Fabrication and Luminescent Properties of Nd3+-Doped Lu2O3 Transparent Ceramics by Pressureless Sintering

The fabrication of transparent Nd³⁺ ion-doped Lu₂O₃ ceramics is investigated by pressureless sintering under a flowing H₂ atmosphere. The starting Nd-doped Lu₂O₃ nanocrystalline powder is synthesized by a modified coprecipitant processing using a NH₄OH+NH₄HCO₃ mixed solution as the precipitant. The thermal decomposition behavior of the precipitate precursor is studied by thermogravimetric analysis and differential thermal analysis. After calcination at 1000°C for 2 h, monodispersed Nd³⁺:Lu₂O₃ powder is obtained with a primary particle size of about 40 nm and a specific surface area of 13.7 m²/g. Green compacts, free of additives, are formed from the as-synthesized powder by dry pressing followed by cold isostatic pressing. Highly transparent Nd³⁺:Lu₂O₃ ceramics are obtained after being sintered under a dry H₂ atmosphere at 1880°C for 8 h. The linear optical transmittance of the polished transparent samples with a 1.4 mm thickness reaches 75.5% at the wavelength of 1080 nm. High-resolution transmission electron microscopy observations demonstrate a "clear" grain boundary between adjacent grains. The luminescent spectra showed that the absorption coefficient of the 3 at.% Nd-doped Lu₂O₃ ceramic at 807 nm reached 14 cm⁻¹, while the emission cross section at 1079 nm was 6.5 × 10⁻²⁰ cm².     

X-Ray, Micro-Raman, Optical Absorption/Emission Studies of ErNbO4 Grown by Vapor Transport Equilibration

Vapor transport equilibration (VTE) treatments were performed on a Y-cut bulk Er (1.6 mol%)-doped congruent LiNbO₃ crystal and an X-cut pure congruent crystal, on one surface of which a 40 nm-thick film of erbium metal was coated before the VTE treatment. Scanning electron microscope, powder or single-crystal X-ray diffraction (XRD), polarized infrared absorption/emission of Er³⁺ as well as micro-Raman spectroscopy were used to study the two VTE crystals. The results are discussed in comparison with a corresponding as-grown bulk Er-doped crystal, calcined ErNbO₄ powder, and a locally Er-doped congruent LiNbO₃ crystal prepared by using the standard Er-diffusion technique. The experimental results show that the VTE treatment induces the formation of micrometer-sized ErNbO₄ precipitates with the crystallographic morphology of a flat polyhedron not only on the surfaces of both crystals but also in the bulk of the homogeneously Er-doped one. The optical absorption and emission studies show that the formation of the precipitates results in substantial spectral changes in both the 0.98 and 1.5 μm regions. The micro-Raman studies allow to resolve four additional Raman peaks around 800 cm⁻¹ in the E(TO) spectra of the two VTE crystals. These additional Raman peaks are associated with the characteristic vibrations with respect to the NbO₄³⁻ group. Characteristic XRD, optical absorption, and emission and Raman peaks for identifying the ErNbO₄ phase are proposed. Finally, the formation mechanism and light-scattering effect of the precipitates are discussed.     

Electroceramics from Source Materials via Molecular Intermediates: PbTiO3 from TiO2 via [Ti(catecholate)3]2-

The precursor [NH₄]₂[Ti(catecholate)₃] · 2H₂O is known to react with Ba(OH)₂· 8H₂O in an acid/base process that generates Ba[Ti(catecholate)₃] · 3H₂O, a compound which undergoes low-temperatue calcination to produce BaTiO₃ powder. Attempts to develop similar routes to PbTiO₃ have been frustrated, since lead(II) hydroxide does not exist. The amphoteric yellow PbO and the basic oxide, Pb₆O(OH)₆⁴⁺, are both insufficiently basic to react with [NH₄]₂[Ti(catecholate)₃] · 2H₂O. Based on the large sizes of both the [Ti(catecholate)₃]^2- anion and the Pb²⁺ cation, a precipitation method has been developed in which lead nitrate and [NH₄]₂[Ti(catecholate)₃] · 2H₂O are added together in an aqueous medium causing precipitation and leaving only NH₄NO₃ in solution. The lead-titanium-catecholate complex that forms in this manner undergoes low-temperature pyrolysis to produce PbTiO₃. SEM indicates a submicrometer ultimate crystallite size.     

