Refractory α-SiAlON Containing La2O3

Refractory Y-α-SiAlON with elongated grain morphology was obtained by utilizing La₂O₃ as a densification aid, which resulted in excellent room-temperature and high-temperature strength. Room-temperature strength of 1000 MPa was achieved when La₂O₃ was augmented by adding Y₂O₃ or removing AlN. With only La₂O₃, a temperature-independent strength of 800–950 MPa was maintained up to 1100°C, then gradually decreasing by 25% when reaching 1300°C. The R-curve measurements of fracture toughness showed relatively little dependence on microstructure, consistent with a strong interface that suppresses grain boundary decohesion. Compared with other densification aids such as SiO₂, Al₂O₃, Sc₂O₃, Y₂O₃, and Lu₂O₃, a finer microstructure was obtained by using La₂O₃. High nitrogen content in the residual La–Si–Al–O–N glass in equilibrium with the nitrogen-rich α-SiAlON is suggested to be the cause of these findings.     

Synthesis and Properties of Porous Single-Phase β'-SiAlON Ceramics

Single-phase β'-SiAlON (Si_{6− z} Al _z O _z N_{8− z} , z = 0–4.2) ceramics with porous structure have been prepared by pressureless sintering of powder mixtures of á-Si₃N₄, AlN, and Al₂O₃ of the SiAlON compositions. A solution of AlN and Al₂O₃ into Si₃N₄ resulted in the β'-SiAlON, and full densification was prohibited because no other sintering additives were used. Relative densities ranging from 50%–90% were adjusted with the z -value and sintering temperature. The results of X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses indicated that single-phase β'-SiAlON free from a grain boundary glassy phase could be obtained. Both grain and pore sizes increased with increasing z -value. Low z -value resulted in a relatively high flexural strength.     

Effect of Liquid Phase Sintering on Microstructure and Mechanical Properties of Yb2O3-AlN Containing SiC-Based Ceramics

A series of silicon carbide-based ceramics with different sintering additives were liquid-phase sintered to high densities. Yb₂O₃ in combination with AlN was used as the additive, instead of the commonly used Y₂O₃–AlN, to improve the refractoriness of the secondary phase. Thermo-chemical decomposition of AlN was sufficiently suppressed with the use of nitrogen overpressure and reasonable weight loss was achieved in the different additive containing SiC ceramics without a reactive powder bed. Use of the heavier rare-earth element modified the liquid phase formed during sintering and reduced the phase transformation controlled grain growth rate, compared with Y₂O₃ doped materials. It also permitted microstructure tailoring through post-sintering heat treatments in nitrogen. Materials with self-reinforced microstructures, formed as a result of anisotropic grain growth, were obtained. Improved fracture toughness (4.5–5 MPa/m^1/2) and good flexural strength retention up to 1400°C were also observed.     

Sintering of Si3N4 with the Addition of Rare-Earth Oxides

The effect of rare-earth oxide additives on the densification of silicon nitride by pressureless sintering at 1600° to 1700°C and by gas pressure sintering under 10 MPa of N₂ at 1800° to 2000°C was studied. When a single-component oxide, such as CeO₂, Nd₂O₃, La₂O₃, Sm₂O₃, or Y₂O₃, was used as an additive, the sintering temperature required to reach approximate theoretical density became higher as the melting temperature of the oxide increased. When a mixed oxide additive, such as Y₂O₃–Ln₂O₃ (Ln=Ce, Nd, La, Sm), was used, higher densification was achieved below 2000°C because of a lower liquid formation temperature. The sinterability of silicon nitride ceramics with the addition of rare-earth oxides is discussed in relation to the additive compositions.     

