Phase relationships in the systems RE2O3-Al2O3-SiO2 (RE = rare earth element, Y, and Sc)

A literature survey and recent results on phase relationships in the quasi-ternary systems RE₂O₃-Al₂O₃-SiO₂ are given. The investigated systems exhibit extended ternary solid solutions, RE_9.33+2x(Si_{1_x}Al_xO₄)₆O₂ (withx up to ~0.33) and/or RE₄Al_{2(1_X)}Si_2xO_9+x (withx up to ~0.3), which are based on the quasi-binary phases RE_9.33(SiO₄)₆O₂ and RE₄A1₂O₉, respectively. The former is encountered only in systems with laige RE³⁺ ions (e.g., La³⁺), whereas the latter is found in systems with small RE³⁺ ions (e.g., Yb³⁺); in systems with medium-sized KE³⁺ ions (e.g., Gd³⁺) both types exist Quasi-ternary compounds are known only in the La, Ce, and Sc systems. Severe discrepancies in reported ternary eutectic temperatures led to a need for their accurate redeteimination.     

Luminescence and energy transfer of Mn and Tb in Y3Al5O12 phosphors

Mn²⁺ is an excellent luminescent ion with variable color from green, yellow to red in different hosts and has been widely utilized in recent years. The luminescent intensity of Mn²⁺ in many hosts is so low that the correlative application is restricted. In the present paper, two methods, i.e. employing a charge compensator and introducing a sensitizer, were adopted to enhance the luminescence of Mn²⁺ in Y₃Al₅O₁₂ (YAG). By employing Si⁴⁺ as a charge compensator, the doping content of Mn²⁺ (x) in Y₃Mn_xAl_5−2xSi_xO₁₂ can be lifted up to 0.4. Mn²⁺ in YAG emits orange light in a broad band. The peak wavelength shifts from 586 to 593 nm with the increasing x. The luminescent intensity of Mn²⁺ reaches its maximum when x = 0.1. Co-doping Tb³⁺ into Mn²⁺ doped YAG, the sensitization effect of Tb³⁺ on Mn²⁺ was observed clearly. The resonance energy transfer from Tb³⁺ to Mn²⁺ occurs because there is a well overlapping between emission spectrum of Tb³⁺ and excitation spectrum of Mn²⁺. A reasonable explanation for the sensitization effect of Tb³⁺ on the luminescence of Mn²⁺ was brought forward.     

Synthesis and luminescent properties of Ln3+ (Ln3+ = Eu3+, Dy3+) -doped Bi2ZnB2O7 phosphors

The new phosphors Bi2ZnB2O7:Ln3+ (Ln3+ =Eu3+,Dy3+) were synthesized by solid-state reaction technique.The obtained phosphors were investigated by means of X-ray powder diffraction (XRD),photoluminescence excitation and emission spectra with the aim of enhancing the fundamental knowledge about the luminescent properties of Eu3+ and Dy3+ ions in the Bi2ZnB2O7 host lattice.XRD analysis shows that all these compounds are of a single phase of Bi2ZnB2O7.The excitation and emission spectra of Bi2ZnB2O7:Ln3+ (Ln3+ =Eu3+,Dy3+) at room temperature show the typical 4f-4f transitions of Eu3+ and Dy3+,respectively.The hypersensitive transitions of 5D0→7F2 (Eu3+) and 4F9/2→ 6H13/2 (Dy3+) are relatively higher than those of the insensitive transitions in Bi2ZnB2O7.It is conceivable that the Bi2ZnB2O7 structure provides asymmetry sites for activators (Eu3+,Dy3+).The optimum concentrations of Eu3+ and Dy3+ ions in Bi2ZnB2O7 phosphors are both x =0.05.     

Synthesis and characterization of Al2O3-Ce0.5Zr0.5O2 powders prepared by chemical coprecipitation method

Al₂O₃-Ce_0.5Zr_0.5O₂ catalytic powders were synthesized by the coprecipitation (ACZ-C) and mechanical mixing (ACZ-M) methods, respectively. As-synthesized powders were characterized by XRD, Raman spectroscopy, surface area and thermogravimetric analyses. It was found that the mixing extent of Al³⁺ ions affected the phase development, texture and oxygen storage capacity (OSC) of the Ce_0.5Zr_0.5O₂ powder. Single phase of ACZ-C could be maintained without phase separation and inhibit α-Al₂O₃ formation up to 1200 °C. The specific surface area value of ACZ-C (81.5 m²/g) was larger than that of ACZ-M (62.1 m²/g) and Ce_0.5Zr_0.5O₂ (17.1 m²/g) powders, which were calcined at 1000 °C. In comparison with ACZ-C and Al₂O₃, which were calcined at high temperature (900–1200 °C), it was found that the degradation rate of specific surface area of ACZ-C was lower than that of Al₂O₃. ACZ-C sample showed a higher thermal stability to resist phase separation and crystallite growth, which enhanced the oxygen storage capacity property for Ce_0.5Zr_0.5O₂ powders.     

