Low-Temperature Synthesis of Praseodymium-Doped Ceria Nanopowders

Praseodymium-doped ceria (CeO₂) nanopowders have been synthesized via a simple but effective carbonate-coprecipitation method, using nitrates as the starting salts and ammonium carbonate as the precipitant. The precursors produced in this work are ammonium rare-earth double carbonates, with a general formula of (NH₄)_0.16Ce_{1− x} Pr _x (CO₃)_1.58·H₂O (0 < x ≤ 0.20), which directly yield oxide solid solutions on thermal decomposition at a very low temperature of ∼400°C. Praseodymium doping causes a gradual contraction of the CeO₂ lattice, because of the oxidation of Pr³⁺ to smaller Pr⁴⁺, and suppresses crystallite coarsening of the oxides during calcination. Dense ceramics have been fabricated from the thus-prepared nanopowders via pressureless sintering for 4 h at a low temperature of 1200°C.     

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.     

Reactive Ceria Nanopowders via Carbonate Precipitation

Nanocrystalline CeO₂ powders have been successfully synthesized via a carbonate precipitation method, using ammonium carbonate (AC) as the precipitant and cerium nitrate hexahydrate as the cerium source. The AC/Ce³⁺ molar ratio ( R ) affects significantly precursor properties, and spherical nanoparticles can be produced only in a narrow range of 2 < R ≤ 3. The precursor, having an approximate composition of Ce(OH)CO₃·2.5H₂O, decomposes to CeO₂ at temperatures ≥300°C. The CeO₂ powder calcined at 700°C exhibits high reactivity and can be densified to >99% of theoretical at 1000°C.     

Densification, Structure, and Thermophysical Properties of Ytterbium–Gadolinium Zirconate Ceramics

(Yb _x Gd_{1− x} )₂Zr₂O₇ (0≤ x ≤1.0) ceramic powders synthesized with the chemical-coprecipitation and calcination method were pressureless-sintered at 1550–1700°C to develop new thermal barrier oxides with a lower thermal conductivity than yttria-stabilized zirconia ceramics. (Yb _x Gd_{1− x} )₂Zr₂O₇ ceramics exhibit a defective fluorite-type structure. The linear thermal expansion coefficients of (Yb _x Gd_{1− x} )₂Zr₂O₇ ceramics increase with increasing temperature from room temperature to 1400°C. The measured thermal conductivity of (Yb _x Gd_{1− x} )₂Zr₂O₇ ceramics first gradually decrease with increasing temperature and then slightly increase above 800°C because of the increased radiation contribution. YbGdZr₂O₇ ceramics have the lowest thermal conductivity among all the composition combinations studied.     

Phase Relations and Thermal Expansion Studies in the Ceria–Yttria System

The synthesis, characterization, and bulk and lattice thermal expansions of a series of compounds with general composition Ce_{1– x} Y _x O_{2– x /2} (0.0 ≤ x ≤ 1.0) are reported. The XRD pattern of each product was refined to learn the solid solubility limit and the homogeneity range. The solid solubility limit of YO_1.5 in CeO₂ lattice, under the conditions of slow cooling from 1400°C, is represented as Ce_0.55Y_0.45O_1.775 (i.e., 45 mol% of YO_1.5). The subsequent compositions were biphase. There was no solubility of CeO₂ into the lattice of YO_1.5. The bulk thermal expansion measurements from ambient to 1123 K, as investigated using a dilatometer, revealed that the α_l (293–1123 K) values, within the homogeneity range, decreased on increased Y³⁺ content. A similar trend was observed for average lattice thermal expansion coefficient, α_a (293–1473 K), as investigated using high-temperature XRD. No ordered phases were obtained in this system under the used conditions. These studies on Ce_{1– x} Y _x O_{2– x /2} (0.0 ≤ x ≤ 1.0) system can be used to simulate the phase relation and thermal expansion behavior of Pu_{1– x} Y _x O_{2– x /2} (0.0 ≤ x ≤ 1.0), because CeO₂ is widely used as a surrogate material for PuO₂.     

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.     

Homogeneity Region of Strontium- and Magnesium-Containing LaGaO3 at Temperatures between 1100° and 1500°C in Air

Phase stability studies were performed within the quasi-ternary system LaGaO₃-SrGaO_2.5-"LaMgO_2.5". Emphasis was cast on the temperature dependence of the homogeneity region of La_{1− x} Sr _x Ga_{1− y} Mg _y O_3−δ perovskite solid solutions. Isothermal sections were determined at 1100°, 1250°, 1400°, and 1500°C in a static air atmosphere. The single-phase homogeneity region was found to considerably diminish with decreasing temperature, indicating a reduction of the solid solubility of Sr and Mg, and below 1100°C the doped perovskite becomes unstable. Consequently, the cubic perovskite phase was found to exist only at elevated temperatures and for high Sr and Mg amounts. Sample preparation was performed by the mixed-oxide process as well as by a modified combustion synthesis.     