Low Temperature Sintering of Zn3Nb2O8 Ceramics from Fine Powders

A possibility to produce microwave (MW) dielectric materials by liquid-phase sintering of fine particles was investigated. Zn₃Nb₂O₈ powders with a grain size 50–300 nm were obtained by the thermal decomposition of freeze-dried Zn–Nb hydroxides or frozen oxalate solutions. The crystallization of Zn₃Nb₂O₈ from amorphous decomposition products was often accompanied by the simultaneous formation of ZnNb₂O₆. Maximum sintering activity was observed for single-phase crystalline Zn₃Nb₂O₈ powders obtained at the lowest temperature. The sintering of as-obtained powders with CuO–V₂O₅ sintering aids results in producing MW dielectric ceramics with a density 93%–97% of the theoretical, and a Q × f product up to 36 000 GHz at sintering temperature ( T _s)≥680°C. The high level of MW dielectric properties of ceramics was ensured by intensive grain growth during the densification and the thermal processing of ceramics.     

Effect of Europium Concentration on Densification of Transparent Eu:Y2O3 Scintillator Ceramics Using Hot Pressing

Europium (Eu) was found to act as a solid-state sintering aid in Y₂O₃ optical ceramics by controlling ionic diffusivity, which in turn leads to enhanced optical transparency. Transparent ceramic samples of Eu-doped Y₂O₃, with no additional additives, were sintered by uniaxial vacuum hot pressing under 40 MPa and maximum temperature of 1580°C. Optical attenuation was found to decrease with increasing Eu concentrations between 0 and 5 at% for ceramics processed under the same sintering conditions. In order to study the effect of Eu concentration on ceramic densification, the strain rate and grain size during sintering at constant temperature and varied pressure were measured. A diffusional flow densification model was used to derive instantaneous effective diffusion constants for the densification process. Diffusion constants were found to increase with increasing Eu concentration according to a log–linear relationship. Eu²⁺ was detected in samples after hot pressing through fluorescence spectroscopy, and the extrinsic defect chemistry was found to be dominated by the reduced Eu in solid solution with Y₂O₃. A sintering model with diffusion rate limited by yttrium interstitial transport and controlled by the incorporation of Eu²⁺ onto the cation sublattice was found to be in good agreement with experimental diffusivity data.     

Effect of Bi2O3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Zn2SiO4 Ceramics

Bi₂O₃ was added to a nominal composition of Zn_1.8SiO_3.8 (ZS) ceramics to decrease their sintering temperature. When the Bi₂O₃ content was <8.0 mol%, a porous microstructure with Bi₄(SiO₄)₃ and SiO₂ second phases was developed in the specimen sintered at 885°C. However, when the Bi₂O₃ content exceeded 8.0 mol%, a liquid phase, which formed during sintering at temperatures below 900°C, assisted the densification of the ZS ceramics. Good microwave dielectric properties of Q × f =12,600 GHz, ɛ_r=7.6, and τ_f=−22 ppm/°C were obtained from the specimen with 8.0 mol% Bi₂O₃ sintered at 885°C for 2 h.     

Rapid Rate Sintering of Nanocrystalline ZrO2−3 mol% Y2O3

Conventional ramp-and-hold sintering with a wide range of heating rates was conducted on submicrometer and nanocrystalline ZrO₂–3 mol% Y₂O₃ powder compacts. Although rapid heating rates have been reported to produce high density/fine grain size products for many submicrometer and smaller starting powders, the application of this technique to ZrO₂–3 mol% Y₂O₃ produced mixed results. In the case of submicrometer ZrO₂–3 mol% Y₂O₃, neither densification nor grain growth was affected by the heating rate used. In the case of nanocrystalline ZrO₂–3 mol% Y₂O₃, fast heating rates severely retarded densiflcation and had a minimal effect on grain growth. The large adverse effect of fast heating rates on the densification of the nanocrystalline powder was traced to a thermal gradient/differential densification effect. Microstructural evidence suggests that the rate of densification greatly exceeded the rate of heat transfer in this material; consequently, the sample interior was not able to densify before being geometrically constrained by a fully dense shell which formed at the sample exterior. This finding implies that rapid rate sintering will meet severe practical constraints in the manufacture of bulk nanocrystalline ZrO₂–3 mol% Y₂O₃ specimens.     

