Synthesis of Nanosized Titanium-Chromium Oxynitride Powders by Ammonolysis of Coprecipitated TiO2/Cr2O3 Precursors

Interstitial titanium-chromium oxynitrides in the solid solution series Ti_{1− z} Cr _z (O _x N _y ) ( z = 0.2, 0.4, 0.5, 0.6, 0.8) have been obtained by ammonolysis of the TiO₂/Cr₂O₃ precursors resulting from the coprecipitation method. The precursors and the resulting oxynitrides were characterized by auger electron spectroscopy, X-ray diffraction analysis, electron probe microanalysis, transmission electron microscopy, and BET surface area techniques. Compounds in the Ti_{1− z} Cr _z (O _x N _y ) series are prepared as single phases by nitridation at 1073 K for 8 h. The as-synthesized oxynitride powders contain only Ti_{1− z} Cr _z (O _x N _y ) with cubic structure and the particle size is in the nanometer scale.     

Oxygen Position, Octahedral Distortion, and Bond-Valence Parameter from Bond Lengths in Ti1−xSnxO2 (0 ≤x≤ 1)

Based on the virtual crystal approximation (or Vegard's law), the bond lengths of Ti_{1− x} Sn _x O₂ were deduced from those of TiO₂ and SnO₂, to allow the oxygen position and octahedral distortion to be determined as a function of x . The oxygen positional parameter ( u ) increased linearly when the Sn⁴⁺ cation (which has a larger ionic radius) was substituted for the Ti⁴⁺ cation, whereas the octahedral distortion exhibited a nonlinear decay with increasing x in Ti_{1− x} Sn _x O₂. At the same time, the bond-valence parameter, which relates bond valence to bond length, so that the central atom in the octahedron can retain a constant valence of +4.0, exhibited a correlation with u for Ti_{1− x} Sn _x O₂. The present results indicate that the different phonon/physical properties of TiO₂ and SnO₂ and/or their dependence on x in Ti_{1− x} Sn _x O₂ can be associated with different octahedral distortions.     

Enhanced Visible Light-Driven Photocatalytic Performance of La-Doped TiO2−xFx

La-doped TiO_{2− x} F _x (La–TiO_{2− x} F _x ) powders were prepared by the sol–gel method. X-ray diffraction results showed that La efficiently inhibited grain growth. X-ray photoelectron spectroscopy spectra revealed that La₂O₃ and O–Ti–F bonds have formed, the La₂O₃ maintained the high surface area of TiO_{2− x} F _x after calcination at a temperature above 500°C, while the O–Ti–F bonds increased the oxidation potential of the photogenerated hole in the valence band. The UV-vis spectroscopy of the La–TiO_{2− x} F _x showed that the presence of intraband gap states was likely responsible for its absorption of visible light. When the molar ratios of La and F to Ti were 1.5:100 and 5:100, respectively, and calcined at 500°C, the photocatalytic degradation rate of methylene blue over La–TiO_{2− x} F _x was about 1.5 times higher than that of F-doping TiO₂.     

Effects of Coffee-Bean-Like Morphology and Graded Interlayer on Texture Evolution of Plasma-Enhanced Chemical-Vapor-Deposited Ti-C-N Films

Titanium nitride (TiN), titanium carbide (TiC), and titanium carbonitride (TiC _x N_1−x) were prepared by plasma-enhanced chemical vapor deposition. A graded interlayer was introduced to explore its effects on the texture of the TiC and TiN. The results showed that the topography of the TiC _x N_1−x, which resembled coffee beans, resulted from a twinning core structure that caused the dendritic grain shape and enhanced the 〈211〉 texture of TiC_0.62·N_0.38and TiC_0.75·N_0.25. As graded coating was used as a transition layer, the texture of TiC was changed from (220) to (200), and TiN was changed from (200) to (220) due to the pseudomorphic forces provided by the first layer plus graded layer. The residual stress contributions to this phenomenon are also discussed.     

