Thermal Expansion of Nb2O5

The high-temperature thermal expansion of monoclinic Nb₂O₅ was studied with X-ray and dilatometric techniques. The X-ray axial thermal expansion was anisotropic; the mean coefficients in the a, b , and c directions, respectively, were 5.3, 0, and 5.9×10⁻⁶°C^-1 from room temperature to 1000°C. It is proposed that this anisotropy causes microcrack formation in sintered polycrystalline samples. The bulk linear thermal expansion of both sintered and hot-pressed samples was determined with a dilatometer from room temperature to 1200°C. A hysteresis effect between heating and cooling data observed for sintered samples was attributed to the occurrence and recombination of internal microcracks.     

Ta2O5/Nb2O5 and Y2O3 Co-doped Zirconias for Thermal Barrier Coatings

Zirconia doped with 3.2–4.2 mol% (6–8 wt%) yttria (3–4YSZ) is currently the material of choice for thermal barrier coating topcoats. The present study examines the ZrO₂-Y₂O₃-Ta₂O₅/Nb₂O₅ systems for potential alternative chemistries that would overcome the limitations of the 3–4YSZ. A rationale for choosing specific compositions based on the effect of defect chemistry on the thermal conductivity and phase stability in zirconia-based systems is presented. The results show that it is possible to produce stable (for up to 200 h at 1000°–1500°C), single (tetragonal) or dual (tetragonal + cubic) phase chemistries that have thermal conductivity that is as low (1.8–2.8W/m K) as the 3–4YSZ, a wide range of elastic moduli (150–232 GPa), and a similar mean coefficient of thermal expansion at 1000°C. The chemistries can be plasma sprayed without change in composition or deleterious effects to phase stability. Preliminary burner rig testing results on one of the compositions are also presented.     

Formation and Transformation of Solid Solutions in the System Nb2O5–Ta2O5

In the system Nb₂O₅–Ta₂O₅, a continuous series of δ-Nb₂O₅ (δ-Ta₂O₅) solid solutions with a hexagonal cell is formed while heating amorphous materials prepared by the simultaneous hydrolysis of niobium and tantalum alkoxides. The lattice parameters a and c change linearly with increasing Ta₂O₅ content; the former value increases from 0.3604 to 0.3620 nm, and the latter value decreases from 0.3923 to 0.3883 nm. They transform to γ-Nb₂O₅ (β-Ta₂O₅) solid solutions with an orthorhombic cell at higher temperatures. The changes in lattice parameters a and c as functions of composition are the same as those of hexagonal solid solutions, whereas parameter b is relatively constant.     

The Binary System CaO–Nb2O5

The binary system CaO-Nb₂O₅ has been shown to include three compounds: CaO·Nb₂O₅, which melts congruently at 1560°C; 2CaO·Nb₂O₅, which melts congruently at 1576°C; and 3CaO·-Nb₂O₅, which melts incongruently at 1560°C. Three eutectic compositions occur at 6% CaO (1362°C), 23% CaO (1492°C), and 34% CaO (1535°C). These results were obtained by the cone-fusion technique. The compound 3CaO-Nb₂O₅ has been shown to exist in two forms: type I, face-centered cubic with a = 7.978 A, having a superlattice with a = 23.934 A, and type II, orthorhombic (pseudotetragonal, distorted cubic) with a = 11.51 A, b = 11.10 A, c = 15.98 A, having a pseudocell with a = 5.754 A, b = 5.551 A, and c = 7.990 A. The conditions controlling the formation of these two forms were not determinable from the experiments conducted.     

Crystallization of Monoclinic 2TiO2·5Nb2O5

Monoclinic 2TiO₂·5Nb₂O₅ crystallizes at 810° to 835°C from an amorphous material prepared by the simultaneous hydrolysis of titanium and niobium alkoxides. Crystallization isotherms are described by the contracting cube equation 1 − (1 − f)¹¹³= k(t − t₀); the activation energy is 315 kJ·mol⁻¹. Monoclinic 2TiO₂·5Nb₂O₅ transforms to the orthorhombic modification at ∼1200° to 1300°C.     

