Preparation and luminescent properties of Cr3+:Al2O3 nano-powders by low-temperature combustion synthesis

Cr³⁺:Al₂O₃ nano-powders were prepared through low-temperature combustion synthesis (LCS) method by using glucose as a dispersion agent for the first time. The Cr³⁺:Al₂O₃ nano-powders samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and luminescence spectrometer. XRD results showed that pure α-Al₂O₃ phase was obtained for the sample fired at 1100 °C for 0.5 h. TEM results indicated that nano-powders were well dispersed. Luminescence spectrum analysis results indicated that the excitation spectrum of Cr³⁺:Al₂O₃ nano-powders consisted of two bands peaking at 462 nm and 579 nm, respectively, and the emission spectrum consisted of two bands peaking at 692 nm and 668 nm, respectively.     

Hydrothermally-mediated preparation and photoluminescent properties of Sr3Al2O6:Eu3+ phosphor

Hydrogarnet Sr₃Al₂(OH)₁₂ (SAH) has been obtained from hydrothermal systems with a wide range of pH values under mild conditions. The influence of reaction conditions on the formation of various phases has been considered. The addition of sodium hydroxide can favor the yield of pure SAH phase. Stoichiometric Sr₃Al₂O₆ (SAO) has been prepared from SAH through thermal decomposition over 600 °C for 4 h. SAO can act as a red phosphor host with doping of Eu³⁺ ions. The Eu³⁺ ions as activators can be introduced directly under hydrothermal conditions before thermal decomposition.     

Structural,morphological and electrical properties of Cr2O3 nanoparticles

Chromium oxide (Cr₂O₃) nanoparticles have been prepared by chemical precipitation followed by calcination at high temperatures. The influence of calcination temperature on the particle size, microstructure, surface area and morphology was examined by X-ray diffraction, Fourier transform infrared, N₂ adsorption–desorption isotherms, transmission electron microscopy and thermal analysis techniques. The results indicate the formation of a nanosized single Cr₂O₃ phase. The particles possess high specific surface area and mesoporous structure, and their sizes increase with increasing the calcinations temperature. DC conductivity was measured in the temperatures range of 170–475 K. For the high temperature region, the conduction was found to be due to small polaron hopping of holes. While for the low temperatures region, the conduction was attributed to variable range hopping mechanism of holes. The temperature dependence of the AC conductivity and dielectric constant was investigated in the same temperature range at four test frequencies. In addition, the impedance spectra of these nanoparticles were investigated only at temperatures above 350 K.     

Al2O3:Cr3+ microfibers by hydrothermal route: Luminescence properties

Uniform Al₂O₃:Cr³⁺ microfibers were synthesized by using a hydrothermal route and thermal decomposition of a precursor of Cr³⁺ doped ammonium aluminum hydroxide carbonate (denoted as AAHC), and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) spectra and decay curves. XRD indicated that Cr³⁺ doped samples calcined at 1473 K were the most of α-Al₂O₃ phase. SEM showed that the length and diameter of these Cr³⁺ doped alumina microfibers were about 3–9 μm and 300 nm, respectively. PL spectra showed that the Al₂O₃:Cr³⁺ microfibers presented a broad R band at 696 nm. It is shown that the 0.07 mol% of doping concentration of Cr³⁺ ions in α-Al₂O₃:Cr³⁺ was optimum. According to Dexter's theory, the critical distance between Cr³⁺ ions for energy transfer was determined to be 38 Å. It is found that the curve followed the single-exponential decay.     

