A new phase diagram for the CaOAl2O3SiO2H2O hydroceramic system at 200 °C

A new phase diagram is reported for the CaOAl₂O₃SiO₂H₂O (CASH) system at 200 °C. This system is rare in nature but has applications in cementing geothermal and deep oil wells. The phase diagram was constructed by synthesising a range of hydroceramics with CASH assemblages from oilwell cement, silica flour (quartz) and alumina (corundum). A hydroceramic is defined as any ceramic material incorporating water as H₂O or OH. At 200 °C, gyrolite, hillebrandite, jaffeite, portlandite, quartz, 11 Å tobermorite, xonotlite, hibschite and katoite were observed as product phases. The mineral assemblages produced the following three-phase triangles in the CaOAl₂O₃SiO₂ diagram: Gyr + Qtz + Xon; Crn + Tob + Xon; Crn + Hib + Xon; Crn + Hib + Jaf; Crn + Jaf + Kat; Hib + Jaf + Por; Hib + Jaf + Xon; and two reactions are found to be in progress at 200 °C. When alumina is present in the reaction mixture, the thermal stability of tobermorite is extended to higher temperature, and the crystallinity of tobermorite and xonotlite enhanced.     

Synthesis of nanocrystalline Mn3O4 at 100 °C

A simple gel to crystal conversion route has been followed for the preparation of nanocrystalline tetragonal Mn₃O₄ powders at 80-100 °C under refluxing conditions. Freshly prepared manganese hydroxide gel is allowed to crystallize under refluxing and stirring conditions for 4-6 h. Formation of nano crystallites of Mn₃O₄ is confirmed by X-ray diffraction (XRD) study. Transmission electron microscope (TEM) investigations revealed that the average particle size is 50 nm for these powders.     

CO2 absorption and desorption of Bi2O3-La2O3 powders prepared by mechanical synthesis

In order to obtain CO₂-absorbents to eliminate CO₂ concentration locally, Bi₂O₃-La₂O₃ mixed powders were prepared by mechanical alloying (MA) method using a planetary ball-milling machine. CO₂-absorption and desorption properties were checked by TG-DTA for the obtained powder samples. As a result, the sample shown by (Bi₂O₃)_1−x(La₂O₃)_x [x≤0.50] was found to form α-Bi₂O₃-solid solution with repeated CO₂-adsorption and desorption around 400- 500 °C. Absorbed and desorbed CO₂ contents varied with MA time: the 72 h MA’ed sample had a larger CO₂ content than the 24 h MA’ed sample. The performance depended on the sample composition, and (Bi₂O₃)_0.70(La₂O₃)_0.30 was found to have the highest performance in the present system.     

Itinerant ferromagnetism to insulating spin glass in SrRu1−xCuxO3 (0 ≤ x ≤ 0.3)

The ferromagnetic metallic oxide, SrRuO₃ (T_C ∼ 165 K) undergoes structural, magnetic and metal-insulator transitions upon substitution of Cu at the Ru-site. For x = 0.2 in SrRu_1−xCu_xO₃, the structure becomes a tetragonal with the space group I4/mcm and there is a signature of both ferromagnetic (T_C = 65 K) and antiferromagnetic (T_N = 32 K) ordering due to possible magnetic phase separation. The antiferromagnetism arises due to short range ordering of Cu- and Ru-moments. Jahn-Teller distortion of (Ru,Cu)-O₆ octahedra indicates that the copper ions are in 2+ oxidation state with ⁶t2g³eg electronic configuration. For x ≥ 0.1, narrowing of Ru-4d bandwidth by the substitution of Cu ions results in semiconducting behavior. For x = 0.3, the ac and dc susceptibility measurements indicate a spin glass behavior. The origin of spin glass behavior has been attributed to competing ferromagnetic and antiferromagnetic interactions.     

Subsolidus phase equilibria in the Al2O3-CeO2-PbO and Al2O3-CeO2-RuO2 systems

The subsolidus phase equilibria in air for the Al₂O₃-CeO₂-PbO and Al₂O₃-CeO₂-RuO₂ systems were studied with the aim of obtaining information on possible interactions between a CeO₂-based solid electrolyte in solid-oxide fuel cells (SOFCs) and other oxides. No ternary compound was found in either of the systems. The tie line in the Al₂O₃-PbO-CeO₂ system is between Al₂Pb₂O₅ and the CeO₂.     

