized materials.     

Liquid-Phase Growth of Small Crystals for Seeding α-SiAlON Ceramics

Single-phase small crystals of Li-, Mg-, Ca-, Y-, Nd-, and Yb-α-SiAlONs have been obtained by liquid-phase sintering for various compositions and processing conditions. These crystals are suitable for seeding grain growth in α-SiAlON ceramics. The influence of chemical and processing parameters (starting composition and powders, green density, liquid content, heating schedule, nitrogen pressure, and temperature) on the size and morphology of seed crystals has been investigated. The results are compared with those for β-Si₃N₄ crystal formation, and the differences are discussed in terms of nucleation and growth kinetics during liquid-phase sintering.     

R-Curve Behavior of In Situ Toughened α-SiAlON Ceramics

R -curves of single-phase Y- and Ca-containing α-SiAlON ceramics have been measured. They range from flat ones for fine-grain ceramics to pronounced rising ones when large elongated grains are present. The highest toughness measured reached 11.5 MPa·m^1/2 over a crack extension of about 1000 μm.     

Microstructural Tailoring and Characterization of a Calcium α-SiAlON Composition

Three calcium α-SiAlON microstructures—namely, fine-grained, bimodal, and large elongated—were developed using powders of the same composition and then characterized. The evolution of grain size and morphology was determined to be a process of nucleation and growth that could be controlled with a two-step sintering technique. The extent of texture was identified in the as-hot-pressed materials as a function of sintering conditions. Samples with different microstructures exhibited different hardness and fracture toughness. The true hardness was derived from the intrinsic relation between applied loads and indent sizes. The effect of microstructure on hardness and fracture toughness was analyzed.     

Hollow Beads Composed of Nanosize Ca α-SiAlON Grains

Carbothermal reduction—nitridation (CRN) of SiO₂ is an attractive method to manufacture Si₃N₄ powders with controlled grain morphology. Moreover, β-SiAlON powders could also be synthesized from either pure powder mixture or some inexpensive raw minerals by CRN and the resulting powders favored the sintering of SiAlON product. However, there have been few works on preparing α-SiAlON powders so far. In this work, Ca α-SiAlON powder was synthesized by CRN of a SiO₂—Al₂O₃—CaCO₃ mixture. An unusual morphology of hollow beads 200 to 500 nm in diameter with a great deal of nanosize α-SiAlON particles around 10 to 30 nm in diameter was observed from the resultant Ca α-SiAlON powders, which has not been reported for SiAlON ceramics before.     

Highly Transparent Lu-α-SiAlON

Novel Lu-α-SiAlON ceramics were produced by hot pressing mixtures of Si₃N₄, Lu₂O₃, AlN, and Al₂O₃ at 1950°C for 2 h in a nitrogen atmosphere. The resultant SiAlON was fully dense and possessed a uniform, equiaxed microstructure with a grain size of ∼1 μm, which resulted in a high hardness of >19 GPa. In addition to high hardness, the sample showed very high optical transparency in the visible light region, with >70% transmission at higher wavelengths. This high transparency was attributed to the uniform, dense microstructure and lack of residual grain-boundary phase.     

Fabrication of Elongated α-SiAlON via a Reaction-Bonding Process

A reaction-bonding process, which offers low sintering shrinkage and is a low-cost process, was applied to fabricate Y–α-SiAlON ceramics. The green compacts composed of Si, Y₂O₃, Al₂O₃, and AlN were nitrided and subsequently postsintered. Dense single-phase Y–α-SiAlON with elongated grain morphology could be achieved in the specimen postsintered at 1900°C. The material exhibited high hardness (1850 HV10) and high fracture toughness (5.1 MPa·m^1/2).     

Grain Growth of α-SiAlON in the Calcium-Doped System

Two calcium-doped α-SiAlON compositions (Ca_0.6Si_10.2Al_1.8−O_0.6N_15.4 and Ca_1.8Si_6.6Al_5.4O_1.8N_14.2) were prepared by hot pressing at 1600° and 1500°C, respectively, for complete phase transformation from α-Si₃N₄ to α-SiAlON. Both samples were subsequently fired at different temperatures for different periods of time to study the grain growth of α-SiAlON. Elongated α-SiAlON grains were developed in both samples at high temperatures. The kinetics of grain growth was investigated based on the variations in length and width of the α-SiAlON grains under different sintering conditions. Different growth rates were found between the length and width directions of the α-SiAlON crystals, resulting in anisotropic grain growth in the microstructural development.     

Preparation and Luminescence Spectra of Calcium- and Rare-Earth (R = Eu, Tb, and Pr)-Codoped α-SiAlON Ceramics

Rare-earth-doped oxynitride or nitride compounds have been reported to be luminescent and may then serve as new phosphors with good thermal and chemical stabilities. In this work, we report the photoluminescence (PL) spectra of europium-, terbium-, and praseodymium-doped Ca-α-SiAlON ceramics. The highly dense ceramics were prepared by hot pressing at 1750°C for 1 h under 20 MPa in a nitrogen atmosphere. Europium-doped Ca-α-SiAlON displayed a single broad emission band peaking at λ= 550–590 nm depending on the europium concentration. The emission bands in the spectra of europium-doped Ca-α-SiAlONs were assigned to the allowed transition of Eu²⁺ from the lowest crystal field component of 4 f ⁶5 d to ⁸S_7/2 (4 f ⁷) ground-state level. The emission spectra of terbium- and praseodymium-doped Ca-α-SiAlON ceramics both consisted of several sharp lines, which were attributed to the ⁵D₄→⁷F _j ( j = 3, 4, 5, 6) transitions of Tb³⁺ and ³P₀→³H _j ( j = 3, 4, 5) transitions of Pr³⁺, respectively. In particular, the terbium-doped α-SiAlON ceramics showed a strong green emission among these phosphors.     