H3BO3对化学共沉淀法制备Sr4Al14O25：Eu^2＋、Dy^3＋的影响

采用化学共沉淀法制备Sr4Al14O25:Eu^2 、Dy^3 长余辉发光粉体。研究了H3BO3的加入对粉体的相组成，晶体结构，发光性能与长余辉特性的影响。结果表明．加入的H3BO3大部分不进入晶格．作为助熔剂有利于Sr4Al14O25相的形成．一小部分H3BO3进入晶格中取代Al^3 离子并且对Sr4Al14O25:Eu^2 、Dy^3 长余辉发光粉体的发光性能与长余辉特性都有显著的提高．然而过量的H3BO3加入则会降低粉体的长余辉特性．本实验所获得H3BO3合适的添加量为0．7mol。     

Yb3+ and Er3+ co-doped Y2Ce2O7 nanoparticles: synthesis and spectroscopic properties

Yb³⁺ and Er³⁺co-doped Y₂Ce₂O₇ nanoparticles sintered at different temperatures were prepared by homogeneous co-precipitation method. The products were characterized by X-ray powder diffraction (XRD), energy-dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). The results indicated that the particle sizes and morphologies of the samples were heavily influenced by the sintering temperature. As temperature increased, the particle sizes became gradually larger and more agglomerate. The emissions including green and red upconversion emissions were investigated under 980 nm excitation. The emission intensities of the samples also depended on the sintering temperature. Two photon processes were mainly responsible for green and red upconversion emissions.     

Polyol-mediated synthesis and photoluminescent properties of Ce3+ and/or Tb3+-doped LaPO4 nanoparticles

Rare-earth ion (Ce3+, Tb3+) doped LaPO4 nanoparticles were prepared by the polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), UV-vis absorption spectroscopy, photoluminescence (PL) spectroscopy, and lifetimes. The results of XRD indicate that the as-prepared nanoparticles are well-crystallized at 160 degrees C and assigned to the monoclinic monazite structure of the LaPO4 phase. The obtained LaPO4:Ce3+, Tb3+ nanoparticles are spherical with narrow size distribution and average size of 20 nm. The doped rare-earth ions show their characteristic emission in LaPO4 nanoparticles, i.e., Ce3+ 5d-4f and Tb3+ 5D4-7FJ (J = 6-3) transitions, respectively. The optimum doping concentration for Tb3+ in La(0.8-x)Ce0.2TbxPO4 nanoparticles is determined to be 15 mol% (x = 0.15). The luminescence decay curves of Ce3+ in LaPO4:Ce3+ and LaPO4:Ce3+, Tb3+ nanoparticles present a single-exponential behavior, and the lifetimes (tau) of Ce3+ decrease with increasing Tb3+ concentrations (at the constant Ce3+ concentration) in LaPO4:Ce3+, Tb3+ nanoparticles due to the energy transfer from Ce3+ to Tb3+. The energy-transfer efficiency from Ce3+ to Tb3+ was calculated, which depends on the doping concentrations of Tb3+ if the concentration of Ce3+ is fixed.     

Controllable synthesis and luminescence properties of TiO2:Eu3+ nanorods,nanoparticles and submicrospheres by hydrothermal method

Eu³⁺-doped TiO₂ nanocrystals with three kinds of morphologies (nanorods, nanoparticles, and submicrospheres) have been successfully fabricated in cetyltrimethylammonium bromide (CTAB)/water/cyclohexane/n-pentanol reverse micelle by hydrothermal method for the first time and their photoluminescence (PL) properties have also been studied. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), FT-IR, and PL spectra were used to characterize the samples. The acidic and alkaline conditions of the microemulsion play an important role in determining the geometric morphologies of the final products. TiO₂:Eu³⁺ with three different morphologies all exist only in anatase phase and show high luminescence intensity without further calcinations, which show its advantages of energy saving. The shape of emission spectra was independent of the morphologies of the products but the luminescence intensity of the TiO₂:Eu³⁺ materials is strongly dependent on their morphology. The results show that TiO₂:Eu³⁺ nanorods possess the strongest luminescence intensity among the three nanostructured samples.     

