Phase structures in n-Y2O3

The phase structure of nanostructured Y₂O₃ (n-Y₂O₃) at low temperature was studied by x-ray diffraction profile refinement (XRDPR) method. All maximum X-ray diffraction peaks of Y₂O₃ were observed. The results show that the sample compacted at room temperature consists of two monoclinic phases B1 and B2 and a cubic phase. The samples sintered at 300°C and at 600°C for 5 hours, respectively, are also composed of monoclinic B1, B2 and cubic phases.The results show that with increasing temperature, grain growth, migration of grain boundary and phase transformation occur. This paper presents some quantitative information.     

Phase stabilization and structural studies of nanocrystalline La<Superscript>2</Superscript>O<Superscript>3</Superscript>-ZrO<Superscript>2</Superscript>

La²O³ doped nanocrystalline zirconia (ZrO²) has been prepared by chemical co-precipitation method for various dopant concentrations, varying from 3 to 30 mol%. Structural phases have been characterized by X-ray diffraction technique. All the as-synthesized samples were found to be in monoclinic phase. Annealing of the samples at different temperatures from 400 to 1000∘C stabilized ZrO² either partially or fully the tetragonal/cubic phases. When they were annealed at 1200∘C, the monoclinic phase appeared again with a new cubic pyrochlore structured La²Zr²O⁷ at the expense of stabilized tetragonal phase. Formability of the tetragonal/cubic phase has been influenced by the dopant concentration and the annealing temperature. Sample with 8 mol% La²O³ has been stabilized completely in tetragonal/cubic phase after annealing at 900∘C for 1 h. Smallness of the grain in these nanocrystalline materials may also have assisted in the formation of La²O³-ZrO² solid solution.     

Anomalous phase formation during annealing of La2O3 thin films deposited by ion beam assisted electron beam evaporation

The fifty seven nm thick La₂O₃ thin films were deposited on Si (100) substrates. After deposition, the amorphones thin films, were amorphous, were annealed at 750 and 900 °C for 1 h. It was found that their amorphous structure had been crystallized to hexagonal and cubic structures, respectively. The phase formation of the La₂O₃ thin films was anomalous at higher annealing temperatures. The theory of heterogeneous nucleation was used to interpret the anomalous phase formation of La₂O₃ films. To investigate the effects of the phase structure on these properties, Refractive indexes and dielectric constants of different structures of La₂O₃ films were measured.     

Phase relationships in the system Si3N4-SiO2-La2O3

Phase relationships in the system Si₃N₄-SiO₂-La₂O₃ have been investigated after cooling from 1700° C. Two phases, 2Si₃N₄·La₂O₃ (monoclinic) and La₅ (SiO₄)₃N (hexagonal), were identified; the other two phases in the system, LaSiO₂N (monoclinic) and La₄Si₂O₇N₂ (monoclinic), were found to dissociate to La₅ (SiO₄)₃N and a glass after cooling from temperatures above 1650° C. The unit cells of 2Si₃N₄·La₂O₃, LaSiO₂N and La₄Si₂O₇N₂ have been determined and compared with those of preceding works. The results are discussed in relation to the intergranular phases observed when Si₃N₄ is sintered with La₂O₃ additions.     

Chemical and structural properties of the system Fe2O3-In2O3

The system Fe₂O₃-In₂O₃ was studied using X-ray diffraction,⁵⁷Fe Mössbauer spectroscopy and infrared spectroscopy. The samples were prepared by chemical coprecipitation and thermal treatment of the hydroxide coprecipitates. For samples heated at 600 °C, a phase, α- (Fe_1?x In _x )₂O₃, isostructural with α-Fe₂O₃, exists for 0?x?0.8, and a phase C-(Fe_1?x In _x )₂O₃, isostructural with cubic In₂O₃, exists for 0.3?x?/1. In the two-phase region these two phases are poorly crystallized. An amorphous phase is also observed for 0.3?x?0.7. For samples heated at 900 °C the two-phase region is wider and exists for 0.1?x?0.8 with the two phases well crystallized. In these samples an amorphous phase is not observed.⁵⁷Fe Mössbauer spectroscopy of samples prepared at 600 °C indicated a general tendency of the broadening of spectral lines and the decrease of numerical values of the hyperfine magnetic field (HMF) with increasing molar fraction In₂O₃ in the system Fe₂O₃-In₂O₃. The samples prepared at 900 °C, in the two-phase region, are characterized by a constant HMF value of 510 kOe at room temperature. Infrared spectroscopy was also used to follow the changes in the infrared spectra of the system Fe₂O₃-In₂O₃ with gradual increase of molar fraction of In₂O₃. A correlation between X-ray diffraction, Mössbauer spectroscopic and infrared spectroscopic results was obtained.     