Effects of Al and Al4C3 contents on combustion synthesis of Cr2AlC from Cr2O3-Al-Al4C3 powder compacts

Preparation of the ternary carbide Cr₂AlC was conducted by combustion synthesis in the mode of self-propagating high-temperature synthesis (SHS) from the Cr₂O₃-Al-Al₄C₃ powder compact. Effects of the contents of Al and Al₄C₃ on the product composition and combustion behavior were studied by formulating the reactant mixture with a stoichiometric proportion of Cr₂O₃:Al:Al₄C₃ = 3:5x:y, where x and y varied from 1.0 to 1.5. When compared to those of the powder compact with Cr₂O₃:Al:Al₄C₃ = 3:5:1 (i.e., x = y = 1.0), the combustion temperature and reaction front velocity increased with content of Al, but decreased with that of Al₄C₃. Besides Cr₂AlC and Al₂O₃, the final products always contained a secondary phase Cr₇C₃ that was substantially reduced by adopting additional Al and Al₄C₃ in the reactant compacts. For the sample with Cr₂O₃:Al:Al₄C₃ = 3:7.5:1 (x = 1.5), solid state combustion reached a peak temperature of 1245 °C and yielded Cr₂AlC with a trivial amount of Cr₇C₃. Although Cr₇C₃ was lessened by introducing extra Al₄C₃, the increase of Al₄C₃ from y = 1.1 to 1.5 produced almost no further reduction of Cr₇C₃ in the final product. This is partly attributed to the low combustion temperature in the range of 1065-1095 °C for the samples with additional Al₄C₃, and in part, due to the role of Al₄C₃ which might react with Cr to form Cr₇C₃, Cr₂Al, and Cr₂AlC.     

Synthesis, characterization and magnetic properties of complex oxides Ln2Mn2/3Re4/3O7 (Ln = Er, Y) and Y2Zn2/3Re4/3O7

Complex oxides Ln₂Mn_2/3Re_4/3O₇ (Ln = Y, Er) and Y₂Zn_2/3Re_4/3O₇ with a zirkelite structure and hexagonal unit cells (space group P3₁21, z = 6) have been obtained. Static and dynamic magnetic susceptibility measurements show that these oxides possess spin-glass behavior at low temperatures. Valence combinations of d-metals in the oxides are Mn²⁺(Zn²⁺)–Re⁵⁺. It is supposed that the examined specimens Ln₂Mn_2/3Re_4/3O₇ (Ln = Y, Er) contain the second magnetic phase of an unknown composition.     

Influence of B site substituent Ti on the structure and thermophysical properties of A2B2O7-type pyrochlore Gd2Zr2O7

Since the structural integrity of A₂B₂O₇-type pyrochlores relies mostly on the interconnecting BO₆ octahedra, Ti⁴⁺ was selected to partially substitute Zr⁴⁺ in Gd₂Zr₂O₇ in order to distort the pyrochlore structure in order to improve the material’s thermophysical properties for potential use as high-temperature thermal insulation. As evidenced by X-ray diffraction and Raman spectroscopy studies, incorporation of Ti⁴⁺ simultaneously leads to long-range ordering of the pyrochlore structure as well as local lattice distortion. These two effects have been shown to be competitive in determining the crystal energy of the Gd₂(Zr_1−xTi_x)₂O₇ series and result in a minimum value of the Young’s modulus at x = 0.3 and a maximum value of the coefficient of thermal expansion at x = 0.2. At lower temperatures, the thermal conductivity of Gd₂Zr₂O₇ was significantly reduced by Ti⁴⁺ doping, and its composition dependence was accurately modeled by taking into account the phonon scattering by mass and strain fluctuations at the B site.     

Magnetic study of Ti-substituted NiFe2O4 ferrite

The Ni_1+xTi_xFe_2−2xO₄ (0 ≤ x ≤ 0.1) ferrite systems prepared by a semi-chemical route, have been studied by electron paramagnetic resonance (EPR) at X-band, Mössbauer spectroscopy and magnetization measurements at various temperatures. EPR spectra of these samples comprise generally a broad and asymmetric EPR signal. The variation of g_eff and peak-to-peak line width ΔH_pp, with Ti concentration and temperature are attributed to the variation of dipole–dipole interaction and the superexchange interaction. Mössbauer spectra comprise two sets of sextet attributed to Fe³⁺ at two distinct sites-A and -B. Ti⁴⁺ ions are concluded to occupy the octahedral B-sites. Magnetic moment is found to decrease with the increase of Ti⁴⁺ concentration. The effective magnetic field H_eff at the A-sites also follows a similar trend. The reason is attributed to the canted structure of spins in the Ti-doped samples. An anomalous behavior at x = 0.015 is observed in the properties studied here and some sort of phase change is believed to occur at 473 K in these ferrites.     