Vibrational Spectra of Water- and Ammonium-Chloride-Related Residues and Upconversion Fluorescence of Er3+ in ZnCl2-Based Glasses

Chloride glasses of the ZnCl₂ and 20KCl-20BaCl₂-60ZnCl₂-0.5ErCl₃ systems were prepared using NH₄Cl as a dehydrating and chlorinating agent, under the melt-quenching method. Water- and ammonium-chloride-related residues in ZnCl₂ glasses were investigated by infrared and near-infrared absorption spectra. Water, Zn—OH, ClO, ClO₂⁻, Zn²⁺-coordinated water, free NH₃, NH₄⁺, and Zn²⁺-coordinated NH₃ were identified in ZnCl₂ glasses. 20KCl-20BaCl₂-60ZnCl₂-0.5ErCl₃ glasses prepared by melting at 500°C for 20 min, under reduced pressure, contained the smallest amounts of water, Zn—OH, and Zn²⁺-coordinated NH₃ and showed strong Er³⁺ upconversion fluorescence.     

Defect Centers in Gamma-Irradiated Single-Crystal Al2O3

The γ-irradiation-induced optical absorption spectra of annealed Al₂O₃ single crystals were analyzed. The samples were beat-treated in O₂ or vacuum from 1600° to 1800°C. Four absorption bands are reported with average peak positions at 3.4,4.8,5.5, and 6.6 eV for samples annealed in O₂ at ≥ 1750°C. Vacuum anneals up to 1800°C and O₂ anneals at < 1700°C failed to generate observable bands in the energy range studied. There is also evidence that one or more bands exist at >6.6 eV. The radiation-induced change in the absorption spectra is reported and the defect centers responsible for the measured optical absorption bands are discussed with respect to the aliovalent impurities in the host lattice. Special attention is given to the role of the Fe³⁺ impurity ion.     

Ion Exchange in Alkali Layers of Potassium β -Ferrite ((1 + x)K2O · 11Fe2O3) Single Crystals

The potassium ions in potassium β-ferrite ((1 + x)K₂O ·11Fe₂O₃) crystals were exchanged with Na⁺, Rb⁺, Cs⁺, Ag⁺, NH₄⁺, and H₃O⁺ in molten nitrates or in concentrated H₂SO₄. On the other hand, spinel and hexagonal ferrites were formed by soaking the crystals in the melt of divalent salts. The crystals of K⁺, Rb⁺, and Cs⁺β-ferrites decomposed to form α-Fe₂O₃ at high temperatures of 800° to 1100°C. In addition, H₃O⁺, NH₄⁺, and Ag⁺β-ferrites decomposed to form α-Fe₂O₃ at relatively low temperatures of 350° to 650°C, in accordance with the stabilities of the inserted ions. The electrical properties of some β-ferrites were measured.     

Single Crystals of (PbxSr1-x) TiO3 Grown by Traveling Heater Method

A procedure is presented for growing single crystals of (Pb_xSr_1-x)TiO₃ by passing solvent zones through poly-crystalline rods of the same composition (THM). The solvent zone composition for homogeneous solid solution growth was chosen from the pseudoquaternary system 2PbO: 1B₂O₃-2SrO:1B₂O₃-PbTiO₃-SrTiO₃. Crystals with compositions throughout the complete range of PbTiO₃-SrTiOs solid solutions were grown. Emphasis was placed on crystal compositions near (Pb_0.25Sr_0.78) TiO₃ which have Curie temperatures just below room temperature. The dielectric constants, Curie temperatures, and optical properties of these single crystals are presented. Nonlinear dielectric and electrooptic behaviors are also demonstrated.     