Polymorphism of BaTiO3 Acceptor Doped with Mn3+, Fe3+, and Ti3+

The effect of Mn doping on the cubic to hexagonal phase transition temperature in BaTiO₃ has been determined by quenching samples with different Mn contents from a range of temperatures. Under conditions of equilibrating samples in air over the range 1000°–1400°C, cubic solid solutions BaTi_{1− x} Mn _x O_3−δ form over the range 0≤ x ≤0.015(5), whereas hexagonal solid solutions form for x ≥0.02, depending on the temperature. The results are compared with those on doping BaTiO₃ with Fe³⁺ and observations made concerning acceptor doping with Ti³⁺.     

Effects of Annealing Temperature on Microstructural Development at the Interface Between Zirconia and Titanium

The interfacial reaction layers in the Ti/ZrO₂ diffusion couples, isothermally annealed in argon at temperatures ranging from 1100° to 1550°C for 6 h, were characterized using scanning electron microscopy and transmission electron microscopy, both attached with an energy-dispersive spectrometer. Very limited reaction occurred between Ti and ZrO₂ at 1100°C. A β'-Ti(Zr, O) layer and a two-phase α-Ti(O)+β'-Ti(Zr, O) layer were found in the titanium side after annealing at T ≥1300°C and T ≥1400°C, respectively. A three-phase layer, consisting of Ti₂ZrO+α-Ti(O, Zr)+β'-Ti (O, Zr), was formed after annealing at 1550°C. In the zirconia side near the original interface, β'-Ti coexisted with fine spherical c- ZrO_{2− x} , which dissolved a significant amount of Y₂O₃ in solid solution at T ≥1300°C. Further into the ceramic side, the α-Zr was formed due to the exsolution of Zr out of the metastable ZrO_{2− x} after annealing at T ≥1300°C: the α-Zr was very fine and dense at 1300°C, continuously distributed along grain boundaries at 1400°C, and became coarsened at 1550°C. Zirconia grains grew significantly at T ≥1400°C, with the lenticular t -ZrO_{2− x} being precipitated in c -ZrO_{2− x} . Finally, the microstructural development and diffusion paths in the Ti/ZrO₂ diffusion couples annealed at various temperatures were also described with the aid of the Ti–Zr–O ternary phase diagram.     

Fatigue-Free Lead Zirconate Titanate (Pb(Zr,Ti)O3)-Based Capacitors Co-modified by Lanthanum and Lithium for Nonvolatile Memories

Pb_0.98(La_{1− x} Li _x )_0.02(Zr_0.55Ti_0.45)O₃(PLLZT with 0.1 ≤ x ≤ 0.7) thin films were sol-gel-grown on Pt(111)/Ti/SiO₂/Si substrates, employing a thin lead zirconate titanate (PZT) template layer. Films annealed at >550°C showed a highly (111)-oriented preferential growth. Typical values of the switchable remanent polarization (2 P _r) and the coercive field ( E _c) of the PLLZT/PZT/Pt film capacitor for x = 0.3 were 50 μC/cm² and 39 kV/cm, respectively, at 5 V. All the PLLZT/PZT/Pt capacitors (for 0.1 ≤ x ≤ 0.7) exhibited fatigue-free behavior up to 6.5 × 10¹⁰ switching cycles, a quite stable charge retention profile with time, and high 2 P _rvalues, all which assure their suitability for nonvolatile ferroelectric memories.     

Sintering Behavior, Phase Evolution, and Microwave Dielectric Properties of Bi(Sb1−xTax)O4 Ceramics

Sintering behavior, phase evolution, and microwave dielectric properties of Bi(Sb_{1− x} Ta _x )O₄ ceramics (0.05≤ x ≤0.60) were studied and their relationships were discussed in detail. Phase studies revealed that a pure monoclinic phase could be formed when x ≤0.20 and a pure orthorhombic phase could be obtained when x ≥0.50. As the x value increased from 0.05 to 0.60, the densified temperature of Bi(Sb_{1− x} Ta _x )O₄ ceramics decreased from 1050° to about 960°C whereas the density increased from 8.07 to 8.41 g/cm³. The microwave dielectric constant increased from 20.5 to 34 whereas the Q × f value decreased from 60 000 to 29 000 GHz. In the monoclinic phase region, the temperature coefficients of resonant frequency shifted linearly from −58 to −45 ppm/°C as the x value increased from 0.05 to 0.2 and then remained constant at about −12 ppm/°C when x ≥0.40. The Bi(Sb_{1− x} Ta _x )O₄ ceramics are promising for application of low-temperature cofired ceramics technology.     