Structural and morphological properties of RE3+ doped sesquioxide Y2O3 spherical nanoparticles

Effects of rare earth (Er³⁺, Yb³⁺, Sm³⁺, Ce³⁺) doping of yttrium oxide nanoparticles on the crystal structure and morphology have been investigated. X-ray diffraction, thermal analysis and scanning electron microscopy show that chemical and structural transformations are taking place in as-prepared carbonate spherical particles in the temperature range of 400–1200 K. In the final form crystalline agglomerates are compositionally homogeneous with a diameter range of 165–185 nm and an average crystalline grain size of 45 nm. Rare earth (RE) doped yttria particles are found to be up to 40% smaller in crystal grain size. The development of surface texture is due to nanocrystalline substructure which is related to the applied thermal treatment: carbonate decomposition and yttria crystallization processes.     

Field-dependent spin-lattice relaxation of Cr3+ in Al2O3

The variation of spin-lattice relaxation time (T ₁) with magnetic field (B) for the Cr³⁺ ion in ruby has been measured under non-Kramers conditions for fields between 0.3 and 2.6 tesla, corresponding to microwave frequencies in the range 9 to 71 GHz. Below about 0.8 tesla there is a slow variation, approximately asT ₁, B ^–0.4; at higher fields the variation becomes more rapid, approachingT ₁, B ^–2.0 at 2.6 tesla. This behaviour is explained in terms of the non-linear divergence of the energy levels with field.     

Structural and luminescence study of Ce3+ and Tb3+ doped Ca3Sc2Si3O12 garnets obtained by freeze-drying synthesis method

Ca₃Sc₂Si₃O₁₂ garnets doped with Ce³⁺ and Tb³⁺ ions were synthesized by a freeze-drying precursor method. The structural characterization was performed by X-ray diffraction (XRD) and Raman spectroscopy. Scanning Electron Microscopy (SEM) images of the calcined material were studied. High temperature treatments and doping with RE³⁺ ions resulted in a reduction of the secondary phases (Sc₂O₃) and an increase of the mean size of the nanocrystals, from 75 to 149 nm. These effects were confirmed by means of Raman spectra. Moreover, luminescence features of Ce³⁺ and Tb³⁺ doped samples indicated that these ions are effectively incorporated into the crystalline phase. In addition, the energy transfer processes between Ce³⁺ and Tb³⁺ ions in codoped garnets have been studied.     

Fabrication and photoluminescent properties of Gd2O3 : EU3+ nanowires in AAO template

Uniform Gd2O3 : Eu3+ nanowires were fabricated by using anodic aluminum oxide template (AAO). The spectral measurements indicate that with the increasing annealing temperature the excitation band of Eu3+ in Gd2O3 : Eu3+ nanowires/AAO shifted blue, the intensity ratio of 5D0-7F2 to 5D0-7F1, decreased, and the lifetime became longer. In the sample annealed at 1000 degrees C two spectral components, the sharper and broader lines were identified, corresponding to two different local environments, the Eu3+ ions in cubic phase and in amorphous phase, respectively. The 5D0-7F1 transitions of Eu3+ ions in cubic phase had longer lifetime than that in amorphous phase. In contrast to the lifetime of the 5D0-7F(j) transitions in the bulk, that in Gd2O3 : Eu3+/AAO composite films increased due to influence of the surrounding media (AAO).     

改进溶液燃烧法制备Fe3+掺杂Bi24O31Cl10及其光催化性能的研究

采用改进溶液燃烧法,以硝酸铋、柠檬酸、氯化铵和硝酸铁为原材料制备Fe-Bi24O31Cl10光催化物质,并通过在可见光下降解RhB评价Fe^3+掺杂对其光催化性能的影响。采用XRD,XPS,UV-vis,SEM,HTEM,FT-IR等表征手段研究了不同Fe^3+掺杂量对Bi24O31Cl10的物相、元素价态、光吸收性能、微观形貌以及颗粒分布、晶面间距、化学结构组成等的影响。结果表明:掺杂Fe^3+未改变Bi24O31Cl10的物相,片状形貌,但其片状大小明显变小且厚度变薄,光吸收性能增强,光生电子-空穴复合率下降,与纯Bi24O31Cl10相比,Fe^3+掺杂能显著提高Bi24O31Cl10的光催化活性,当Fe^3+掺杂量为0.5%(摩尔分数)时,对Bi24O31Cl10的光催化性能促进最高,在可见光下光照50 min,对RhB的脱色率可达75%,较纯Bi24O31Cl10提高了44%。     

