High-Temperature Mechanical Properties and Chemical Stability of Ba1+xZr4P6–2xSi2XO24 Low-Thermal-Expansion Ceramics

The NaZr₂P₃O₁₂ (NZP) family of materials is attracting increasing attention due to its low-thermal-expansion behavior. The system Ba_1+xZr₄P_6–2xSi_2xO₂₄ (0 ≤ x ≤ 1), belonging to the NZP family, shows ultralow thermal expansion over a wide temperature range. It also shows anisotropy in its lattice thermal expansion. This causes microcracking as the sintered specimens are cooled, which results in degradation of the mechanical properties. In this work, the chemical stability, strength, and Young's modulus of Ba_1+xZr₄P_6–2xO₂₄ ( X = 0.25 and 0.5) ceramics at high temperatures have been determined. An attempt has been made to correlate the mechanical properties to the thermal expansion anisotropy.     

Structure and Microwave Dielectric Characteristics of Ca1+xNd1−xAl1−xTixO4 Ceramics

CaNdAlO₄ microwave dielectric ceramics were modified by Ca/Ti co-substitution, and their dielectric characteristics were evaluated along with their structure and microstructures. Ca_{1+ x} Nd_{1− x} Al_{1− x} Ti _x O₄ ( x =0, 0.025, 0.05, 0.10, 0.15, 0.20) ceramics with the relative density of over 95% theoretical density were obtained by sintering at 1400°–1450°C in air for 3 h, where the K₂NiF₄-type solid solution single phase was determined from the compositions of x <0.20, while a small amount of CaTiO₃ secondary phase was detected for x =0.20. With Ca/Ti co-substitution in CaNdAlO₄ ceramics, the dielectric constant (ɛ_r) increased with increasing x , and the temperature coefficient of resonant frequency (τ_f) was adjusted from negative to positive, while the Q × f ₀ value increased significantly at first and reached an extreme value at x =0.025 and the maximum at x =0.15. The best combination of microwave dielectric characteristics were achieved at x =0.15 (ɛ_r=19.5, Q × f ₀=93 400 GHz, τ_f=−2 ppm/°C). The improvement of the Q × f ₀ value primarily originated from the reduced interlayer polarization with Ca/Ti co-substitution, while the decreased tolerance factor, the subsequent increased interlayer stress, and the appearance of CaTiO₃ secondary phase brought negative effects upon the Q × f ₀ value.     

Synthesis and Thermal Expansion of MZr4P6O24 (M=Mg, Ca, Sr, Ba)

MZr₄P₆O₂₄ (M=Mg, Ca, Sr, Ba), which belongs to a new, low-thermal-expansion family of materials known as [NZP] or [CTP], were synthesized by solid-state reaction (oxide mixing) and sol-gel methods, and their sinterability in two cases was investigated and compared. Thermal-expansion measurements were made on sintered samples by dilatometry, high-temperature X-ray diffractometry, and the laser speckle technique. An anisotropy in axial thermal-expansion coefficients was observed in these materials. CaZr₄P₆O₂₄ and SrZ₄P₆O₂₄ showed reverse anisotropy as well as opposite bulk thermal expansion; i.e., CaZr₄P₆O₂₄ had negative bulk thermal expansion and SrZr₄P₆O₂₄ positive bulk thermal expansion in the temperature range 25° to 500°C. The microstructure of the sintered samples was also examined by scanning electron microscopy.     

Formation Mechanism and Synthesis of Apatite-Type Structure Ba2+xLa8−x(SiO4)6O2−δ

The formation process of Ba₂La₈(SiO₄)₆O₂ was clarified using thermogravimetry–differential thermal analysis (TG-DTA) and a high-temperature powder X-ray diffraction (HT-XRD) method. Phase changes identified from the HT-XRD data surprisingly corresponded to the weight loss and/or endothermic peaks observed in the TG-DTA curves. Raw material with the composition Ba₂La₈(SiO₄)₆O₂ was completely reacted at 1400°C and produced only an apatite-type compound without a secondary phase. Moreover, the synthesis of Ba_{2+ x} La_{8− x} (SiO₄)₆O_2−δ crystals with x = 0–2 was attempted using a solid-state reaction.     

Grain Growth in Ca0.16Zr0.84O1.84

Isothermal grain growth in Ca_0.16Zr_0.84O_1.84, a cubic solid solution of the fluorite type, was studied between 1600° and 2000°C. The grain size increased as the 0.4 power of time. The growth rate was found to be slower than in metals. The activation energy for grain-boundary migration was about 80 kcal per mole. The influence of sintering atmosphere on grain growth is shown.     