Modification of MgAl2O4 Microwave Dielectric Ceramics by Zn Substitution

MgAl₂O₄ microwave dielectric ceramics were modified by Zn substitution for Mg, and their dielectric characteristics were evaluated, along with their structures. Dense (Mg_{1− x} Zn _x )Al₂O₄ ceramics were obtained by sintering at 1550°–1650°C in air for 3 h, and the (Mg_{1− x} Zn _x )Al₂O₄ solid solution was determined in the entire composition range. With Zn substitution for Mg, the dielectric constant ɛ of MgAl₂O₄ just varied from 7.90 to 8.56, while the Q × f value had significantly improved up to a maximal value of 106 000 GHz at x =1.0. Moreover, the τ_f of MgAl₂O₄ ceramics had declined from −73 to −63 ppm/°C.     

Formation of Pores and Y2BaCuO5-Free Regions during Melt Processing of Y1.6 Ba2.3Cu3.3Ox

The formation of spherical pores and regions free of Y₂BaCuO₅ (2-1-1) has been studied by melt processing Y_1.6Ba_2.3Cu_3.3O _x: in two different atmospheres (air and oxygen). When the sintered Y_1.6Ba_2.3Cu_3.3O _x specimens are melted at 1050°C, many spherical pores form in the melted specimens. During the subsequent cooling, the pores are filled by liquid flow and finally solidified to Y₂BaCuO₅-free regions. Melt processing in an oxygen atmosphere produces more pores and regions free of 2-1-1 than in air. Because peritectic melting of YBa₂Cu₃O_7-y in an oxygen atmosphere produces more oxygen gas than that in air, the formation of the pores and Y₂BaCuO₅-free regions is suggested to be attributed to the oxygen evolution during the peritectic melting of YBa₂Cu₃O_7−y     

Influence of BaCuO2 on the Sintering and the Properties of YBa2Cu3O7−δ-Based Ceramics

The preparation of YBa₂Cu₃O_{7 - δ}-based ceramics was made from a mixture of oxides taken in the molar proportions α:1:2 BaCuO₂:Y₂BaCuO₅:CuO(0.95 α 3). The densification of the ceramics is strongly dependent on the initial amount of BaCuO₂. The highest density is obtained when α= 1. All the ceramics present a superconducting transition. A sintering mechanism is proposed in which the densification is mainly governed by the appearance of a metastable BaCuO₂-based liquid at around 900°C.     

Effect of Li2CO3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Mg2V2O7 Ceramics

Li₂CO₃ was added to Mg₂V₂O₇ ceramics in order to reduce the sintering temperature to below 900°C. At temperatures below 900°C, a liquid phase was formed during sintering, which assisted the densification of the specimens. The addition of Li₂CO₃ changed the crystal structure of Mg₂V₂O₇ ceramics from triclinic to monoclinic. The 6.0 mol% Li₂CO₃-added Mg₂V₂O₇ ceramic was well sintered at 800°C with a high density and good microwave dielectric properties of ɛ _r=8.2, Q × f =70 621 GHz, and τ_f=−35.2 ppm/°C. Silver did not react with the 6.0 mol% Li₂CO₃-added Mg₂V₂O₇ ceramic at 800°C. Therefore, this ceramic is a good candidate material in low-temperature co-fired ceramic multilayer devices.     

Processing and Properties of in Situ-Reinforced α-SiAlONs Stabilized with Y2O3 and Lu2O3

α-SiAlONs with equiaxed and elongated microstructures stabilized with Y₂O₃ and Lu₂O₃ were produced by hot pressing, and the phase structure and room- and high-temperature mechanical properties were assessed. Additional liquid added to the starting composition in the form of 5 wt% rare-earth monosilicate resulted in the formation of elongated microstructures and improvements in room-temperature strength and fracture toughness. The elongated grain growth was promoted by the additional liquid phase, which crystallized to form a secondary grain-boundary phase thought to be J ' (Re₄Si_{2– x} Al _x O_{7+ x} N_{2– x} ). For the equiaxed and the elongated samples, those sintered with Lu₂O₃ showed higher hardness than the comparable Y₂O₃-sintered materials, and, at elevated temperature, the strength retention of the elongated Lu₂O₃ SiAlON was much higher than that of the Y₂O₃ sample, which was attributed to properties of the residual grain-boundary phase associated with the difference in the cationic radius of the stabilizing cation.     