Analysis of second phase particles in a powder metallurgy HIP nickel-base superalloy

The nature of the second phase particles associated with LC Astroloy prepared using powder metallurgy techniques has been examined. The individual particles have been identified using energy dispersive X-ray analysis and convergent beam electron diffraction. Four distinct types of particles have been observed: a cubic MC carbide in which M is either titanium or titanium plus molybdenum, a monoclinic phase ZrO₂, a trigonalα-Al₂O₃ and a tetragonal M₃B₂ phase in which M is molybdenum or molybdenum and chromium. The observations indicate that, although some MC carbides are associated with the ZrO₂ phase, the majority of the prior particle boundary precipitates are separate entities. Hot isostatic pressing or subsequent heat treatments above or below the γ′ solvus were observed to have little effect on the incidence or distribution of the precipitation associated with the prior particle boundaries. In contrast, heat treatments above the γ′ solvus resulted in the dissolution of the M₂B₃ phase and its preferential precipitation on the grain boundaries.     

Acoustic emission study of phase relations in low-Y2O3 portion of ZrO2-Y2O3 system

The (metastable) tetragonal phase in 3–4 mol% Y₂O₃-ZrO₂ alloys undergoes a transition to the monoclinic form in the 200–300 °C temperature range. Microcracking due to the volume change at this transition has been detected in these compositions by sharp acoustic emission during heating. The phase change was confirmed by X-ray diffraction, dilatometry and scanning electron microscopy. The monoclinic tetragonal transition in ZrO₂-1 mol% Y₂O₃ alloy at 850–750 °C and the same phase change in 2, 3, 4 and 6 mol% Y₂O₃ compositions at the eutectoid temperature of about 560 °C was also clearly signalled by the acoustic emission counts during heating and cooling. There was no significant acoustic emission activity on heating and cooling the 9 and 12 mol% Y₂O₃ compositions, which are cubic. The acoustic emission data thus confirm the phase relations in the 1–12 mol% Y₂O₃ region, established by conventional methods such as differential thermal analysis, dilatometry and X-ray diffraction.     

Influence of composition on the T→M transformation in the systems ZrO2-Ln2O3 (Ln=La,Nd, Sm,Eu)

The systems ZrO₂-Ln₂O₃ have been studied on samples annealed at 600,1170,1450°C in the 0–15 mol % Ln₂O₃ (where Ln is the rare-earth La, Nd, Sm or Er) range using X-ray diffraction, thermal analysis and dilatometry. The microstructure of annealed samples was examined mainly by electron microscopy. It was found that rare-earth oxides-doped zirconia formed monoclinic, tetragonal, cubic and pyrochlore-type phases. The existing region of the tetragonal phase is 1–15 mol % Ln₂O₃, which is independent of the species but dependent on the dopant content and temperature. The equilibrium phase diagrams and non-equilibrium diagrams have been deduced. The temperature and composition of eutectoid ZrO_2,ss (T)→ZrO_2,ss (M) + Py, as well as interconnection between grain size, Ln₂O₃ content and the martensitic transformation temperature, (M _s), were determined.     

The effect of Bi2O3 on the microstructure and electrical conductivity of ZrO2-Y2O3 ceramics

ZrO₂-Y₂O₃ ceramics with varying Bi₂O₃ contents were prepared and their microstructures and electrical conductivities investigated. The phase stability of cubic fluorite zirconia was disturbed by the introduction of Bi₂O₃ and tetragonal or monoclinic second phases appeared. The effect of the second phases on the intragrain and the grain boundary conductivities was investigated in the 300–550 C range using complex plane analysis in the frequency range of 5 Hz to 13 MHz. It showed that conductivity data could readily be interpreted in terms of possible physical models and electrical equivalent circuits. Tetragonal phases had a small positive influence on the intragrain conductivity. The grain 9boundary resistivity could be diminished by discrete monoclinic second phases which offered more conductive intergranular contacts.     

Polymorphism of Bismuth Sesquioxide. I. Pure Bi2O3

Stability relationships of the four polymorphs of bismuth oxide have been determined by means of DTA and high-temperature x-ray studies. The stable low-temperature monoclinic form transforms to the stable cubic form at 730 ±5 °C, which then melts at 825 ± 5 °C. By controlled cooling, the metastable tetragonal phase and/or the metastable body-centered cubic (b.c.c.) phase appear at about 645 °C. Whereas b.c.c. can be preserved to room temperature, tetragonal will transform to monoclinic between 550 and 500 °C. Tetragonal Bi₂O₃, however, is easily prepared by decomposing bismutite (Bi₂O₃·CO₂) at 400 °C for several hours. The greatest transition expansion occurs at the monoclinic to cubic inversion, and cubic Bi₂O₃ shows the greatest coefficient of volume expansion. With exposure to air, Bi₂O₃ carbonates and partially transforms to bismutite and an unknown phase.     