Thermal Expansion of SrY2O4

Crystals of SrY₂O₄ (space group Pnam ) were examined by high-temperature powder X-ray diffractometry to determine the changes in unit-cell dimensions with temperature. The individual cell dimensions linearly increased with increasing temperature up to 1473 K. The expansion coefficients (K⁻¹) were 1.263(8) × 10⁻⁵ along the a- axis, 7.46(6) × 10⁻⁶ along the b- axis, and 9.93(10) × 10⁻⁶ along the c- axis. The coefficient of mean linear expansion was 1.001(8) × 10⁻⁵ K⁻¹.     

Electrical Conduction Behavior of La1+xSr1−xGa3O7–δ Melilite-Type Ceramics

Ceramics of the melilite-type compound La_{1+ x} Sr_{1− x} Ga₃O_7−δ were prepared by conventional ceramic processing. Samples prepared represented the entire homogeneity region of the phase (i.e., x =−0.15 to 0.60). Electrochemical characterization under variable temperature and atmospheric conditions in the vicinity of air entailed four-point direct-current conductivity measurements and electromotive force measurements. La_{1+ x} Sr_{1− x} Ga₃O_7−δ samples exhibited a p -type behavior with generally increased conductivity with increased substitution of lanthanum for strontium, which reached a saturation value of ∼10⁻¹ S·cm⁻¹ at 950°C.     

Nonisothermal Reaction Kinetics of SrNb2O6 and BaNb2O6 for the Formation of SrxBa1−xNb2O6

The solid-state reaction of SrNb₂O₆ and BaNb₂O₆ to form Sr _x Ba_{1− x} Nb₂O₆(SBN) at different temperatures and heating rates was investigated. The reaction kinetics were analyzed by X-ray diffractometry for quenched samples, and the internal-standard method was applied to quantify the extent of the reaction. A nonisothermal kinetic empirical model was proposed to evaluate the activation energy and rate constant of SBN with different Sr:Ba ratios. It was found that the kinetic form would change above and below a transition at a reaction fraction of ∼60%, which might be due to the change of the frequency factor. It was also verified that the model that was presented was more favorable to describe the nonisothermal reaction kinetics of SBN.     

Thermal Expansion Anisotropy and Acoustic Emission of NaZr2P3O12 Family Ceramics

Most members of the NaZr₂P₃O₁₂ (NZP) family possess low, near zero, overall thermal expansion coefficients. However, they also exhibit anisotropy of axial thermal expansion. Some compounds have opposite anisotropy; for example, the a parameter of CaZr₄P₆O₂₄ contracts on heating and that of SrZr₄P₆O₂₄ expands, while the c parameter expands for the Ca compound and contracts for the Sr compound. The anisotropy of the axial thermal expansion of these materials is believed to induce microcracking. The acoustic emission method was employed here to detect microcracking in ceramics due to the axial thermal expansion anisotropy. Acoustic signals were observed during cooling of the Ca and Sr compounds from 500°C, and Na and K compounds from 600°C. On the other hand, no acoustic emission signal is detected in Ca_0.5Sr_0.5Zr₄P₆O₂₄ ceramics, in which the lattice parameters a and c remain nearly unchanged in the temperature range of room temperature to 500°C. Thus, a direct correlation between microcracking of ceramics and their anisotropic axial thermal expansion coefficients was established by employing acoustic emission monitoring techniques.     

Effects of Sm3+ Substitution on Dielectric Properties of Ca1−xSm2x/3TiO3 Ceramics at Microwave Frequencies

Microwave dielectric properties of Ca_{1- x} Sm_{2 x /3}TiO₃ ceramics were investigated as a function of the amount of Sm³⁺ substitution (0.0 ≤ x ≤ 0.8). The structure was changed from orthorhombic perovskite at x = 0.0 to tetragonal at x = 0.6. As the calcium vacancy concentration increased with increased Sm³⁺ substitution, the unloaded Q value (similar/congruent 1/tan delta) increased up to the solid-solution limit at x = 0.6 and then decreased because of formation of the secondary phase Sm₂Ti₂O₇. The dielectric constant decreased with increased Sm³⁺ substitution. The effects of Sm³⁺ substitution on dielectric loss and dielectric constant of the specimens were analyzed by the infrared reflectivity spectra in the range 50–4000 cm⁻¹, which were evaluated using the Kramers-Kronig analysis and classical oscillator model. The correlations among dielectric constant, dielectric loss, and dispersion parameters were studied.     

