Effects of V and Mn Colorants on the Crystallization Behavior and Optical Properties of Ce-Doped Li-Disilicate Glass–Ceramics

The critical cooling rate and fluorescence properties of lithium (Li) disilicate glasses and glass–ceramics, doped with 2.0 wt% CeO₂ and with up to 0.7 wt% V₂O₅ and 0.3 wt% MnO₂ added as colorants, were investigated. The critical cooling rates, R _c, of glass melts were determined using differential thermal analysis and were found to be dependent on the relative concentrations of V₂O₅ and MnO₂, decreasing from 25±3° to 16±3°C/min. Annealed glasses were heat treated first to 670°C, and then to 850°C to form Li metasilicate and Li disilicate glass–ceramics, respectively. The fluorescence intensities of the Ce-doped glasses and glass–ceramics decrease by a factor of 100 with the addition of the transition metal oxides. This optical quenching effect is explained by the association of the Ce³⁺ ions with the transition metal ions in the residual glassy phase of the glass–ceramics.     

Humidity-Sensitive Characteristics of Porous La-Ti-V-O Glass-Ceramics

The humidity-sensitive characteristics of La₂O₃–TiO₂–V₂O₅ glass-ceramics were investigated as a function of additive amount of V₂O₅ to the precursor glass and the heating temperature of the glass to iduce phase separation. The microstructure of each glass-ceramic was strongly dependent upon the heating temperature. The specific impedance was lowered by increasing the amount of V₂O₅ additive. Among the elements studied, the LTV 2–2 element, which was prepared from as-cast glass, consisted of Na₂O:B₂O₃:La₂O₃: TiO₂: V₂O₅= 8.3:32.9:7.2:31.6:20.0 (molar ratio) after heating at 450°C for 12 h and subsequent leaching at 85°C for 24 h, and was found to be the most suitable material from the standpoint of humidity sensitivity, measurability, and response time.     

Electrical Conductivity of PbO-P2O5-V2O5Glasses

The dc conductivities (α) of PbO-P₂O₅-V₂O₅ glasses containing up to 80 mol% V₂O₅ were measured at T = 100°C to T = 10°C below the glass transition temperature. Dielectric constants at 1 MHz, densities, and the fraction of reduced V ion were measured at room temperature. The conduction mechanism of glasses containing >10 mol% V₂O₅ was considered to be small-polaron hopping, as previously reported for other vanadate glasses. The temperature dependence of α was exponential, with α= (αo/ T ) exp(− W/kT ). When the V₂O₅ content was ≥50 mol%, W decreased and α increased with increasing V₂O₅ content, and the adiabatic approximation could be applied. In the composition range between 10 and 50 mol% V₂O₅, α increased with increasing V₂O₅ content, but W varied little. In this region, the hopping conduction was characterized as nonadiabatic. The effect of dielectric constants and V ion spacing on W is discussed.     

Structure and Mechanism of Conduction of Semiconductor Glasses

The area of glass formation in the system GeO₂-P₄O₁₀-V₂O₅ and the properties of the glasses in this area were determined. The glasses displayed electronic conduction at room temperature (25°C). Resistivity ranged from 500 ohm-cm to 10⁹ ohm-cm at 25°C. Some of the glasses had unusual negative temperature coefficients of resistance of the order of -760,000 ppm °C⁻¹ in the range 25° to -55°C. Volt-ampere characteristics indicated nonlinearity suitable for thermistor application. Other unusual properties included high refractive indices from 1.6 to >2.0 and dielectric constants from 6 to 33 at 1 Mc and 25°C. Values of loss-tangents, however, were high. Infrared spectra indicated that the V⁵⁺ ion existed in sixfold coordination in the glassy state as well as in the devitrified crystalline state. The normal vibrational frequency of the V–O bond at 1015 cm⁻¹ was observed for all glasses in the system. Property versus composition curves indicated that density, refractive index, and dielectric constant of ternary glasses in the system do not obey the additivity rule. The density versus mole % V₂O₅ curve goes through a minimum. Derived quantities from experimental data indicate pronounced influence of V₂O₅ on oxygen packing in the system. Addition of SiO₂, even in small quantities, destroys glass formation. The structure of these glasses, which differs from that of silicate glasses, is discussed. A mechanism of conduction is suggested, based on evidence from magnetic susceptibility, chemical analysis, activation energy, and infrared spectra.     