Phase Relations in the Pyrochlore-Rich Part of the Bi2O3−TiO2−Nd2O3 System

In this study we used solid-state synthesis to determine the phase relations in the pyrochlore-rich part of the Bi₂O₃−TiO₂−Nd₂O₃ system at 1100°C. The samples were analyzed using X-ray powder diffraction and scanning electron microscopy with energy- and wavelength-dispersive spectroscopy. A single-phase pyrochlore ceramic was obtained with the addition of 4.5 mol% of Nd₂O₃. We determined the solubility limits for the three solid solutions: (i) the pyrochlore solid solution Bi_{(1.6–1.08 x )}Nd _x Ti₂O_{(6.4+0.3 x )}, where 0.25< x <0.96; (ii) the solid solution Bi_{4− x} Nd _x Ti₃O₁₂, where 0< x <2.6; and (iii) the Nd_{2− x} Bi _x Ti₂O₇ solid solution, where 0< x <0.35. The determined phase relations in the pyrochlore-rich part are presented in a partial phase diagram of the Bi₂O₃−TiO₂−Nd₂O₃ system in air at 1100°C.     

Subsolidus Phase Relationships in the Ga2O3–Al2O3–TiO2 System

Subsolidus phase relationships in the Ga₂O₃–Al₂O₃–TiO₂ system at 1400°C were studied using X-ray diffraction. Phases present in the pseudoternary system include TiO₂ (rutile), Ga_{2−2 x} Al_{2 x} O₃ ( x ≤0.78 β-gallia structure), Al_{2−2 y} Ga_{2 y} O₃ ( y ≤0.12 corundum structure), Ga_{2−2 x} Al_{2 x} TiO₅ (0≤ x ≤1 pseudobrookite structure), and several β-gallia rutile intergrowths that can be expressed as Ga_{4−4 x} Al_{4 x} Ti _{n −4}O_{2 n −2} ( x ≤0.3, 15≤ n ≤33). This study showed no evidence to confirm that aluminum substitution of gallium stabilizes the n =7 β-gallia–rutile intergrowth as has been mentioned in previous work.     

Electrical Properties of Cerium-Doped BaTiO3

The high-temperature equilibrium electrical conductivity of Ce-doped BaTiO₃ was studied in terms of oxygen partial pressure, P (O₂), and composition. In (Ba_1−xCe _x )TiO₃, the conductivity follows the −1/4 power dependence of P (O₂) at high oxygen activities, which supports the view that metal vacancies are created for the compensation of Ce donors, and is nearly independent of P (O₂) where electron compensation prevails at low P (O₂). When Ce is substituted for the normal Ti sites, there is no significant change in conductivity behavior compared with undoped BaTiO₃, indicating the substitution of Ce as Ce⁴⁺ for Ti⁴⁺ in Ba(Ti_1−yCe _y )O₃. The Curie temperature ( T _c) was systematically lowered when Ce³⁺ was incorporated into Ba²⁺ sites, whereas the substitution of Ce⁴⁺ for Ti⁴⁺ sites resulted in no change in this parameter.     

Synthesis of New Nanocrystalline Titanium–Niobium Oxynitride Powders

New titanium–niobium oxynitride (Ti_{1− z} Nb _z O _x N _y ) powders were synthesized by ammonolysis of nanosized TiO₂/Nb₂O₅ composite powders at 700°–900°C for 5 h. The products were characterized by X-ray diffraction (XRD), chemical analysis, and transmission electron microscopy. The results indicated that the as-synthesized powders were pure cubic structures with sizes of 30–60 nm. With increasing value of z , XRD peaks of Ti_{1− z} Nb _z O _x N _y powders tended to shift toward low 2θ angle and the cell parameter showed a linear increase.     

Influence of Iron Doping on the Microstructure of YBa2(Cu1−xFex)3O7−δ Ceramics

Porosity, grain growth, phase composition, and microstructural defects were studied in sintered YBa₂ (Cu_1−x)₃O_7−x ceramics for x values up to 0.3. The porosity of the samples, related to the sintering mechanism, was independent of iron concentration. A linear dependence of the grain size with the inverse of the iron concentration was found, strongly suggesting grain boundary segregation of iron. The solubility limit was estimated to be x = 0.18 at 950°C in O₂. Beyond this limit, a new microstructural component was found consisting of YBa₂(Cu_1−xFe_x)₃O_7−δ, YBaCuFeO₅ and Ba(Cu,Fe)O₂. The transition from an orthorhombic twin to an orthorhombic tweed phase and a tetragonal phase was detected by polarized light microscopy.     