Effects of SiF4 and NH3 Concentrations on the Low-Pressure CVD of Polycrystalline α-Si3N4

The effects of SiF₄ and NH₄ concentrations on the growth rate of polycrystalline α-Si₃N₄ were examined in the pressure range of 1.5 to 10.0 torr (1 torr ∽ 1.33 × 10² Pa). At low SiF₄ partial pressures, the growth rate increased almost linearly with the SiF₄ partial pressure. The relationship appeared to become zeroth-order at high SiF₄ partial pressures. Under excess NH₃ conditions, the growth rate was not significantly affected in any consistent manner by changes in the NH₃ partial pressure. A surface kinetic rate mechanism which qualitatively described the observed deposition behavior was postulated and discussed.     

Optical Spectra of 3d Transition Metal Ions in MgO 3·52O3 Spinel

Large gem-quality boules of MgO·3.5A1₂, O₃ spinel, both pure and incorporating controlled amounts of Ti³, V₃₊, Cr³⁺, Mn₂, Fe₂₊, Co²⁺, or Ni₂₊ were synthesized by a modified verneuil technique. Each crystal was characterized by measuring the lattice parameter, chemical composition, and density. Using thin polished slices as specimens, the absorption spectrum of each crystal was measured from 400 to 50, 000 cm⁻¹, and band centers and order-of-magnitude oscillator strengths were calculated from the spectrum for each specimen. For these well characterized crystals, the absorption spectra were interpreted satisfactorily in terms of crystal field theory when the complete individual spectrum as well as the spectrum of the host matrix was considered. On this basis, the oxidation state and coordination of the 3d ion could be determined. Covalent bonding effects were of definite significance in these spinels and caused an inexact correspondence between observed band centers and those predicted by the Orgel diagrams. The ratio Dq (tetrahedral)/ Dg (octahedral) was 0.67 in the 1:3.5 spinel and verified the theoretical relation expressing this ratio in terms of a constant, 4/9, times the fifth power of the ratio of the site radii. Coordination preferences of the incorporated transition metal ions are also discussed.     

Optical Spectra of the Various Valence States of Vanadium in Na2 O.2SiO2 Glass

Optical absorption data are presented for Na₂O₂SiO₂ glass containing vanadium equilibrated in various states of oxidation. Spectra of 5⁺, 4⁺, and 3⁺ vanadium were derived. The variation in amounts of the three species is in accord with mass action considerations. The spectra are related to crystal field assignments.     

Preparation and Upconversion Properties of Yb3+, Ho3+: Lu2O3 Nanocrystalline Powders

Yb³⁺, Ho³⁺: Lu₂O₃ nanocrystalline powders were synthesized by a reverse-strike co-precipitation method using NH₄HCO₃ and NH₃·H₂O as precipitators. X-ray diffraction analysis and field emission scanning electron microscopy observation showed that the phase composition of the powders was cubic and the particle size was 30–50 nm. Under the excitation of a 980 nm continuous wave diode laser, green and red emissions centered around 548 and 667 nm, respectively, were observed and the green emission dominated the upconversion spectrum. Power studies revealed that a two-photon process was involved in the upconversion emissions and the possible upconversion mechanisms were discussed.     

Structural Characterization and Luminescent Properties of a Red Phosphor Series: Y2−xEux(MoO4)3 (x=0.4–2.0)