Subsolidus Phase Relations and Transparent Conductors in the Cadmium-Indium-Tin Oxide System

Subsolidus phase relations have been determined in the CdO–InO_1.5–SnO₂ system at 1175°C. A cubic-bixbyite solution In_{2−2 x} (Cd,Sn)_{2 x} O₃ (0 < x < 0.34), a cubic spinel solution (1− x )CdIn₂O₄– x Cd₂SnO₄ (0 < x < 0.75), and an orthorhombic-perovskite solution Cd_{1− x} Sn_{1− x} In_{2 x} O₃ (0 < x < 0.045) having the GdFeO₃ structure have been discovered. The CdO phase field exists over a small range of InO_1.5 (<3%) and SnO₂ (<1%). Orthorhombic Cd₂SnO₄ (Sr₂PbO₄ structure) and rutile SnO₂ appear to be point compounds with negligible solubility. The vertical section between spinel CdIn₂O₄ and orthorhombic Cd₂SnO₄ was determined between 900° and 1175°C. The spinel phase field (1− x )CdIn₂O₄– x Cd₂SnO₄ was found to extend between x = 0 and x = 0.75 at 1175°C or x = 0.78 at 900°C. All of the phases in this system appear to allow small excess quantities of the donors In and/or Sn (vs cation stoichiometry) which may be the source of the electrons that give these oxides their n-type character. The electrical and optical properties of bulk and thin-film specimens in this system are compared and contrasted with each other and the relative merits of each are assessed.     

Processing and Properties of Strontium Bismuth Vanadate Niobate Ferroelectric Ceramics

The processing conditions, microstructure, and dielectric properties of strontium bismuth niobate vanadate ceramics, SrBi₂(V _x Nb_{1− x} )₂O₉ (SBVN, with 0 ≤ x ≤ 0.3), were systematically studied. A relative density of >90% was obtained for all the samples using a two-step sintering process. XRD showed that a single phase with the layered perovskite structure of SrBi₂Nb₂O₉ (SBN) was formed with a vanadium content of up to 30 at.%. SEM revealed that the average grain size decreased gradually with an increase in vanadium content. The Curie point was found to gradually increase from ∼418°C for SBN to ∼459°C for SBVN with 30 at.% vanadium. Dielectric constants at room temperature and their respective Curie points were found to peak at a composition with 10–15 at.%; vanadium. Moreover, a high concentration of vanadium (>5 at.%) resulted in a significant increase in tangent loss at low frequencies (<1000 Hz). The relationships between chemical composition, processing condition, microstructure, and dielectric properties of SBVN ferroelectric ceramics are discussed.     

Thermodynamic and Structural Properties of Sodium Lithium Niobate Solid Solutions

Thermodynamics of the Na_1−xLi _x NbO₃ system is investigated by high-temperature drop-solution calorimetry in molten 3Na₂O–4MoO₃ solvent at 973 K. Standard molar enthalpies of formation are derived. The estimated heats of transition between hypothetical and stable structures, lithium niobate and perovskite for NaNbO₃ and vice versa for LiNbO₃ are −6 kJ/mol and −10 kJ/mol, respectively. X-ray diffraction studies at room temperature showed for 0 ≤ x ≤ 0.14 there are three phases based on different ordering of the perovskite type lattice: orthorhombic with a quadrupled reduced perovskite cell at 0 ≤ x ≤ 0.02, orthorhombic with a doubled reduced perovskite cell at 0.015 ≤ x ≤ 0.14, and rhombohedral at 0.08 ≤ x ≤ 0.13. There are two two-phase (morphotropic) regions with coexistence of the two orthorhombic phases at 0.015 ≤ x ≤ 0.02 and with the second orthorhombic phase coexisting with the rhombohedral phase at 0.08 ≤ x ≤ 0.13. A reproducible anomaly in specific heat at ∼600 K, not reported previously, has been observed in pure NaNbO₃. Heat-capacity measurements confirm a phase transition at 553 K for 0.07 ≤ x ≤ 0.09. With increasing lithium concentration, a gradual disappearance of high-temperature phase transitions associated with tilting of oxygen octahedra has been observed.     

Enhanced Thermal Stability of Zinc-Based Titanate (Dielectric) Ceramics Prepared by the Modified Sol–gel Route

A multi-component substitution of Co and Ni was incorporated into ZnTiO₃ to form pure hexagonal Zn_{1− x} (Co_1/2Ni_1/2) _x TiO₃ ( x =0,0.8,0.9,1.0) dielectric ceramic powders by a modified sol–gel route, following heat treatments at 600°C for 3 h and at 800°C for 6 h. Differential scanning calorimetry measurements revealed that the order of increasing thermal stability of solid solution compound Zn_{1− x} (Co_1/2Ni_1/2) _x TiO₃ was ZnTiO₃ (945°C), Zn_0.1Ni_0.9TiO₃ (1346°C), Zn_0.1(Co_1/2Ni_1/2)_0.9TiO₃ (1390°C), and Zn_0.1Co_0.9TiO₃ (>1400°C). Both the dielectric constant and loss tangent reached a maximum at x =0.8 and then decreased with solubility, x , and measurement frequency.     