Subsolidus phase equilibria in the RuO2-Bi2O3-ZrO2 system

Subsolidus equilibria in air in the RuO₂-Bi₂O₃-ZrO₂ system were studied with the aim of obtaining information on possible interactions between a Bi₂Ru₂O₇-based cathode and a ZrO₂-based solid electrolyte in solid-oxide fuel cells (SOFCs). No ternary compound was found in the system. The tie lines are between Bi₂Ru₂O₇ and ZrO₂, and between Bi₂Ru₂O₇ and gamma-Bi₂O₃—the ZrO₂ stabilised Bi₂O₃ phase, stable at temperatures over 710 °C.     

Influence of grain size on the phase transition β2 → ? in Bi4La2O9 material

This paper deals on a study realized in order to elaborate dense ceramic of Bi₄La₂O₉ oxide conductor. A wet method in nitric media, usually favorable to obtain low grain size, did not allow to isolate the stable phases. Material with particle low size has been obtained by attrition treatment after conventional solid state powder synthesis. The decrease of particle size (≅4 times), evidenced by X-ray diffraction and SEM, influences the reversibility of transitions between monoclinic ? and rhombohedral β₂ varieties on powder, as well as ceramics, leading to an improvement of the conductivity level of these ones after a thermal cycle.     

Study on properties of CaO-SiO2-B2O3 system glass-ceramic

Low temperature co-fired ceramic (LTCC) is prepared by sintering a glass selected from CaO-SiO₂-B₂O₃ system, and its sintered bodies are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). It is found that the optimal sintering temperature for this glass-ceramic is 820 °C for 15 min, and the major phases of this material are CaSiO₃, CaB₂O₄ and SiO₂. The glass-ceramic possesses excellent dielectric properties: ?_r = 6.5, tan δ < 2 × 10⁻³ at 10 MHz, temperature coefficient of dielectric constant about −51 × 10⁻⁶ °C⁻¹ and coefficient of thermal expansion about 8 × 10⁻⁶ °C⁻¹ at 20-400 °C. Thus, this material is supposed to be suitable for the tape casting process and be compatible with Ag electrode, which could be used as the LTCC materials for the application in wireless communications.     

Microstructure and microwave dielectric characteristics of (1 − x)Ba(Zn1/3Ta2/3)O3-xBaTi4O9 ceramics

(1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ (0.1 ≤ x ≤ 0.85) composites are prepared by mixing 1150 °C-calcined BaTi₄O₉ with 1150 °C-calcined Ba(Zn_1/3Ta_2/3)O₃ powders. The crystal structure, microwave dielectric properties and sinterabilites of the (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramics have been investigated. X-ray diffraction patterns reveal that BaTi₄O₉, ordered and disordered Ba(Zn_1/3Ta_2/3)O₃ phases exist independently over the whole compositional range. The sintering temperatures of (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramics are about 1240 - 1320 °C and obviously lower than those of Ba(Zn_1/3Ta_2/3)O₃ ceramics. The dielectric constants (?_r) and the temperature coefficient of resonant frequency (τ_f) of (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramics increase with the increase of BaTi₄O₉ content. Nevertheless, the bulk densities and the quality values (Q × f) of (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramics increase with the increase of Ba(Zn_1/3Ta_2/3)O₃ content. The results are attributed to the higher density and quality value of Ba(Zn_1/3Ta_2/3)O₃ ceramics, the better grain growth, and the densification of sintered specimens added a small BaTi₄O₉ content. The (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramic with x = 0.1 sintered at 1320 °C exhibits a ?_r value of 31.5, a maximum Q × f value of 68500 GHz and a minimum τ_f value of 4.1 ppm/°C.     

Dielectric properties of B2O3-doped (1 − x)LaAlO3-xSrTiO3 ceramic system at microwave frequency

The effects of B₂O₃ addition on the microwave dielectric properties and the microstructures of (1−x)LaAlO₃-xSrTiO₃ ceramics prepared by conventional solid-state routes have been investigated. Doping with 0.25 wt.% B₂O₃ can effectively promote the densification and the microwave dielectric properties of (1−x)LaAlO₃-xSrTiO₃ ceramics. It is found that LaAlO₃-SrTiO₃ ceramics can be sintered at 1400°C due to the liquid phase effect of a B₂O₃ addition observed by scanning electronic microscopy (SEM). The dielectric constant as well as the Q×f value decreases with increasing B₂O₃ content. At 1460°C, 0.46LaAlO₃-0.54SrTiO₃ ceramics with 0.25 wt.% B₂O₃ addition possesses a dielectric constant (ε_r) of 35, a Q×f value of 38,000 (at 7 GHz) and a temperature coefficients of resonant frequency (τ_f) of −1 ppm/°C.     