Synthesis of Vanadium Oxide Powders by Evaporative Decomposition of Solutions

Powders of the vanadium oxides V₂O₄, V₆O₁₃, and V₂O₅were produced by thermal decomposition of aqueous solutions of vanadyl sulfate hydrate in atmospheres of N₂, H₂mixed with N₂, or air. The composition of the oxide powder was determined by the reactor temperature and gas composition. Residual sulfur concentrations in powders produced by decomposition at 740°C were less than 1 at.%, and these powders consisted of hollow, roughly spherical aggregates of particles less than 1 μm in diameter.     

Electrical Conductivity of TiO2-V2O5-P205 Glasses

The dc conductivities (σ) of V₂O₅-P₂O₅ glasses containing up to 30 mol% TiO₂ were measured at T=100° to ∼10°C below the glass-transition temperature. Dielectric constants from 30 to 10⁶ Hz, densities, and the fraction of reduced V ion were measured at room temperature. The conduction mechanism was considered to be small polaron hopping between V ions, as previously reported for V₂O₅-P₂O₅ glass. The temperature dependence of σ was exponential with σ = σ₀ exp(-W/kT ) in the high-temperature range. When part of the P₂O₅ was replaced by TiO_2,σ increased and W decreased. The hopping energy depended on the reciprocal dielectric constant which, in this case, increased with increasing TiO₂ content.     

Preparation of Alkoxy-Derived Tantalum Vanadate

Compound formation in the system Ta₂O₅–V₂O₅ has been studied using amorphous materials prepared by the simultaneous hydrolysis of tantalum and vanadyl alkoxides. Three compounds exist in this system: 9Ta₂O₅· V₂O₅, 9Ta₂O₅·2V₂O₅, and Ta₂O₅·V₂O₅ (TaVO₅). Solid solutions of δ-Ta₂O₅ are formed at low temperatures up to 10 mol% V₂O₅. They transform to β-Ta₂O₅ solid solutions at higher temperatures; the transformation temperature falls with increasing V₂O₅ A new compound, 9Ta₂O₅·V₂O₅, 670° to 755°. It has an orthorhombic unit cell with a = 0.7859 nm, b = 1.733 nm, and c = 1.766 nm. Orthorhombic TaVO₅ crystallized at 535° to 560° decomposes into 9Ta₂O₅°V₂O₅ at 1010°.     

Synthesis of V2O3 Powder by Evaporative Decomposition of Solutions and H2 Reduction

The evaporative decomposition of solutions method was used to form V₂O₅. Spraying above the congruent melting temperature of V₂O₅ (690°C) resulted in dense spherical particles with a smooth surface. Spraying below the V₂O₅ melting temperature yielded porous V₂O₅ powder with a rough surface. Reduction of the V₂O₅ to V₂O₃ was done in a H₂ atmosphere. Spherical V₂O₃ powder was attained when the reduction temperature was low enough to reduce the V₂O₅ surface before partial sintering (necking) between V₂O₅ particles occurred. The resulting V₂O₃ particle size was smaller than the precursor V₂O₅ powder as expected by the differences in densities between V₂O₅ ( p = 3.36 g/cm³) and V₂O₃ ( p = 4.87 g/cm³).     