Influence of combined doping of tricalcium silicate with MgO, Al2O3 and Fe2O3: synthesis, grindability, X-ray diffraction and 29Si NMR

Tricalcium silicate is the major component of ordinary Portland cement and as recently demonstrated is an alternative to ceramic implant material for clinical applications, because of its good biocompatibility. It is known, that the crystal structure of tricalcium silicate depends on the kind and amount of foreign oxides incorporated into the lattice that correlates with materials properties like hydration activity. Up to now, the correlation between structure and materials properties was only quantified for single oxide doping, but nothing is known about combined doping, which is the standard for industrial applications of tricalcium silicate. In this study the influence of single and multiple doping with MgO, Al₂O₃ and Fe₂O₃ on the crystal structure and materials properties was quantified. This first part deals with the synthesis, grindability, X-ray diffraction with Rietveld refinement and ²⁹Si nuclear magnetic resonance of the unhydrated compound, a second paper deals with the hydration reaction.

Synthesis of Sr4Al14O25:Eu2+ green emitting luminescent nano-pigment by solution combustion method

Luminescent nano-pigments based on strontium aluminates doped with various amounts of europium rare earth ion (Sr₄Al₁₄O₂₅:Eu²⁺) were synthesized by solution combustion method which involves the exothermic reaction of an oxidizer and an organic fuel. It is a suitable method for producing chemically homogenous and pure powders with very fine particle size. Phases studies by X-ray diffractometer indicated formation of pure phase Sr₄Al₁₄O₂₅ with crystallite sizes about 52.46 nm and peak shift of about 2θ = 0.26° due to Eu²⁺ doping. scanning electron microscope micrographs also revealed that the particles have irregular morphology and wide particle size distribution. The emission spectrum showed main emission peak at about 480 nm. Energy transfer mechanism between the two emission centers and the effect of Eu²⁺ ion concentration on emission spectrum was studied and it was deduced that the maximum emission intensity occurred at 4 at% of Eu²⁺. Absorption spectrum of the samples were lower than 0.5 %, especially in emission region of the doped pigments.     

One-step synthesis of diopside (CaMgSi2O6) ceramic powder by solution combustion method

We report the synthesis of diopside (CaMgSi₂O₆) ceramic powder, a multifunctional material, through an energy efficient, quick and one-step solution combustion (SC) method. Synthesis of diopside by SC method requires oxidizers, especially metal-nitrates, and a suitable fuel. However, unavailability of the silicon-nitrate makes the process of diopside formation by SC method challenging, which forces researchers to synthesize diopside by alternate high temperature solid state reaction route. Here, we demonstrate a simple way to overcome this difficulty by using an extra amount of ammonium nitrate (AN, as the suitable oxidizer), but still using the fumed-silica (an economical ceramic powder) and the solution of Ca-nitrate, Mg-nitrate and the fuel. A systematic investigation was carried out using different extra amounts (0, 5 or 10 mol) of AN, in combination with stoichiometric amounts of one of the three chosen fuels, viz., urea, glycine and alanine. For a specific combination of the fuel and extra oxidizer, namely ‘alanine and 10 mol of AN’, we observed the formation of nano-crystalline diopside phase, which generates enough heat for the incorporation of Si atoms from the SiO₂ precursor into diopside phase directly during the combustion process in one-step. This one-step process does not require any extra high temperature calcination step, thereby saving time, cost and complex equipments, whereas all other powders synthesized using other fuels require an extra calcination step, although the calcination temperature is low (≤ 900 °C), for crystalline diopside phase formation. Hence, our work demonstrates the one-step synthesis of diopside nanopowders by SC method through the direct use of the earth abundant SiO₂ ceramics.     