Piezoelectric and dielectric properties of Dy2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + x wt% Dy₂O₃ with x = 0-0.3 ceramics were synthesized by conventional solid-state processes. The effects of Dy₂O₃ on the microstructure, the piezoelectric and dielectric properties were investigated. X-ray diffraction pattern confirmed that the coexistence of tetragonal and rhombohedral phases in the (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition was not changed by adding 0.05-0.3 wt% Dy₂O₃. SEM images indicate that all the ceramics have pore-free microstructures with high density, and that doping of Dy₂O₃ inhibits the grain growth of the ceramics. The addition of Dy₂O₃ shows the double effects on decreasing the piezoelectric and dielectric properties for 0 < x < 0.15 when Dy³⁺ ions substitute B-site Ti⁴⁺ ions, and increasing the properties for 0.15 < x < 0.3 when Dy³⁺ ions enters into A-site of the perovskite structure. The optimum electric properties of piezoelectric constant d₃₃ = 170 pC/N and the dielectric constant ?_r = 1900 (at a frequency of 1 kHz) are obtained at x = 0.3.     

Magnetic properties of Al2O3-Cr2O3 solid solutions

Solid solution ceramics (Al₂O₃)_x(Cr₂O₃)_1−x with different x in the range of 0 < x < 1 were synthesized via traditional ceramic production method. X-ray diffraction results and Rietveld refinements indicated that all samples possessed rhomb-centered structure and continuous solid solutions were synthesized. The samples were composed of irregular grains with several micrometers in diameter. Temperature dependence of magnetization measurements showed monotonous decreasing Néel temperature with increasing x and percolation effect happened with threshold of x = 0.65. As x became higher, weak ferromagnetism was observed in the samples. Field dependence of magnetization measurements further confirmed the weak ferromagnetism in the samples with x = 0.7, 0.8 and 0.9.     

Synthesis, structure and optical properties of CoAl2O4 spinel nanocrystals

CoAl₂O₄ nanocrystals were synthesized by sol-gel method using citric acid as a chelating agent at low temperature. The as-synthesized samples were characterized by thermal analysis, X-ray powder diffraction, infrared spectroscopy and transmission electron microscopy. The results show that CoAl₂O₄ spinel is the only crystalline phase with a size of 10-30 nm in the temperature range 500-1000 °C. The temperature dependence of the distribution of Al³⁺ and Co²⁺ ions in the octahedral and tetrahedral sites in nanocrystals was investigated by X-ray photoelectron spectroscopy (XPS). It is observed that the inversion parameter decreases with increasing annealing temperature. Analysis of the absorption properties indicates that Co²⁺ ions are located in the tetrahedral sites as well as in the octahedral sites in the CoAl₂O₄ nanocrystals. The origin of the green color (300-500 nm absorption band) should be due to the octahedrally coordinated Co²⁺ ions.     

Growth and annealing properties of Mg0.4Al2.4O4 crystal

Mg_0.4Al_2.4O₄ single crystals with good optical quality were successfully grown by the Czochralski method. The transmission spectrum indicated that the absorption edge of the crystal was at 220 nm, while no apparent absorption peaks were found. The X-ray diffraction and DSC curve analysis showed that Mg_0.4Al_2.4O₄ crystal was stable at room temperature. While after annealing in the air and hydrogen atmosphere at about 1200 °C, Mg_0.4Al_2.4O₄ decomposed into Al₂O₃ and (MgO)_0.4(Al₂O₃)_x (0.4 < x < 1.2). The reaction mainly occurred on the crystal surface, barely inside.     