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.     

Electrical properties of BaTiO3-based NTC thermistors doped by BaBiO3 and La2O3

In our research it has been firstly found that BaTiO₃ materials doped with BaBiO₃ only show negative temperature coefficient effect over a wide temperature range. Major phases present in the sintered bodies are BaTiO₃ compounds with a perovskite structure and BaBiO₃ compounds with a monoclinic structure. Also, at a given BaTiO₃ and BaBiO₃ content, the influence of La₂O₃ content on the microstructure and electrical properties has been investigated. The mean grain size of samples decreases with an increase in La₂O₃ content. However the mean grain size remains unchanged with a further increase in La₂O₃ content when the La₂O₃ content in material is more than 0.20. As the amount of La₂O₃ in BaTiO₃-based ceramics thermistors increases, the resistivity decreases to a minimum value and then slowly increases again.     

Characterization and densification of lanthana-zirconia powders prepared by high temperature hydrolysis

Zirconia-lanthana powders containing 4.5, 7, 10, 15 and 20 mol % La₂O₃ were prepared by hydrolysis. The hydrolysis process was carried out in a laboratory stainless steel autoclave for their equivalent hydroxides for 2 h at 200‡ C. The powders were investigated using X-ray diffraction, infrared spectrometry, and transmission electron microscopy techniques. No other phases except the cubic phase zirconia of fluorite-type structure were detected. The prepared materials were examined for their thermal stability and phase constitution, by X-ray and infrared analyses, on heating up to 1400‡ C. The cubic phase zirconia remains stable up to 1000‡ C at which it starts to decompose yielding monoclinic zirconia and lanthanum zirconate. At 1200‡ C, the cubic phase nearly disappears in the sample containing 4.5 mol % La₂O₃. Increasing La₂O₃ content up to 20 mol % retards its destabilization, reduces the yielded monoclinic phase, and in the same time increases the formed lanthanum zirconate phase. At 1500‡ C only monoclinic ZrO₂ and La₂Zr₂O₇ are present. The La₂Zr₂O₇/monoclinic ZrO₂ ratio increases with increasing La₂O₃ content. Pressed specimens of the prepared materials were fired for 2 h at 800 to 1400‡ C. The sintering activity of the prepared powders resulted in a 92% theoretical density body for the 4.5 mol % ZrO₂ material. The densification properties in relation to changes in the phase constitution are discussed.     

Effect of dopant concentration on electrical conductivity in the Sc2O3-ZrO2 system

Electrical conductivity measurements have been made as a function of dopant concentration (4 to 8 mol% Sc₂O₃) in the scandia-zirconia system, All the compositions studied had a tetragonal structure. The hombohedral phase was present only in samples prepared from mechanical mixtures of Sc₂O₃ and ZrO₂. In specimens prepared by coprecipitation, no phase lines were observed and the monoclinic zirconia (m-ZrO₂) phase was present for only Sc₂O₃ contents 5 mol %. The conductivity of Sc₂O₃-ZrO₂ decreased continuously with time up to 300 h anneal time between 700 and 1000° C. X-ray diffraction of coprecipated specimens of 7.8 mol % Sc₂O₃-ZrO₂ composition annealed at 1000° C (28 days), 750° C (42 days) or 460° C (189 days) did not reveal any changes to account for this. However, transmission electron microscopy showed that changes associated with the formation of very fine precipitates had occurred. The activation energy for conduction in the low-temperature region decreased monotonically with decrease in the scandia content. Jumps in the conductivity curves and hysterisis effects were observed in specimens containing m-ZrO₂.     

Metastable phase relation and phase equilibria in the Cr2O3-Fe2O3 system

In order to ascertain the metastable phase relation in the Cr₂O₃-Fe₂O₃ system, the existing phases were investigated by X-ray analysis using samples obtained by heating the coprecipitated powders for 1 h at 600–1000°C. There was a metastable two-phase region of Cr₂O₃-rich (CC) and Fe₂O₃-rich (FC) phases below about 940°C. Equilibrium state of 1:1 composition at 600–900°C was considered to be a single phase of the corundum solid solution. The metastable two-phase CC + FC region was suggested to appear probably due to the compositional inhomogeneity in the coprecipitated powders.     