Origin of Microwave Dielectric Loss in ZnNb2O6-TiO2

(1− x )ZnNb₂O₆· x TiO₂ ceramics were prepared using both anatase and rutile forms of TiO₂. At a composition of x = 0.58, a mixture region of ixiolite (ZnTiNb₂O₈) and rutile was observed and the temperature coefficient of resonant frequency (τ_f) was ∼0 ppm/°C. We found that although ɛ_r and τ_f were comparable, the quality factor ( Q × f , Q ≈ 1/ tan δ, f = resonant frequency) of 0.42ZnNb₂O₆·0.58TiO₂ prepared from anatase and rutile was 6000 and 29 000, respectively. The origin of the difference in Q × f of both samples was investigated by measuring electrical conductivity and by analysis of the anatase–rutile phase transition. The anatase-derived sample had higher conductivity, which was related to the reduction of Ti⁴⁺. It is suggested that the increase of dielectric loss originates from an increase in Ti³⁺ and oxygen vacancies due to an anatase–rutile phase transition.     

Tailoring the Microwave Dielectric Properties of MgNb2O6 and Mg4Nb2O9 Ceramics

The columbites MgNb₂O₆, MgTa₂O₆, and corundum-type Mg₄Nb₂O₉ ceramics were prepared by the conventional solid-state ceramic route. The structure and microstructure of the sintered samples were investigated by X-ray diffraction and scanning electron microscopic techniques. The microwave dielectric properties of the samples were measured by the resonance method in the frequency range 4–6 GHz. The dielectric properties have been tailored by forming a solid solution between MgNb₂O₆ and MgTa₂O₆ and by the substitution of TiO₂ for Nb₂O₅ in both MgNb₂O₆ and Mg₄Nb₂O₉ ceramics. The Mg(Nb_0.7Ta_1.3)O₆ has ɛ_r=29, Q _u× f =67 800 GHz, and τ_f=0.8 ppm/°C and the MgO–(0.4)Nb₂O₅–(1.5)TiO₂ composition has ɛ_r=34.5, Q _u× f =81 300 GHz, and τ_f=−2 ppm/°C.     

Factors Determining Grain Orientation in Bismuth Sodium Potassium Titanate–Lead Zirconate Titanate Solid Solutions Made by the Reactive Templated Grain Growth Method

Grain-oriented Bi_0.5(Na_0.85K_0.15)_0.5TiO₃-Pb(Zr_{1− x} Ti _x )O₃ (BNKT-PZT) ceramics were prepared via the reactive templated grain growth method, using platelike Bi₄Ti₃O₁₂ particles. Factors that determine the degree of orientation were examined. Prereacted PZT gave a larger degree of orientation than PZT raw materials (PbO, ZrO₂, and TiO₂) in the 75BNKT-25PZT ( x = 0.5) system. Increases in the titanium concentration in the PZT of the 75BNKT-25PZT system and in the BNKT concentration in the y BNKT-(100 − y )PZT ( x = 0.5) system increased the degree of orientation. The direction of material transport between BNKT and PZT was important to obtain ceramics with a large degree of orientation.     

Structure-Property Phase Diagram of BaZrxTi1−xO3 System

In the course of searching environmental friendly lead-free relaxor ferroelectrics a complete phase diagram of barium zirconate titanate, Ba(Zr _x Ti_{1− x} )O₃ system with compositions 0.00≤ x ≤1.00 has been developed based on their dielectric behavior. It has been shown that BaZr _x Ti_{1− x} O₃ system depending on the composition, successively depicts the properties extending from simple dielectric (pure BaZrO₃) to polar cluster dielectric, relaxor ferroelectric, second order like diffuse phase transition, ferroelectric with pinched phase transitions and then to a proper ferroelectric (pure BaTiO₃). A comprehensive structure–property correlation of BaZr _x Ti_{1− x} O₃ ceramics has been studied to understand the various ferroelectric phenomena in the whole phase diagram.     