Upconversion luminescence in Er/Yb codoped Y2CaGe4O12

Calcium yttrium tetrametagermanates Y₂CaGe₄O₁₂ doped with Er³⁺ and Er³⁺/Yb³⁺ reveal upconversion emission in visible spectral range under near-infrared excitation, λ_ex = 980 nm. For the solid solution Er_xY_2−xCaGe₄O₁₂ concentration dependencies for the green and red lines of the visible emission around 526 nm (²H_11/2 → ⁴I_15/2), 545 nm (⁴S_3/2 → ⁴I_15/2) and 670 nm (⁴F_9/2 → ⁴I_15/2) show the optimal value for the sample x = 0.2. The power dependence of the visible luminescence measured at room temperature in the low-power limit indicates two-photon upconversion process. Direct intensification of the upconversion emission signals has been achieved by ytterbium sensitizing. The other upconversion excitation mechanism in Y₂CaGe₄O₁₂:Er³⁺ is discussed for an 808 nm incident laser irradiation. A scheme of excitation and emission routes involving ground/excited state absorption, energy transfer upconversion, nonradiative multiphonon relaxation processes in trivalent lanthanide ions in Y₂CaGe₄O₁₂:Er³⁺ and Y₂CaGe₄O₁₂:Er³⁺, Yb³⁺ has been proposed. Conditions for visible emission occurrence under quasi-resonance λ_ex = 1064 nm excitation depending on pump power values are considered. In the low-power regime only near-infrared emission caused by the transition ⁴I_13/2 → ⁴I_15/2 in erbium ions has been detected.     

Thermodynamic reassessment of the BaO-B2O3 system

The BaO-B₂O₃ pseudobinary system is assessed. A two-sublattice ionic solution model, (Ba²⁺) _P (O²⁻, BO ₃ ³⁻ , B₄O ₇ ²⁻ , B₃O_4.5) _Q , is adopted to describe the liquid phase. All the solid phases are treated as stoichiometric compounds. A set of parameters consistent with most of the available experimental data on both phase diagram and thermodynamic properties is obtained by using CALPHAD technique. A comparison between the calculated results and experimental data as well as a previous assessment is presented.     

Spectroscopy features of Pr and Er ions in Li2O-ZrO2-SiO2 glass matrices mixed with some sesquioxides

The glasses of the composition Li₂O-ZrO₂-SiO₂: Pr₂O₃/Er₂O₃ mixed with three interesting sesquioxides (viz., Al₂O₃, Sc₂O₃, Y₂O₃) were synthesized. Optical absorption and fluorescence spectra (in the spectral range 350-2100 nm were studied at ambient temperature. The Judd-Ofelt theory was applied to characterize the absorption and luminescence spectra of Pr³⁺ and Er³⁺ ions in these glasses. Following the luminescence spectra, various radiative properties like transition probability A, branching ratio β and the radiative life time τ for different emission levels of two rare earth ions have been evaluated. The radiative life times for the upper levels ³P₀ (Pr³⁺) and ⁴S_3/2 (Er³⁺) have also been measured and quantum efficiencies were estimated. The variations observed in these parameters were discussed in the light of changing environment of rare earth ions due to mixing of different sesquioxides in the glass network.     

Spectroscopic and crystal field analysis of absorption and photoluminescence properties of red phosphor CaAl12O19:Mn modified by MgO

The spectroscopic properties of a series of red phosphors with general composition of CaAl₁₂O₁₉:yMn⁴⁺ and (Ca_1−xAl₁₂O₁₉, xMgO):yMn⁴⁺ (x = 0-1, y = 0.001-1.5%) synthesized by a modified solid state method in air have been investigated in detail. Addition of MgO is necessary for Mn⁴⁺ charge compensation and leads to the formation of separate crystal phases of Al₂O₃ and MgAl₂O₄, which was confirmed by the XRD studies. Enhancement of Mn⁴⁺ luminescence with increasing content of MgO was observed and a mechanism for explanation of this phenomenon is suggested. For an analysis of the crystal phases and luminescent efficiency of the phosphors in the prepared series, crystal field calculations of the Mn⁴⁺ energy levels have been performed. This theoretical approach allowed for assigning the observed excitation and emission spectra. Red shift of the Mn⁴⁺ luminescence with increasing concentration of Mg ions is explained from the point of view of enhanced nephelauxetic effect after doping.     