Structural properties of Al2O3-La2O3 binary oxides prepared by sol-gel

The structural properties of La₂O₃ and Al₂O₃-La₂O₃ binary oxides prepared by sol-gel were studied by XRD, HRTEM and UV-vis. The binary oxides with high lanthana contents show an amorphous structure after calcination at 650 °C. At calcination temperatures higher than 1000 °C there is a phase transformation from the amorphous state to the crystalline LaAlO₃ with a perovskite structure. The structure of La₂O₃ is consistent with the hexagonal system; however, some crystalline microdomains with a monoclinic structure were detected by HRTEM. Islands of La₂O₃ and LaAl₁₁O₁₈ phases were detected at high lanthana concentration in the binary oxide. The modification in the coordination shell of the Al³⁺ cations due to the interaction with La³⁺ cations confirms the formation of phases with a perovskite structure and the presence of islands of the LaAl₁₁O₁₈ phase.     

Experimental study and simulation of a vertical section mullite-ternary eutectic (985 °C) in the SiO2-Al2O3-K2O system

The global thermal behavior of some common ceramics is represented in the ternary diagram SiO₂-Al₂O₃-K₂O, in a zone where no experimental data are available. In this study, we experimented the thermal transformations of compounds belonging to two vertical sections between mullite and the eutectic point at 985 °C or the peritectic at 1140 °C. In both sections, results indicate the particular shape of liquidus curves, which show accentuated slopes at the vicinity of eutectic and peritectic points. Data from liquidus curves were used for the purpose of simulation, using a thermodynamic approach involving a subregular model for the excess Gibbs energy of mixing. The particular sigmoid shape of the liquidus curve and the concave downward shapes of Gibbs energy of mixing with two minimums, strongly suggest the existence of a large subliquidus immiscibility zone in the mullite-rich region. Experiments validated the existence of two horizontal lines at 985 and 1140 °C, below which mullite, orthoclase, and silica crystallize.     

Novel composition above the limit of Bi:Zr solid solution; synthesis and physical properties of Bi1.33Zr0.67O3+δ

This paper presents an increase to x = 0.67 of the zirconium content in the conductive Bi_2−xZr_xO_3+δ solid solution. Complete incorporation of Zr in the β_III-Bi₂O₃ structure, confirmed by X-ray powder diffraction, has produced a phase with a lower volume and superior conductivity than those predicted by an earlier study. The observed β_III-δ Bi_2−xZr_xO_3+δ phase transition around 730 °C has been characterised for the first time and shows a segregation of a mixture of predominantly γ-Bi₂O₃ and approximately 30% of the ZrO₂, before total reincorporation of the Zr in the high temperature δ-phase.     

(5 − x)BaO-xMgO-2Nb2O5 ceramics prepared using a reaction-sintering process

(5 − x)BaO-xMgO-2Nb₂O₅ (x = 0.5 and 1; 5MBN and 10MBN) microwave ceramics prepared using a reaction-sintering process were investigated. Without any calcinations involved, the mixture of BaCO₃, MgO, and Nb₂O₅ was pressed and sintered directly. MBN ceramics were produced after 2-6 h of sintering at 1350-1500 °C. The formation of (BaMg)₅Nb₄O₁₅ was a major phase in producing 5MBN ceramics, and the formation of Ba(Mg_1/3Nb_2/3)O₃ was a major phase in producing 10MBN ceramics. As CuO (1 wt%) was added, the sintering temperature dropped by more than 150 °C. We produced 5MBN ceramics with these dielectric properties: ?_r = 36.69, Qf = 20,097 GHz, and τ_f = 61.1 ppm/°C, and 10MBN ceramics with these dielectric properties: ?_r = 39.2, Qf = 43,878 GHz, and τ_f = 37.6 ppm/°C. The reaction-sintering process is a simple and effective method for producing (5 − x)BaO-xMgO-2Nb₂O₅ ceramics for applications in microwave dielectric resonators.     