A series of rare earth molybdates, Y_{2− x} Eu _x (MoO₄)₃ for x =0.4, 0.8, 1.2, 1.6 and 2.0 were prepared by solid-state method and their crystal structures, photo luminescent characteristics were investigated. The powders are mainly studied for their red light emission efficiency under near UV excitation. The crystal structures of the powders were found to depend on annealing temperature and the yttrium concentration. Mixtures of monoclinic ( C 2 /c ) and orthorhombic ( Pba 2, Pbna ) structures were formed in varying proportions depending on the value of x and annealing temperatures (700°–800°C). The luminescence behavior depended on the resultant composition of the crystal phase and the Eu³⁺ concentration. The excitation spectra showed the characteristic and broad O→Mo charge transfer (CT) band of the MoO₄ tetrahedra and the sharp intra-configurational 4 f –4 f transitions of Eu³⁺ in the host lattice. The integrated emission ratio (⁵D₀→⁷F₂/⁵D₀→⁷F₁) of Eu³⁺ depends on the annealing temperature and reveals that the local site symmetry of Eu³⁺ ions decreases with increasing concentration of Eu³⁺. The emission spectra obtained by exciting at 396 nm, gave highest red emission intensity for Y_0.4Eu_1.6(MoO₄)₃ annealed at 700°C/6 h among this series of samples.     

Crystallization and Properties of Fe2O3—CaO—SiO2 Glasses

Nucleation and crystal growth rates and properties were studied in a two-stage heat treatment process for Fe₂O₃-CaO-SiO₂ glasses. Glass transition (T_g) and crystallization temperatures (T _c ) for the glasses lay between about 612.0° and 710.0°C, and 858.5° and 905.0°C, respectively, and magnetite was the main crystal phase. For a glass of 40Fe₂O₃. 20CaO·40SiO₂ (in wt%) the maximum nucleation rate was (68.6 ± 7) × 10⁶/mm³·s at 700°C, and the maximum crystal growth rate was 9.0 nm/min^1/2 at 1000°C. The mean crystal size of the magnetite increased from 30 to 140 nm with variation of nucleation and crystal growth conditions. The glass showed the maxima in saturation magnetization and coercive force, 212.1 × Wb/m² and 30.8 × 10³ A/m, when heat-treated for 4 h at 1000°C and 1050°C, respectively. The variation of the saturation magnetization could be quantitatively interpreted well in terms of the volume fraction of the magnetite, whereas that of the coercive forces could be explained only qualitatively in terms of the particle size of the magnetite. Hysteresis losses showed the maximum value of 1493 W/m³ when heat-treated at 1000°C for 4 h prenucleated at 700°C for 60 min, and increased linearly with increasing heat treatment time under a magnetic field up to 800 × 10³ A/m.     

Synthesis of Anatase-Type TiO2 Nanocrystallites Via a Redox Route

Anatase nanocrystallites showing high surface area (∼62 m²/g) and good photocatalytic property have been obtained by pyrolyzing at 600°C for 4 h an ammonium titanyl double sulfate precursor (α-(NH₄)₂TiO(SO₄)₂) synthesized via a redox approach, that is, by oxidizing an aqueous solution of titanium trichloride (TiCl₃) with ammonium peroxodisulfate ((NH₄)₂S₂O₈), followed by reacting with ammonium sulfate ((NH₄)₂SO₄).     

Neutron Powder Diffraction of Nb2BN1-x

The crystal structure of Nb₂BN_1-x was determined from X-ray powder photographs; precise atom parameters, atom occupancies, and atom order were derived from room-temperature neutron powder diffraction data employing the Rietveld profile analysis method. The final reliability value of the refinement was R=0.031. Nb₂BN_1-x is the first boron nitride representative of the Mo₂BC-type structure crystallizing with the space group Cmcm-D¹⁷_2h No. 63. Boron atoms in triangular prismatic coordination [Nb₆B] are at a distance of 0.184 nm and form zigzag chains parallel to the c axis; the angle in the boron zigzag chain is 115.4°. Nitrogen atoms occupythe octahedral voids and are coordinated by six Nb atoms. With no N-N and no N-B contacts, the crystal structure of Nb₂BN_1-x represents the first typical transition-metal boron nitride.     