Synthesis of hexagonal Al2−x Cr x O3 nanodisks by a thermal decomposition of mesoporous Cr4+:Al2O3 powders

Monodispersed hexagonal Al_2−x Cr _x O₃ nanodisks are synthesized through a reactive doping of Cr⁶⁺ cations in a hydrogenated mesoporous AlO(OH)·αH₂O powder followed by annealing at 1,200 °C in air. The reaction was carried out by a drop wise addition of an aqueous Cr⁶⁺ solution (0.5–1.0 M) to AlO(OH)·αH₂O, at room temperature. Al_2−x Cr _x O₃ nanostructure formation was controlled by the nucleation and growth from the intermediate amorphous mesoporous Cr⁴⁺:Al₂O₃ composites in the temperature range 400–1,000 °C. The nanodisks of ∼50 nm diameter and thickness of ∼16 nm is observed in the sample with x of 0.2 and similar nanodisks with a low dimension is observed at a higher value of x of 1.6 (after 2 h of heating at 1,200 °C). The Cr³⁺ ↔ Al³⁺ substitution, x ≤ 1.2, inhibits grain growth in small crystallites. The crystallites in x = 0.2 composition have 43 nm diameter while it is 15 nm in those with x = 1.2 composition.     

退火对Cr3+离子掺杂Al2O3薄膜的结构及发光性能影响

用脉冲激光沉积技术在Si(100)基底上制备了纯Al2O3、掺杂浓度为0.3%、1%(质量分数)的Cr3+∶Al2O3薄膜。制备态的薄膜为立方γ-Al2O3结构,经800℃真空条件下退火1h样品的结晶度有所提高,呈现α-Al2O3相与γ-Al2O3相的衍射峰。薄膜基本保持了靶材中原有各元素成分比例,平均粒径为250nm,形貌为条形。与Al2O3粉体相比,制备态薄膜在386nm处的发光峰强度明显提高。这可归因于薄膜中氧空位的增加使双氧空位吸收电子所产生的F2+色心浓度提高。薄膜经真空退火后在332、398nm附近的发光峰强度明显增强,这是由于薄膜中氧空位的增加提高了F+、F色心浓度。与此同时,制备态薄膜在386nm附近发光峰经退火后由386nm蓝移至381nm,可归因于退火后制备态薄膜的内应力得到了释放。1%(质量分数)Cr3+掺杂薄膜在646、694nm出现Cr3+离子由4 T2能级跃迁至4 A2能级及由E-能级跃迁至4 A2能级产生的荧光发光峰。     

Mechanical properties of Al2O3 and Al2O3 + ZrO2 ceramics reinforced by SiC whiskers

The effect of the SiC whisker content on the mechanical properties of Al₂O₃ and Al₂O₃ + 20 vol% ZrO₂ (2 mol% Y₂O₃) ceramic composites has been investigated. It is shown that the strength and fracture toughness of the composites are increased by the addition of 0–30 vol% SiC whiskers with only one exception that 30 vol% SiC whisker leads to a decrease in the flexure strength. The addition of 20 vol% ZrO₂ (2 mol% Y₂O₃) significantly improves the mechanical properties of the Al₂O₃ + SiC whisker (SiC_w) composites and the t-m phase transformation of ZrO₂ is enhanced by the residual stresses caused by the thermal incompatibility between the SiC_w and the matrix. The toughening effect of both SiC whiskers and the t-m phase transformation of ZrO₂ (2 mol% Y₂O₃) is shown to be additive, but the addition of ZrO₂ decreases the strengthening effect of the SiC whiskers.