Crystallization and Dielectric Properties of SrO–BaO–Nb2O5–SiO2 Tungsten-Bronze Glass-Ceramics

The crystallization and dielectric properties of SrO–BaO–Nb₂O₅–SiO₂ glass-ceramics have been investigated. Glass-ceramics that contain strontium barium niobate (SBN) as a primary crystalline phase, which has a tungsten bronze structure, are produced. The formation of crystalline secondary phases also has been studied. The SBN phase shows evidence of both surface nucleation and bulk nucleation, and the crystals have an average composition of Sr_0.47Ba_0.53Nb₂O₆. The dendritic morphology of the SBN crystals has been examined. The SBN content and composite dielectric constant each has been studied as a function of heating temperature/time. The highest SBN content and dielectric constant obtained in the present study are 42 vol% and 180, respectively. The dielectric constant of the glass-ceramics is determined primarily by the SBN content and the residual glass phase. The dielectric constant of the randomly oriented SBN crystal in the glass-ceramics is calculated, using dielectric mixture rules, to be ∼400.     

The Binary System Nb2O5— SiO2

The binary system Nb₂O₅— SiO₂ has been shown to include an extensive two-liquid region over the range 5 to 80% Nb₂O₅. The minimum temperature of the two-liquid area is 1695°C. A eutectic composition occurs at 95% Nb₂O₅ and 1448°C. and another at approximately 5% Nb₂O₅ and 1695°C. The experimental results were obtained by the cone-fusion method.     

Effect of Ta2O5, Nb2O5, and HfO2 Alloying on the Transformability of Y2O3-Stabilized Tetragonal ZrO2

The addition of Ta₂O₅, Nb₂O₅, and HfO₂ enhanced the transformability of Y₂O₃-stabilized tetragonal ZrO₂ polycrystal (Y-TZP), which was indicated by an increase in phase transformation temperatures and fracture toughness of Y-TZP. Comparison of the alloying effects of these oxides on the transformability and crystal structure of Y-TZP suggested that an alloying oxide which increases the c/a axial ratio (tetragonality) of TZP also increases the transformability. Empirical equations to predict the tetragonality are proposed. Calculated tetragonalities showed good agreement with measured values in the systems ZrO₂-Y₂O₃-Ta₂O₅, -Nb₂O₅, and -HfO₂.     

Core-Shell Structure Formation in Nb2O5-Doped SrTiO3 by Oxygen Partial Pressure Change

A core-shell structure was observed in SrTiO₃ doped with 1.2 mol% of Nb₂O₅, after sintering in a reducing atmosphere (5H₂-95N₂) and then in an oxidizing atmosphere (air). In undoped and Al₂O₃-doped SrTiO₃ specimens, no core-shell structure formed after the same sintering treatments as those for SrTiO₃ doped with 1.2 mol% of Nb₂O₅. The measured chemical compositions of the core and shell regions of 1.2-mol%-Nb₂O₅-doped SrTiO₃ grains showed that the Sr/(Ti + Nb) ratio of the shell regions grown in air was ~1% less than that of core regions grown in 5H₂-95N₂, which was in good agreement with a value predicted by available defect equations. Therefore, the observed core-shell structure is thought to result from the formation of strontium vacancies in an oxidizing atmosphere.     

Microwave Dielectric Properties of 5Li2O–0.583Nb2O5–3.248TiO2 Ceramics with V2O5

The effects of V₂O₅ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O–0.583Nb₂O₅–3.248TiO₂ (LNT) ceramics have been investigated. With addition of low-level doping of V₂O₅ (≤2 wt%), the sintering temperature of the LNT ceramics could be lowered down to around 920°C due to the liquid phase effect. A secondary phase was observed at the level of 2 wt% V₂O₅ addition. The addition of V₂O₅ does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the excellent microwave dielectric properties of ɛ_r=21.5, Q × f =32 938 GHz, and τ_f=6.1 ppm/°C could be obtained for the 1 wt% V₂O₅-doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as an internal electrode.     