Crystallization of Metastable Aluminas in the Presence of V2O5

In investigating possible effects of high temperatures on a V₂O₅/γ-Al₂O₃ catalyst, it was found that metastable aluminas with unusually well-developed crystallinity can be prepared in the presence of V₂O₅. With control of firing temperature, time, and atmosphere, δ-, θ-, and k -Al₂O₃ could be obtained in this state. X-ray powder diffraction patterns containing many more lines than usually observed were indexed, unit-cell dimensions calculated, and values compared with previous data. All preparations contained small amounts of V which could not be removed by H₂O₂; ESR revealed V⁴⁺ ions in them.     

Phase Equilibria in the System SrO-CdO-V2O5

Phase equilibria in the system SrO-CdO-V₂O₅ in air were established from data obtained by DTA, quenching, and high-temperature solid-state reaction experiments. The SrO-V₂O₅ boundary system contains 4 compounds at SrO to V₂O₅ molar ratios of 4:1, 3:1, 2:1, and 1:1. A fifth compound with a molar composition of ∼10:3 with the apatite crystal structure was also found; it may, however, be a hydroxyapatite phase. The CdO-V₂O₅ system contains the compounds 3CdO·V₂O₅, 2CdO·V₂O₅, and CdO·V₂O₅. The latter compound exhibits a rapid reversible polymorphic transition at 180°C. Complete solid solubility exists in the SrO-CdO system. The most probable compatibility relations were determined from the data available for the SrO-CdO-V₂O₅ ternary system. Limited solid solubility exists between SrO·V₂O₅ and CdO·V₂O₅, and the high-temperature CdO·V₂O₅ polymorph is stabilized to room temperature by solid solution of SrO·V₂O₅. Evidence for the existence of 2 ternary compounds with limited local solid solubility is also presented.     

Some Properties of the Oxides of Vanadium and Their Compounds

Vanadium tetroxide and vanadium pentoxide were prepared and some of their physical properties were measured. A brief survey was then made of some of their binary oxide compounds. Various mixtures of V₂O₄ or V₂O₆ and BeO, MgO, CaO, SrO, BaO, Al₂O₃, SiO₂, TiO₂, CeO₂, ZrO₂, Nb₂O₆, and U₃O₈ were heated. When compounds were formed, some of their properties were determined. Refractoriness, thermal expansion, and optical properties were considered of special interest. Vanadium pentoxide was found to have a linear thermal expansion of only 0.63 × 10⁻⁶ per °C. from 30° to 450°C.     

Low-Temperature Preparation and Magnetic Properties of V-Doped SnO2 Nanoparticles

A solid solution of vanadium (V)-doped tin oxide (SnO₂) particles of average diameter 2 nm and V content of 19 at.% was prepared at normal pressure and low temperature (100°C) by mixing wet SnO₂ gel SnO₂· x H₂O with a boiling solution of vanadium oxide (V₂O₅). Experimental characterizations using X-ray, electron diffraction, and transmission electron microscope show evidence of a pure single phase. The nanoparticles exhibit a mixed magnetic behavior, namely paramagnetic and ferromagnetic. Their thermal stability is also investigated. At higher temperature, 850°C, some amount of Fe precipitates from the solid solution.     

Electrical Conductivity of Glasses in the Systems P4O10-V2O5 and P4O10-WO3

The electrical conductivities of P₄O₁₀-V₂O₅ and P₄O₁₀-WO₃ glasses were compared. The P₄O₁₀ content of a glass from each system was replaced by increasing amounts of several oxides. The conductivity of the vanadium phosphate glass was insensitive to oxide replacement, in contrast to the conductivity of the tungsten phosphate glass, which decreased by almost five decades when a small amount of V₂O₅ was introduced. The change was attributed to the effect of oxidation-reduction on the tungsten ions.     