α-SiAlON Ceramics Obtained by Slip Casting and Pressureless Sintering

Dense α-SiAlON ceramics were obtained by pressureless sintering of green compacts prepared using slip casting. The rheological properties of the reaction SiAlON suspension were optimized to achieve a high degree of dispersion with a high solids volume fraction, which resulted in homogeneous and relatively dense green bodies with high sintering ability, which could be densified by pressureless sintering at 1750°C for 2 h. The sintered samples revealed a high degree of uniformity and almost fully dense microstructures that consisted of many small, elongated grains homogeneously dispersed in the fracture surfaces, which had properties comparable with those of other SiAlONs obtained using hot pressing.     

Self-Reinforced α-SiAlON Ceramics with Improved Damage Tolerance Developed by a New Processing Strategy

Alpha-SiAlON ceramics with a refined self-reinforced microstructure, i.e., containing acicular grains with dimensions much smaller than those obtained in previous studies, embedded in a matrix consisting of submicrometer-sized isotropic grains, were prepared by applying a rapid one-step sintering procedure. To suppress the overabundant formation of α-SiAlON nuclei, a combination of stabilizing cations, Y + Yb, was used; to encourage formation of acicular α-SiAlON grains, a small amount of an extra liquid (∼3 vol%) was introduced; to avoid abnormal grain coarsening resulting from dynamic ripening, the final sintering temperature was set to just slightly above the minimum temperature threshold for activating grain growth (1700°C). The fully dense compacts obtained exhibited excellent thermal-shock resistance, and hardness and fracture toughness values of 20 GPa and 5.1 MPa·m^1/2, respectively.     

Diffusion Bonding of Silicon Nitride Using a Superplastic β-SiAlON Interlayer

A superplastic β-SiAlON was used as an interlayer to diffusionally bond a hot-pressed silicon nitride to itself. The bonding was conducted in a graphite furnace under a constant uniaxial load of 5 MPa at temperatures varying from 1500° to 1650°C for 2 h, followed by annealing at temperatures in the range of 1600° to 1750^oC for 2 h. The bonds were evaluated using the four-point-bend method at both room temperature and high temperatures. The results indicate that strong, void-free joints can be produced with the superplastic β-SiAlON interlayer, with bond strengths ranging from 438 to 682 MPa, and that the Si₃N₄ joints are heat resistant, being able to retain their strength up to 1000°C (635 MPa), and therefore have potential for high-temperature applications.     

Effect of Seeding on the Microstructure and Mechanical Properties of α-SiAlON: III, Comparison of Modifying Cations

Single-phase in situ toughened SiAlON ceramics containing various modifying cations and single-crystal seeds were studied. The modifying cations include rare-earth cations from the smallest to the largest allowed in the α-SiAlON structure (Yb to Y, to Nd), and from monovalent to trivalent (Li to Ca, to rare earths). At low seeding levels, the aspect ratio of grains increases with the size of modifying cations, giving rise to rather different appearances of the microstructure in different SiAlONs. A one-to-one correspondence between seed crystals and large grains at low seeding levels is also observed. An optimal amount of seeds is required to maximize the fracture toughness, which is controlled by grain pullout with the fracture energy that scales with the fraction of elongated grains, their width, and their aspect ratio. The optimal amount of seeds required to reach maximal toughening increases with the aspect ratio of grains and is the lowest (1%) in Y- and Yb-SiAlONs.     

Optical and Mechanical Properties of α/β Composite Sialons

Two-phase α/β composites have been produced with a combination of high hardness, fracture toughness, and strength. Compared with a single-phase α-sialon, the composite showed around a twofold increase in both fracture toughness and bending strength, with only minimal reduction in hardness. Despite being a two-phase material, the optical properties of the composite were very good, showing transparency in sections of around 0.5 mm thickness. The optical properties were in fact better for the composite than for the single-phase α-sialon. Work to date on transparent sialons has focused on single-phase α-materials, which have inherently low fracture toughness unless elongated microstructures are developed. However, this microstructural development appears to adversely affect optical transparency. In this work it has been shown that good combination of mechanical properties can be achieved while maintaining optical transparency in two-phase composite sialons. The development of such materials should widen their range of application.     

Electrical Properties of Cerium-Doped BaTiO3

The high-temperature equilibrium electrical conductivity of Ce-doped BaTiO₃ was studied in terms of oxygen partial pressure, P (O₂), and composition. In (Ba_1−xCe _x )TiO₃, the conductivity follows the −1/4 power dependence of P (O₂) at high oxygen activities, which supports the view that metal vacancies are created for the compensation of Ce donors, and is nearly independent of P (O₂) where electron compensation prevails at low P (O₂). When Ce is substituted for the normal Ti sites, there is no significant change in conductivity behavior compared with undoped BaTiO₃, indicating the substitution of Ce as Ce⁴⁺ for Ti⁴⁺ in Ba(Ti_1−yCe _y )O₃. The Curie temperature ( T _c) was systematically lowered when Ce³⁺ was incorporated into Ba²⁺ sites, whereas the substitution of Ce⁴⁺ for Ti⁴⁺ sites resulted in no change in this parameter.