Study of some aspects of the reactivity of La2O3 with CO2 and H2O

The behaviour of three different samples of La₂O₃ on exposure to atmoshperic CO₂ and H₂O and the influence of the origin is discussed. The thermal evolution of the samples, stabilized in air for months or even years, has been studied by TG, TPD, IR spectroscopy and X-ray diffraction. BET surface areas of the samples were determined from the corresponding nitrogen adsorption isotherms at 77 K. In all three samples, hydration and carbonation occur in bulk. In accordance with our results, lanthana samples stabilized in air would consist of lanthanum hydroxide, La(OH)₃, partially carbonated, La₂(OH)_6–3x (CO₃) _x ,(x1). When hexagonal phases of La₂O₃, obtained by calcining, at 1130 K, the samples stabilized in air were re-exposed, hydration and carbonation levels similar to those observed in the stabilized samples were reached after less than 24 h. Some lanthana samples were soaked in water, at 298 K, and then dried at 380 K. In this way, the evolution of the oxide when treated under similar conditions to those used in both impregnation and ion exchange techniques for preparation of supported metal phases, could be investigated.     

Effect of a Nonequilibrium State on Phase Relations in the System TiO2–Sc2O3 (40–50 mol % Sc2O3)

The phase transitions in TiO₂–Sc₂O₃ (40–50 mol % Sc₂O₃) samples prepared from coprecipitated and mechanically activated oxide mixtures are studied. It is shown that heat treatment below 1000°C leads to the formation of nonstoichiometric, metastable cubic phases with a distorted fluorite structure. With increasing temperature, this structure transforms into a stable fluorite-like structure through (low-symmetry) orthorhombic and hexagonal phases, which is associated with the incorporation of OH groups. Characteristically, the phases studied contain nanoscale regions differing in the degree of ordering, which result from internal stress. The internal stress in mechanically activated phases is shown to be fully relieved by about 1300°C.     

Luminescence and crystallinity of flame-made Y2O3:Eu3+ nanoparticles

Cubic and/or monoclinic Y₂O₃:Eu³⁺ nanoparticles (10–50 nm) were made continuously without post-processing by single-step, flame spray pyrolysis (FSP). These particles were characterized by X-ray diffraction, nitrogen adsorption and transmission electron microscopy. Photoluminescence (PL) emission and time-resolved PL intensity decay were measured from these powders. The influence of particle size on PL was examined by annealing (at 700–1300°C for 10 h) as-prepared, initially monoclinic Y₂O₃:Eu³⁺ nanoparticles resulting in larger 0.025–1 μm, cubic Y₂O₃:Eu³⁺. The influence of europium (Eu³⁺) content (1–10 wt%) on sintering dynamics as well as optical properties of the resulting powders was investigated. Longer high-temperature particle residence time during FSP resulted in cubic nanoparticles with lower maximum PL intensity than measured by commercial micron-sized bulk Y₂O₃:Eu³⁺ phosphor powder. After annealing as-prepared 5 wt% Eu-doped Y₂O₃ particles at 900, 1100 and 1300°C for 10 h, the PL intensity increased as particle size increased and finally (at 1300°C) showed similar PL intensity as that of commercially available, bulk Y₂O₃:Eu³⁺ (5 μm particle size). Eu doping stabilized the monoclinic Y₂O₃ and shifted the monoclinic to cubic transition towards higher temperatures.     

Synthesis, crystal structure and thermal decomposition of [La2(CH3CH2COO)6·(H2O)3]·3.5H2O precursor for high-k La2O3 thin films deposition

Lanthanum acetylacetonate La(C₅H₇O₂)₃·xH₂O has been used in the preparation of the precursor solution for the deposition of polycrystalline La₂O₃ thin films on Si(1 1 1) single crystalline substrates. The precursor chemistry of the as-prepared coating solution, precursor powder and precursor single crystal have been investigated by Fourier Transformed Infrared Spectroscopy (FTIR), differential thermal analysis coupled with quadrupole mass spectrometry (TG-DTA-QMS) and X-ray diffraction. The FTIR and X-ray diffraction analyses have revealed the complex nature of the coating solution due to the formation of a lanthanum propionate complex. The La₂O₃ thin films deposited by spin coating on Si(1 1 1) substrate exhibit good morphological and structural properties. The films heat treated at 800 °C crystallize in a hexagonal phase with the lattice parameters a = 3,89 Å and c = 6.33 Å, while at 900 °C the films contain both the hexagonal and cubic La₂O₃ phase.     

Photoluminescence of Ti3+ in P2O5-Na2O-Al2O3 glass

The optical properties (absorption and luminescence) of Ti³⁺ in a P₂O₅ Na₂O-Al₂O₃ glass have been studied in the temperature range 12 to 300 K. A very broad infrared emission band at 860 nm, has been observed for the first time in an inorganic glass, when excitation is performed in the Ti³⁺ absorption band (T_2g → E_g transition in cubic field approximation). The spectroscopic characteristics of this system are compared with those of the Ti³⁺ as a dopant in AL₂O₃ single crystals.