Calcium as an Acceptor Impurity in BaTiO3

The equilibrium electrical conductivity of polycrystalline, calcium-doped BaTiO₃ was studied over the oxygen partial pressure range 10^-13 to 10⁵ Pa and the temperature range 800° to 1000°C. There is little effect if CaO is substituted for a corresponding amount of BaO, i.e., Ba, _1-xCa_xTiO₃. If CaO is substituted for a corresponding amount of the TiO₂ content, i.e., BaTi_1-xCa_xO_3-x, the equilibrium conductivity shows strong evidence of acceptor-doped behavior. If the corresponding amount of excess CaO is added to stoichiometric BaTiO₃, i.e., BaCa_xTiO_3+x, the conductivity profiles are very close to those for samples with TiO₂ replaced by CaO, and show highly acceptor-doped behavior. This is in agreement with the replacement of a small amount of Ti by Ca²⁺ on the octahedral B-sites of BaTiO₃, where it acts as an acceptor center, Ca_T     

Crystal Field Studies of Co2+ in α-Zn3(VO4)2

Complete solid solubility was found in the system Cog-(VO₄)₂−α-Zn₃(VO₄)₂. Optical spectra of Co²⁺-containing α-Zn₃(VO₄)₂ samples are discussed in the light of crystal field theory. The calculated and theoretical frequencies were in good agreement for octahedral symmetry in the zinc sites. The crystal field parameter Dq was consistent with the ionic approximation rule. The nephelauxetic ratio did not show any relation to cation-anion distance. Most probably the expanding d-d electron clouds of Co²⁺ interacted.     

Addition of GeO2 to Reduce the Viscosity of Parent Glasses for Low-Expansion, Transparent Glass–Ceramics Containing High-Quartz Solid Solutions

Parent glasses for fabricating glass–ceramics with nanometer-sized crystals usually have high viscosities, resulting in high processing temperatures. In this study, GeO₂ was added to a transparent, near-zero thermal-expansion Li₂O–Al₂O₃–SiO₂ glass–ceramic to reduce the viscosity of the parent glass. The effects of this compositional modification on the viscosity and crystal-nucleation rate of the parent glasses, and on the crystal size, thermal expansion, and optical transparency of the resulting glass–ceramics were investigated. It was found that addition of GeO₂ was useful in reducing the glass viscosity. Owing to the reduced nucleating rate with the increase in the GeO₂ content, the nucleating times required for reaching the smallest crystal size, the lowest coefficient of thermal expansion, and the highest transparency were all increased. With increasing GeO₂ content, the lowest coefficient of thermal expansion that can be reached for glass–ceramics increased (0.14–2.9 × 10⁻⁶ K⁻¹). The highest transparency of the GeO₂-containing glass–ceramics is almost as good as that of the GeO₂-free glass–ceramic and is almost independent of GeO₂ content when the crystal size is smaller than about 65 nm.     

Optical Absorption Spectroscopy of ThO2

The optical absorption spectra from 200 to 2700 nm were determined for arc-fused ThO₂ crystals of much higher purity than any available hitherto. The fundamental absorption edge for these crystals lies at a much higher energy (∼5.9 eV) than the apparent edge reported previously for less pure specimens. This apparent edge is shown to result from one or more prominent high-energy absorption bands superimposed on the true edge for such specimens. By comparing the spectra for different specimens subjected to thermal and γ-irradiation treatments, 31 distinct absorption bands were revealed in the ThO₂ spectrum. A full analysis of certain crystals by spark-source mass spectrometry gave no strong correlation between specific band areas and individual impurity-element concentrations. Most of the bands, however, are believed to be associated with the impurity content.     

Phase Equilibria in the Spinel Region of the System FeO-Fe2O3-Al2O3

Phase relations in the spinel region of the system FeO-Fe₂O₃-Al₂O₃ were determined in CO₂ at 1300°, 1400°, and 15000°C and for partial oxygen pressures of 4 × 10⁻⁷ and 7 × 10⁻¹⁰ atmospheres at 15OO°C. The spinel field extends continuously from Fe₃O_4-x to FeAl₂O_4+z.