Sintering and Microwave Dielectric Properties of the LiNb0.63Ti0.4625O3 Ceramics with the B2O3–SiO2 Liquid-Phase Additives

The effect of B₂O₃–SiO₂ liquid-phase additives on the sintering, microstructure, and microwave dielectric properties of LiNb_0.63Ti_0.4625O₃ ceramics was investigated. It was found that the sintering temperature could be lowered easily, and the densification and dielectric properties of LiNb_0.63Ti_0.4625O₃ ceramics could be greatly improved by adding a small amount of B₂O₃–SiO₂ solution additives. No secondary phase was observed for the ceramics with B₂O₃–SiO₂ additives. With the addition of 0.10 wt% B₂O₃–SiO₂, the ceramics sintered at 900°C showed favorable microwave dielectric properties with ɛ_r=71.7, Q × f =4950 GHz, and τ_f=−2.1 ppm/°C. The energy dispersive spectra analysis showed an excellent co-firing interfacial behavior between the LiNb_0.63Ti_0.4625O₃ ceramic and the Ag electrode. It indicated that LiNb_0.63Ti_0.4625O₃ ceramics with B₂O₃–SiO₂ solution additives have a number of potential applications on passive integrated devices based on the low-temperature co-fired ceramics technology.     

Influence of Yttria–Alumina Content on Sintering Behavior and Microstructure of Silicon Nitride Ceramics

The present study investigates the influence of the content of Y₂O₃–Al₂O₃ sintering additive on the sintering behavior and microstructure of Si₃N₄ ceramics. The Y₂O₃:Al₂O₃ ratio was fixed at 5:2, and sintering was conducted at temperatures of 1300°–1900°C. Increased sintering-additive content enhanced densification via particle rearrangement; however, phase transformation and grain growth were unaffected by additive content. After phase transformation was almost complete, a substantial decrease in density was identified, which resulted from the impingement of rodlike β-Si₃N₄ grain growth. Phase transformation and grain growth were concluded to occur through a solution–reprecipitation mechanism that was controlled by the interfacial reaction.     

Influence of the Y2O3 Content and Temperature on the Mechanical Properties of Melt-Grown Al2O3–ZrO2 Eutectics

The effect of Y₂O₃ content on the flexure strength of melt-grown Al₂O₃–ZrO₂ eutectics was studied in a temperature range of 25°–1427°C. The processing conditions were carefully controlled to obtain a constant microstructure independent of Y₂O₃ content. The rod microstructure was made up of alternating bands of fine and coarse dispersions of irregular ZrO₂ platelets oriented along the growth axis and embedded in the continuous Al₂O₃ matrix. The highest flexure strength at ambient temperature was found in the material with 3 mol% Y₂O₃ in relation to ZrO₂(Y₂O₃). Higher Y₂O₃ content did not substantially modify the mechanical response; however, materials with 0.5 mol% presented a significant degradation in the flexure strength because of the presence of large defects. They were nucleated at the Al₂O₃–ZrO₂ interface during the martensitic transformation of ZrO₂ on cooling and propagated into the Al₂O₃ matrix driven by the tensile residual stresses generated by the transformation. The material with 3 mol% Y₂O₃ retained 80% of the flexure strength at 1427°C, whereas the mechanical properties of the eutectic with 0.5 mol% Y₂O₃ dropped rapidly with temperature as a result of extensive microcracking.     