Effect of V2O5 Doping on the Sintering and Dielectric Properties of M-Phase Li1+x−yNb1−x−3yTix+4yO3 Ceramics

The effect of the addition of V₂O₅ on the structure, sintering and dielectric properties of M -phase (Li_{1+ x − y} Nb_{1− x −3 y} Ti _x +4 _y )O₃ ceramics has been investigated. Homogeneous substitution of V⁵⁺ for Nb⁵⁺ was obtained in LiNb_{0.6(1− x )}V_{0.6 x} Ti_0.5O₃ for x ≤ 0.02. The addition of V₂O₅ led to a large reduction in the sintering temperature and samples with x = 0.02 could be fully densified at 900°C. The substitution of vanadia had a relatively minor adverse effect on the microwave dielectric properties of the M -phase system and the x = 0.02 ceramics had [alt epsilon]_r= 66, Q × f = 3800 at 5.6 GHz, and τ_f= 11 ppm/°C. Preliminary investigations suggest that silver metallization does not diffuse into the V₂O₅-doped M -phase ceramics at 900°C, making these materials potential candidates for low-temperature cofired ceramic (LTCC) applications.     

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.     

Infrared Spectra of GeO2-P4O10-V2O5 Glasses and Their Relation to Structure and Electronic Conduction

Infrared spectra of binary and ternary compositions in the glassy state and in the devitrified crystalline state in the system GeO₂-P₄O₁₀-V₂O₅ were studied and compared with infrared spectra of crystalline spinels, which are known to contain V⁵⁺ ions in sixfold coordination. Results indicated that the fundamental vibration frequency of the V—O bond occurred at wave number 1015 cm⁻¹. The spectra also provided evidence that the V⁵⁺ ion existed in sixfold coordination in the glassy state, as well as in the devitrified crystalline state, and that the VO₆ octahedron retained its identity even at low concentrations and melting temperatures of 1450°C. Conductivity measurements indicated that, as the concentration of V₂O₅ decreased below the critical range of 5 to 10 mole %, there was an abrupt loss in the electronic conductivity of the glasses; the conductivity decreased with increasing concentration of the lower valence states of vanadium. A mechanism of conduction compatible with the structure of glasses in the system is suggested to explain these observations.     

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.     

Formation of Frozen α-Agl in Twin-Roller-Quenched Agl─Ag2 O─MxOy (MxOy= WO3, V2O5) Glasses at Ambient Temperature

Superionic conductor α-AgI, which is stable only above 147°C, was successfully frozen at ambient temperature in AgI─Ag₂O─M_xO_y (M_xO_y= WO₃, V₂O₅) glass matrices by a twin-roller-quenching technique. The system with WO₃, provided the larger composition regions where α-AgI was frozen at ambient temperature, compared to the system with V₂O₅. The matrix glasses with higher glass-transition temperatures had a stronger effect in depressing the α–β transformation of AgI. The α-AgI-frozen samples exhibited extremely large conductivities of 3 × 10⁻²-5 × 10⁻²S.cm⁻¹at 25°C.     

Chemical State of Vanadium in Tin-Based Yellow Pigment

Physicochemical states of vanadium in V-doped SnO₂ were studied to clarify the origin of the color of vanadium-tin yellow pigment and its color instability when fired with glaze material. Precision measurements of lattice parameters of V-doped SnO₂ revealed that vanadium was dissolved as V⁴⁺ and its solubility limit was 0.9 wt% as V₂O₅. It was found that the color of vanadium–tin yellow was produced by two types of undissolved vanadium on SnO₂ grains. One is poorly crystallized vandium oxide (v), (V₂O₅)', having a yellow color, and the other is orange-colored crystalline V₂O₅. The structure of (V₂O₅)' was discussed in connection with its color.     

Electronic Conductivity and Related Properties of Amorphous and Crystallized V2O5-Based Glasses

Crystallization of V₂O₃ from V₂O₃P₂O₃, glasses containing 0 to 9 mol% B₂O₃, during heat treatment in the range 220° to 410°C, caused progressive micro structural changes which dramatically affected the electronic conductivity (γ), the activation energy for conduction ( W ), and the resistance to chemical attack. All compositions were ≊83% crystalline after heating to 410°C. As a result, the values of γ and W were almost identical to those observed for pure polycrystalline V₂O₅.