Structure and electrical properties of (1 − x)Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3 ceramics near morphotropic phase boundary

The binary lead-free piezoelectric ceramics with the composition of (1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ were synthesized by conventional mixed-oxide method. The phase structure transformed from rhombohedral to tetragonal phase in the range of 0.16 ≤ x ≤ 0.20. The grain sizes varied with increasing the Bi_0.5K_0.5TiO₃ content. Electrical properties of ceramics are significantly influenced by the Bi_0.5K_0.5TiO₃ content. Two phase transitions at T_t (the temperature at which the phase transition from rhombohedral to tetragonal occurs) and T_c (the Curie temperature) were observed in all the ceramics. Adding Bi_0.5K_0.5TiO₃ content caused the variations of T_t and T_c. A diffuse character was proved by the linear fitting of the modified Curie-Weiss law. Besides, the ceramics with homogeneous microstructure and excellent electrical properties were obtained at x = 0.18 and sintered at 1170 °C. The piezoelectric constant d₃₃, the electromechanical coupling factor K_p and the dielectric constant ?_r reached 144 pC/N, 0.29 and 893, respectively. The dissipation factor tan δ was 0.037.     

Structural characterization of 0.5PbMg1/3Nb2/3O3-0.5BaxPb(1−x)TiO3 powders

The present work reports the effects caused by barium on phase formation, morphology and sintering of lead magnesium niobate-lead titanate (PMN-50PT). Ab initio study of 0.5Pb(Mg_1/3Nb_2/3)O₃-0.5(Ba_xPb_(1−x)TiO₃) ceramic powders, with x = 0, 0.20, and 0.40 was proposed, considering that the partial substitution of lead by barium can reestablish the equilibrium of monoclinic-tetragonal phases in the system. It was verified that even for 40 mol% of barium, it was possible to obtain pyrochlore-free PMN-PT powders. The increase of the lattice parameters of PMN-PT doped-powders confirmed dopant incorporation into the perovskite phase. The presence of barium improved the reactivity of the powders, with an average particle size of 120 nm for 40 mol% of barium against 167 nm for the pure sample. Although high barium content (40 mol%) was deleterious for a dense ceramic, contents up to 20 mol% allowed 95% density when sintered at 1100 °C for 4 h.     

Bi4LnNb3O15 (Ln = La, Pr, Nd) and Bi4LaTa3O15: New intergrowth Aurivillius related phases

We describe the synthesis and characterization of new intergrowth Aurivillius related phases, Bi₄LnNb₃O₁₅ (Ln = La, Pr, Nd) and Bi₄LaTa₃O₁₅. Both powder X-ray diffraction and electron microscopy investigations show that the compounds adopt orthorhombic structures with the cell parameters a ∼ 5.5 Å, b ∼ 5.5 Å and c ∼ 20.9 Å, suggesting an ordered intergrowth structure that consists of n = 1 [Bi₂NbO₆]⁻ and n = 2 [Bi₂LnNb₂O₉]⁺ Aurivillius fragments which are stacked alternately along the c-axis. The oxides do not show a second harmonic generation (SHG) response toward 1064 nm laser radiation; they do not show a ferroelectric-paraelectric transition either between 30 and 900 °C in dielectric measurements, indicating a centrosymmetric structure. Optical absorption studies show that the intergrowth phases possess considerably smaller band gaps than the parent Nb₂O₅ and Ta₂O₅.     

Synthesis and properties of solid solutions of hexagonal YCu0.5Ti0.5O3 with YMO3 (M = Mn, Cr, Fe, Al, Ga, and In)

Solid solutions of the type Y(Cu_0.5Ti_0.5)_1−xM_xO₃ with a hexagonal structure were prepared for M = Mn, Fe, Cr, Al, Ga, and In. A complete solid solution could be obtained only in the case of M = Mn. The green color of YCu_0.5Ti_0.5O₃ was found to be enhanced by small substitutions of Al, Ga, and In. All compositions containing Mn were black in color. Suppression of magnetic transitions is observed upon co-doping of Cu/Ti into YMnO₃. Measurements of dielectric constant suggest some magneto-electric coupling may be present in the Y(Cu_0.5Ti_0.5)_1−xMn_xO₃ solid solution.     

Dielectric properties of a new ceramic system (1 − x)Mg4Nb2O9-xCaTiO3 at microwave frequency

The microstructures and the microwave dielectric properties of the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system were investigated. In order to achieve a temperature-stable material, CaTiO₃ (τ_f ∼ 800 ppm/°C) was chosen as a τ_f compensator and added to Mg₄Nb₂O₉ (τ_f ∼ −70 ppm/°C) to form a two phase system. It was confirmed by the XRD and EDX analysis. By appropriately adjusting the x-value in the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system, near-zero τ_f value can be achieved. A new microwave dielectric material, 0.5Mg₄Nb₂O₉-0.5CaTiO₃ applicable in microwave devices is suggested and possesses the dielectric properties of a dielectric constant ?_r ∼ 24.8, a Q × f value ∼82,000 GHz (measured at 9.1 GHz) and a τ_f value ∼−0.3 ppm/°C.