Microwave Dielectric Properties of CaTiO3-CaAl1/2Nb1/2O3 Ceramics Doped with Li3NbO4

The microwave dielectric properties of CaTi_{1− x} (Al_1/2Nb_1/2) _x O₃ solid solutions (0.3 ≤ x ≤ 0.7) have been investigated. The sintered samples had perovskite structures similar to CaTiO₃. The substitution of Ti⁴⁺ by Al³⁺/Nb⁵⁺ improved the quality factor Q of the sintered specimens. A small addition of Li₃NbO₄ (about 1 wt%) was found to be very effective for lowering sintering temperature of ceramics from 1450–1500° to 1300°C. The composition with x = 0.5 sintered at 1300°C for 5 h revealed excellent dielectric properties, namely, a dielectric constant (ɛ_r) of 48, a Q × f value of 32 100 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −2 ppm/K. Li₃NbO₄ as a sintering additive had no harmful influence on τ_f of ceramics.     

Fabrication of Low-Porosity Indium Tin Oxide Ceramics in Air from Hydrothermally Prepared Powder

Compositionally homogeneous indium tin oxide (ITO) ceramics with low porosity were obtained successfully by sintering hydrothermally prepared powders. The fabrication technique began with the preparation of microcrystalline, homogeneously tin-doped (5 wt%) indium oxyhydroxide powder, under hydrothermal conditions. Low-temperature (∼500°C) calcination of the hydrothermally derived powder led to the formation of a substitutional-vacancy-type solid solution of In₂Sn_{1− x} O_{5− y} , and further heating of this phase at temperatures of >1000°C resulted in the formation of the tin-doped indium oxide phase, which had the C -type rare-earth-oxide structure. The sintering of uniformly packed, calcined powder compacts at 1450°C for 3 h in air resulted in low-porosity (∼0.7%) ITO ceramics.     

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.     

Phase-Selective Pyrolysis and Pr3+ Luminescence in a YF3–Y2O3 System from a Single-Source Precursor

Pr³⁺-doped YF₃ (orthorhombic), YO_0.80F_1.40 (orthorhombic), YOF (rhombohedral), and Y₂O₃ (cubic) films were synthesized on quartz-glass substrates through pyrolysis of a single-source trifluoroacetate precursor at temperatures between 400° and 900°C in air. Phase-selective deposition was achieved by controlling heating temperature and time. YF₃, which formed first from the precursor, was transformed to YO_0.80F_1.40, YOF, and Y₂O₃. Photoluminescent properties of Pr³⁺-doped films were examined using ultraviolet excitation. An intense green photoluminescence was observed in the YOF:Pr³⁺ film, which was deposited at 700°C, through an efficient charge transfer (O²⁻–Pr³⁺) excitation.     

X-ray Diffraction and 151Eu Mössbauer Spectroscopic Study of the Hf1−xEuxO2−x/2(0 ≤x≤ 1.0) System

Powder X-ray diffractometry (XRD) and ¹⁵¹Eu Mössbauer spectroscopy were performed for samples prepared in the temperature range 1500–1500°C for the hafnia–europia (HfO₂–Eu₂O₃) system Eu _x Hf_{1− x} O_{2− x /2}(0 ≤ x ≤ 1.0). The XRD results showed that two types of solid solution phases formed in the composition range 0.25 ≤ x ≤ 0.725: an ordered pyrochlore-type phase in the middle-composition range (0.45 < x < 0.575) and a disordered fluorite-type phase, enveloping the pyrochlore-type phase on both sides, in the composition ranges 0.25 ≤ x ≤ 0.40 and 0.60 ≤ x ≤ 0.725. ¹⁵¹Eu Mössbauer spectroscopy sensitively probes local environmental changes around trivalent europium (Eu³⁺) caused by the formation of these solid solution phases. In addition to the broad, single Mössbauer spectra observed in this study for the Eu³⁺, the values of isomer shift (IS) exhibited a pronounced minimum in the neighborhood of the stoichiometric pyrochlore phase ( x ≈ 0.5). Such IS behavior of Eu³⁺ was interpreted based on the XRD crystallographic information that the ordered pyrochlore phase has a longer (in fact, the longest) average Eu–O bond length than those of the disordered fluorite phases on both sides or the monoclinic (and C-type) Eu₂O₃at x = 1.0.