Crystallization Kinetics of the LiBO2–Nb2O5 Glass Using Differential Thermal Analysis

The crystallization kinetics in the glass system (100− x )LiBO₂− x Nb₂O₅ (5≤ x ≤20, in molar ratio) prepared via the conventional metal-plate quenching technique have been studied by isothermal and non-isothermal methods using differential thermal analyses. X-ray powder diffraction studies carried out on heat-treated (500°C) glasses reveal the evolution of lithium niobate crystalline phase along with a minor phase of LiBO₂. The exponent n in the Jhonson–Mehl–Avrami (JMA) equation applied to the isothermal process is 2.62, which is in excellent agreement with that obtained under the non-isothermal process (2.67). The activation energies for crystal growth obtained from JMA equation under isothermal condition, modified Ozawa and Kissinger equations under non-isothermal conditions, are 293, 311, and 306 kJ/mol, respectively.     

Defects and Charge Transport in β-Ta2O5: II, Analysis of the Conductivity of Nb2O5-doped β-Ta2O5

The model proposed to explain the defect behavior of nominally pure β-Ta₂O₅ was extended to the case of defect equilibria and charge transport in β-Ta₂O₅ doped with a multivalent cation, i.e., Nb₂O₅-doped P-Ta₂O₅. This case is of practical interest in the electronics industry, where Nb₂O₅, is a dominant impurity in capacitor-grade β-Ta₂O₅.     

Effect of Nb2O5 Alloying on Thermal Expansion Anisotropy of 2 mol% Y2O3-Stabilized Tetragonal ZrO2

Tetragonal ZrO₂ ( t -ZrO₂) solid solutions were prepared with addit ons of 2 mol% Y₂O₃ plus up to 0.45 mol% Nb₂O₅. The thermal expansion coefficients in both the a- and c -axis lattice directions increased with Nb₂O₅ alloying and the thermal expansion in the c -axis direction was greater than that in the a -axis direction over the entire composition range. This anisotropic thermal expansion behavior was related to the 4-fold coordination of Nb⁵⁺ with oxygen ions in t -ZrO₂ solid solutions in the system ZrO₂–Y₂O₃–Nb₂O₅. The fracture toughness continuously increased with Nb₂O₅ alloying and suggested that the c/a axial ratio is a more significant factor than the internal stress that arises from the thermal expansion anisotropy, in the determination of the transformability of t -ZrO₂ in this system.     

Phase Equilibria in the System Na2O – Nb2O5

Phase equilibria data, obtained both by differential thermal analysis and by quenching, are presented for the system Na₂O-Nb₂O₅. Five compounds corresponding to the formulas 3Na₂O.1Nb₂0₆, lNa₂O. 1Nb₂O₅, lNa₂O 4Nb₂O₆, lNa_zO.7Nb₂O₅, and lNa₂O. 10Nb₂O₆ have been found. The compound 3Na_z0.lNb₂O₅ melts congruently at 992°C. The compounds 1Na₂O. 4Nb₂O₆, lNa₂O.7Nb₂O, and 1Na₂O. 1Onb₂O₅ melt incongruently at 1265°, 1275°, and 1290°C., respectively. The well-known perovskite structure phase NaNbO₃ was found to melt congruently at 1412°C. The transition temperatures in NaNbO₅ were checked by thermal analysis and only the major structural changes at 368° and 640°C. could be detected. A new disordered form of NaNbO₃ could be preserved to room temperature by very rapid quenching.     

Influence of V2O5 Additions to 5Li2O–1Nb2O5–5TiO2 Ceramics on Sintering Temperature and Microwave Dielectric Properties

The effects of the addition of V₂O₅ on the sintering behavior, microstructure, and microwave dielectric properties of 5Li₂O–1Nb₂O₅–5TiO₂ (LNT) ceramics have been investigated. With low-level doping of V₂O₅ (≤3 wt%), the microstructure of the LNT ceramic changed from a special two-level intergrowth structure into a two-phase composite structure with separate grains. And the sintering temperature of the LNT ceramics could be lowered to around 900°C by adding a small amount of V₂O₅ without much degradation in microwave dielectric properties. Typically, better microwave dielectric properties of ɛ_r=41.7, Q × f =7820 GHz, and τ _f =45 ppm/°C could be obtained for the 1 wt% V₂O₅-doped ceramics sintered at 900°C.