Effects of La2O3/ZnO Additives on Microstructure And Microwave Dielectric Properties of Zr0.8Sn0.2TiO4 Ceramics

Dielectric ceramics of Zr_0.8Sn_0.2TiO₄ containing La₂O₃ and ZnO as sintering aids were prepared and investigated for microstructure and microwave dielectric properties. Low-level doping with La₂O₃ and ZnO (up to 0.30 wt%) is good for densification and dielectric properties. These additives do not affect the dielectric constant and the temperature coefficient. Dielectric losses increase significantly at additive levels higher than 0.15 wt%. The combined additives La₂O₃ and ZnO act as grain growth enhancers. With 0.15 wt% additives, a ceramic having a dielectric constant, a quality factor, and a temperature coefficient of frequency at 4.2 GHz of 37.6, 12 800, and –2.9 ppm/°C, respectively, was obtained. The quality factor was considerably improved by prolonged sintering.     

Influence of Processing Conditions on the Electrical Properties of CaCu3Ti4O12 Ceramics

The electrical properties of a series of CaCu₃Ti₄O₁₂ ceramics prepared by the mixed oxide route and sintered at 1115°C in air for 1–24 h to produce different ceramic microstructures have been studied by Impedance Spectroscopy. As-fired ceramics are electrically heterogeneous, consisting of semiconducting grains and insulating grain boundaries, and can be modelled to a first approximation on an equivalent circuit based on two parallel RC elements connected in series. The grain boundary resistance and capacitance values vary as a function of sintering time and correlate with the ceramic microstructure based on the brickwork layer model for electroceramics. The large range of apparent high permittivity values for CaCu₃Ti₄O₁₂ ceramics is therefore attributed to variations in ceramic microstructure. The grain-boundary resistance decreases by three to four orders of magnitude after heat treatment in N₂ at 800°–1000°C but can be recovered to the original value by heat treatment in O₂ at 1000°C. The bulk resistivity decreases from ∼80 to 30 Ω·cm with increasing sintering time but is independent of heat treatment in N₂ or O₂ at 800°–1000°C. The origin of the bulk semiconductivity is discussed and appears to be related to partial decomposition of CaCu₃Ti₄O₁₂ at the high sintering temperatures required to form dense ceramics, and not to oxygen loss.     

Microstructure and Mechanical Properties of the in situβ-Si3N4/α'-SiAlON Composite

The in situ β-Si₃N₄/α'-SiAlON composite was studied along the Si₃N₄–Y₂O₃: 9 AlN composition line. This two phase composite was fully densified at 1780°C by hot pressing Densification curves and phase developments of the β-Si₃N₄/α'-SiAlON composite were found to vary with composition. Because of the cooperative formation of α'-Si AlON and β-Si₃N₄ during its phase development, this composite had equiaxed α'-SiAlON (∼0.2 μm) and elongated β-Si₃N₄ fine grains. The optimum mechanical properties of this two-phase composite were in the sample with 30–40%α', which had a flexural strength of 1100 MPa at 25°C 800 MPa at 1400°C in air, and a fracture toughness 6 Mpa·m^1/2. α'-SiAlON grains were equiaxed under a sintering condition at 1780°C or lower temperatures. Morphologies of the α°-SiAlON grains were affected by the sintering conditions.     

Reactive Hot-Pressed Alumina–Boron Nitride Composites with Y2O3 Sintering Additive

The effect of Y₂O₃ addition (0–5 wt%) on the densification and properties of reactive hot-pressed alumina (Al₂O₃)–boron nitride composites based on the reaction between aluminum borate (2Al₂O₃·B₂O₃) and aluminum nitride (AlN) was investigated. The densification process was very sensitive to the amount of Y₂O₃. Compared with a low relative density of 79.3 theoretical density (TD)% for material with no Y₂O₃ addition, the material density reached 98.6 TD% with 0.25% Y₂O₃ addition. High Y₂O₃ additions resulted in the formation of a new phase Al₅Y₃O₁₂. The grain growth of the Al₂O₃ matrix was promoted by the Y₂O₃ addition. Owing to the high density and the small Al₂O₃ particle size the sample with 0.25% Y₂O₃ addition demonstrated the highest bending strength of 540 MPa.