The Binary System Anorthite (CaAl2Si2O8)—Åkermanite (Ca2MgSi2O7)

A study of the equilibrium relations in the system anorthite-åkermanite has been made as a part of an investigation of the ternary system diopside-anorthite-åkermanite. The technique employed was the well-known quenching method. The liquidus relations indicate that anorthite and åkermanite form a simple binary system, with a eutectic located at a composition 46 anorthite, 54 åkermanite (by weight) and at a temperature of 1234°± 2°C. There is strong reason to believe that pure åkermanite, rather than an aluminous melilite, crystallizes with anorthite from intermediate compositions. No evidence to support the alleged decomposition of åkermanite at or below 1325°C. was obtained, since åkermanite gave no indication of instability in the liquidus range of temperatures. The study sheds no light on the relations between anorthite and its hexagonal and orthorhombic polymorphs.     

High-Temperature Electrical Properties of the Bi2.1Sr1.9(Ca1–xYx)Cu2Oy Solid Solution

By a combination of conventional physical property measurements and high-temperature electrical property studies, the solid solution limit, transport parameters, and potential defect regimes of the Bi_2.1Sr_1.9(Ca_{1 - x} Y _x )Cu₂O _y solid solution were established. A continuous solid solution extends to x = 0.7 or 0.8. The electrical properties indicate that the product of the hole density-of-states and mobility for semiconducting compositions is approximately an order of magnitude smaller than for the other p -type superconducting cuprates. A pronounced drop in hole concentration accompanies the tetragonal-to-orthorhombic transition at x = 0.5, whereafter superconductivity disappears. The electrical properties also indicate that a composition x change occurred reversibly below 1100°C.     

Thermal Expansion of Pb3O4

Thermal expansion of Pb₃O₄ was investigated by high-temperature X-ray diffraction. The coefficient in the a ₀ direction is 14.6×10⁻⁶/°C. Expansion in the c₀ direction is 32% greater, with a coefficient of 19.3×10⁻⁶/°C. Coefficients of expansion are linear from 25° to 490°C and are comparable with those of tetragonal and orthorhombic PbO.     

Synthesis of Compositionally Homogeneous Sr(CuxZn1−x)1/2W1/2O3

A complex perovskite of Sr(Cu _x Zn_{1- x} )_1/2 W_1/2O₃ (SCZW) is synthesized by a new combination of wet and dry processess. Mixed oxides containing Cu²⁺ and Zn²⁺ (CZ) are prepared by the wet process (coprecipitate method). SCZW is obtained by the dry process (mixed-oxide method) from a mixture of CZ, SrCO₃, and WO₃. SCZW has practically no compositional, unlike solid solutions prepared by the conventional dry method. The wet–dry process method is useful because the wet process is applied to only B-site cations having the same valence.     

Improved Microwave Dielectric Properties of Ba6Ti1−xSnxNb4O18 Ceramics

Single-phase polycrystalline microwave dielectric ceramics Ba₆Ti_{1− x} Sn _x Nb₄O₁₈, with x changing from 0 to 1, were synthesized by the solid-state reaction method. All the solid solutions fitted well with A₆B₅O₁₈ cation-deficient hexagonal perovskite structure. The substitution of Sn for Ti effectively enhanced the quality factor and controlled τ_f. With increasing Sn content, the dielectric constant decreased from ∼47 to ∼32, and the Q × f value increased significantly from 11 530 to 28 496 GHz, with τ_f varying from 64 to 0 ppm/°C. A zero τ_f was realized when Sn was fully replaced by Ti with the composition Ba₆SnNb₄O₁₈.     

High Q Microwave Dielectric Ceramics in (Ni1−x Znx)Nb2O6 System

(Ni_{1− x} Zn _x )Nb₂O₆, 0≤ x ≤1.0, ceramics with >97% density were prepared by a conventional solid-state reaction, followed by sintering at 1200°–1300°C (depending on the value of x ). The XRD patterns of the sintered samples (0≤ x ≤1.0) revealed single-phase formation with a columbite ( Pbcn ) structure. The unit cell volume slightly increased with increasing Zn content ( x ). All the compositions showed high electrical resistivity (ρ_dc=1.6±0.3 × 10¹¹Ω·cm). The microwave (4–5 GHz) dielectric properties of (Ni_{1− x} Zn _x )Nb₂O₆ ceramics exhibited a significant dependence on the Zn content and to some extent on the morphology of the grains. As x was increased from 0 to 1, the average grain size monotonically increased from 7.6 to 21.2 μm and the microwave dielectric constant (ɛ'_r) increased from 23.6 to 26.1, while the quality factors ( Q _u× f ) increased from 18 900 to 103 730 GHz and the temperature coefficient of resonant frequency (τ_f) increased from −62 to −73 ppm/°C. In the present work, we report the highest observed values of Q _u× f =103 730 GHz, and ɛ'_r=26.1 for the ZnNb₂O₆-sintered ceramics.