Study of Nonstoichiometry of 〈U1–zGdzO2±x〉

The extensive nonstoichiometry in the 〈U_{1– z} Gd _z O_{2± x} 〉 † phase was investigated experimentally and the data are represented by a chemical thermodynamic method. The experimental ranges of temperature, oxygen potential, and z were 1273 to 1773 K, 0 to −600 kJ/mol, and 0.1 to 0.8, respectively. For hypostoichiometry, ideal-solution thermodynamics for the equilibrium 3Gd_4/3O₂+ 4UO₂+ (O₂) = 6U_2/3Gd_2/3O_8/3 were used to represent the experimental data, while for hyperstoichiometry a nonideal solution was used for the equilibrium 4UO₂+ (O₂) = 2U₂O₅. The wide ranges in x and z led to an improvement of the previous analysis of literature data and led to partial molal Gibbs free energy values that are useful for any thermodynamic calculation involving the phase.     

Oxidation Resistance of Alumina–Titanium Nitride and Alumina–Titanium Carbide Composites

The presence of TiC or TiN paritcles in an Al₂O₃ matrix affects the thermal stability of the composites in oxidizing environments. In isothermic oxidation tests at 700°, 800°, 900°, 1000°, and 1100°C for up to 20 h, two different oxidation regimes have been observed at T < 900°C and at 900°C ≤ T ≤ 1100°C. At low temperatures ( T < 900°C), the oxidation follows a phase-boundary reaction; the reaction product initially consists of aggregates of submicrometer needlelike TiO₂ rutile crystals that subsequently grow and coalesce. When a continuous TiO₂ rutile layer is formed ( T ≥ 900°C), the oxidation kinetics change to parabolic, and the diffusion of O₂ through a thick TiO₂ layer is proposed as the governing step.     

Phase Relations in the System MgO-V2O3-VO2 at 1200°C

Phase relations in the quasi-ternary system MgO-V₂O₃-VO₂ at 1200°C were studied using the quenching technique under controlled O₂ atmospheres. A new phase of a type z VO _y Mg_{2− x} V_{1+ x} O₄ (0< x <1, y ≥1.5, z >0) was found with a compositional region along the MgV₂O₄-Mg₂VO₄ join. Equilibrium P _{O 2} observed for Mg_{2− x} V_{1+ x} O₄ is quite different from that for V _n O_{2 n -1} with an equal ratio of V³⁺/V⁴⁺, corresponding to the V³⁺ stabilities in two types of compounds. Thus, the phase relations in the ternary system were constructed on a conventional triaxial diagram as a function of P _O2.     

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.     

Influence of Non-Stoichiometry on the Structure and Properties of Ba(Zn1/3Nb2/3)O3 Microwave Dielectrics: I. Substitution of Ba3W2O9

A narrow region of Zn-vacancy-containing cubic perovskites was formed in the (1− x )Ba₃(ZnNb₂)O₉−( x )Ba₃W₂O₉ system up to 2 mol% substitution ( x =0.02). The introduction of cation vacancies enhanced the stability of the 1:2 B-site ordered form of the structure, Ba(Zn_{1− x} □ _x )_1/3(Nb_{1− x} W _x )_2/3O₃, which underwent an order–disorder transition at 1410°C, ∼35° higher than pure Ba(Zn_1/3Nb_2/3)O₃. The Zn vacancies also accelerated the kinetics of the ordering reaction, and samples with x =0.006 comprised large ordered domains with a high lattice distortion ( c/a =1.226) after a 12 h anneal at 1300°C. The tungstate-containing solid solutions can be sintered to a high density at 1390°C, and the resultant ordered ceramics exhibit some of the highest microwave dielectric Q factors ( Q × f =1 18 000 at 8 GHz) reported for a niobate-based perovskite.     

Grain Growth and Phase Transformation of Titanium Oxide During Calcination

Additions of NiO, CoO, MnO₂, Fe₂O₃, and CuO promote the anatase-rutile transformation and grain growth of TiO₂. Additions of Na₂O and WO₃ retard the transformation and have no effect on the grain growth. The addition of MoO₃ strongly promotes the grain growth but has only a slight effect on the phase transformation. Both the grain growth and transformation are promoted slightly by Cr₂O₃. The transformation is significantly affected by the method of preparing TiO₂. The grain size of TiO₂ heated in H₂ exceeds that of TiO₂ heated in O₂, in air, in argon, and in vacuum. The rate of transformation decreases with an increase in the partial pressure of oxygen of the atmosphere.