Phase Relations in the Systems SrO-Y2O3-CuO-O2 and CaO-Y2O3-CuO-O2 at 1173 K

Phase relations in the systems SrO-Y₂O₃-CuO-O₂ and CaO-Y₂O₃-CuO-O₂ at 1173 K were estab-lished by equilibrating different compositions in flowing oxygen gas at a pressure of 1.01 × 10⁵ Pa. The quenched samples were examined by optical microscopy, X-ray diffraction (XRD), energy dis-persive analysis of X-rays (EDAX), and electron spin resonance (ESR). In the system SrO-Y₂O₃-CuO-O₂, except for the limited substitution of Y₃+ for Sr₂+ ions in the ternary oxide Sr₁₄ Cu₂₄O₄₁, no new quaternary phase was found to be stable. The compositions corresponding to the solid solution Sr_14-xY_xCu₂₄O₄₁ and the compound SrCuO₂+δ lie above the plane containing SrO, Y₂O₃, and CuO, displaced towards the oxygen apex. However, in the system CaO-Y₂O₃-CuO-O₂ at 1173 K, all the condensed phases lie on the plane containing CaO, Y₂O₃, and CuO, and a new quaternary oxide YCa₂Cu₃O_6.5 is present. The quaternary phase has a composition that lies at the center of the non-stoichiometric field of the analogous phase YBa₂Cu₃O_7-δ in the BaO-Y₂O₃-CuO-O₂ system. The com-pound YCa₂Cu₃O_6.5 has the tetragonal structure and does not become superconducting at low temperature. Surprisingly, phase relations in the three systems CaO-Y₂O₃-CuO-O₂, SrO-Y₂O₃-CuO-O₂, and BaO-Y₂O₃-CuO-O₂ are found to be quite different.     

Preparation and luminescent characteristics of Sr3RE2(BO3)4:Dy (RE = Y, La, Gd) phosphors for white LED

Dysprosium-activated Sr₃RE₂(BO₃)₄ (RE = Y, La, Gd) phosphors were synthesized by a high temperature solid-state reaction method. The phase uniformity of the phosphors was characterized by X-ray powder diffraction (XRD) and the luminescence characteristics were investigated. The excitation spectra at 575 nm emission show strong spectral bands in the region of 300-500 nm. The emission spectra of the phosphors with 365 nm excitation show three bands centered at 484 nm, 575 nm and 680 nm, which originate from the transitions of ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2 and ⁴F_9/2 → ⁶H_11/2 of Dy³⁺, respectively. The effect of Dy³⁺ concentration on the emission intensity of the phosphors was investigated. The fluorescence decay curves for ⁴F_9/2 → ⁶H_13/2 excited at 365 nm and monitored at λ_em of 575 nm were measured. The decay times decreased slowly with increasing Dy³⁺ doping concentration due to a trap capturing to resonance fluorescence transfer of the activated ions and due to the exchange interactions between activated ion pairs. In order to determine the type of interaction between activated ions, the concentration dependence curves (lg(I/x) versus lg x) of Sr₃RE₂(BO₃)₄:Dy³⁺ (RE = Y, La, Gd) were plotted. The concentration quenching mechanism of the ⁴F_9/2 → ⁶H_13/2 (575 nm) transition of Dy³⁺ is the d-d interaction. All results indicate these phosphors are promising white-color luminescent materials.     

RE2Zr2O7-RETaO4体系中RE50TaxZr50-xO175+0.5x热障涂层氧化物的抗CMAS腐蚀特征(英文)

研究RE₂Zr₂O₇-RETaO₄体系中富稀土RE₅₀Ta_xZr_50-xO_175+0.5x氧化物在1300℃下抗钙镁铝硅酸盐(CMAS)腐蚀特征,并讨论RE³⁺和Ta⁵⁺离子对CMAS熔体腐蚀化学反应和反应结晶的影响。结果表明,伴随着热化学反应,磷灰石、烧绿石、再沉淀的萤石和过剩的Yb(Y)TaO₄相是主要的反应产物。磷灰石相和烧绿石相的形成能力与稀土离子半径成正比。Ta⁵⁺含量的增加能减少形成磷灰石相的稀土原子的有效数目。此外,RE₅₀Ta_xZr_50-xO_175+0.5x热障涂层氧化物的抗CMAS腐蚀能力由磷灰石相和烧绿石相共同决定。紧密混合的磷灰石和烧绿石相在腐蚀反应的前端产生致密的反应层,该结构能够抑制CMAS的继续渗透。萤石和RET...     

Fast consolidation of a nanocrystalline Al2O3 reinforced 3.7Fe0.54Cr0.18Al0.26Si0.016 composite from mechanical synthesized powder through pulsed current activated heating

Nanopowders of Fe_0.54Cr_0.18Al_0.26Si_0.016 and Al₂O₃ were synthesized from Fe₂O₃, Cr, Si, and Al powders using high-energy ball milling. A high-density nanocrystalline 3.7Fe_0.54Cr_0.18Al_0.26Si_0.016-Al₂O₃ composite was consolidated with mechanically synthesized powders of Al₂O₃ and 3.7Fe_0.54Cr_0.18Al_0.26Si_0.016-Al₂O₃ through a pulsed current activated sintering (PCAS) method within 1 min. The hardness of the composite and the average grain sizes of Al₂O₃ and Fe_0.54Cr_0.18Al_0.26Si_0.016 were investigated.