Temperature dependence of magnetic property and photocatalytic activity of Fe3O4/hydroxyapatite nanoparticles

Fe₃O₄/hydroxyapatite (HAP) nanoparticles have been developed as a novel photocatalyst support, based on the embedment of magnetic Fe₃O₄ particles into HAP shell via homogeneous precipitation method. The resultant nanoparticles were characterized by transmission electron microscope (TEM) and X-ray diffraction (XRD). These particles were almost spherical in shape, rather monodisperse and have a unique size of about 25 nm in diameter. The effect of calcination temperature on magnetic property and photocatalytic activity of Fe₃O₄/HAP nanoparticles was investigated in detail. The obtained results showed that the Fe₃O₄/HAP nanoparticles calcined at 400 °C possessed good magnetism and photocatalytic activity in comparison with that calcined at other temperatures.     

Synthesis and photoluminescence properties of SrLu2O4:Eu superfine phosphor

Superfine powder SrLu₂O₄:Eu³⁺ was synthesized with a precursor prepared by an EDTA - sol-gel method at relatively low temperature using metal nitrate and EDTA as starting materials. The heat decomposition mechanism of the precursor, formation process of SrLu₂O₄:Eu³⁺and the properties of the particles were investigated by thermo-gravimetric (TG) - differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence (PL) analyses. The results show that pure SrLu₂O₄:Eu³⁺ superfine powder has been produced after the precursor was calcinated at 900 °C for 2 h and has an elliptical shape and an average diameter of 80-100 nm. Upon excitation with 250 nm light, all the SrLu₂O₄:Eu³⁺ powders show red and orange emissions due to the 4f-4f transitions of Eu³⁺ ions. The highest photoluminescence intensity at 610 nm was found at a content of about 6 mol% Eu³⁺. Splitting of the ⁵D₀-⁷F₁ emission transition revealed that the Eu³⁺ ions occupied two nonequivalent sites in the crystallite by substituting Lu³⁺ ions.     

Luminescent properties of long lasting phosphor Ca2MgSi2O7:Eu

Long afterglow phosphors (Ca_1−xEu_x)₂MgSi₂O₇ (0.002 ≤ x ≤ 0.02) were prepared by solid-state reactions under a weak reductive atmosphere. X-ray diffraction pattern, photoluminescence spectra, decay curve, afterglow spectra and thermoluminescence curves were investigated. The phosphors showed two emission peaks when they were excited by 343 nm, due to two types of Eu²⁺ centers existing in the Ca₂MgSi₂O₇ lattice. However, only one emission peak can be found in their afterglow spectra. Energy transfer between Eu²⁺ ions in inequivalent sites was found. A possible mechanism was presented and discussed. The afterglow decay time of Ca_1.998MgSi₂O₇:Eu_0.002 was nearly 12.5 h which means it was a good long lasting phosphor.     

Vacuum ultraviolet excited photoluminescence properties of novel Na3Y9O3(BO3)8:Eu phosphor

The novel vacuum ultraviolet (VUV) excited Na₃Y₉O₃(BO₃)₈:Eu³⁺ red phosphor was synthesized and the photoluminescence (PL) properties were investigated. The phosphor showed strong VUV PL intensity, large quenching concentration (40 mol%) and good chromaticity (0.649, 0.351). The Eu³⁺-O²⁻ charge transition (CT) was observed to be at a higher energy (232 nm, 5.35 eV). The host absorption at 127-166 nm was broad and strong when monitoring the Eu³⁺ emission, which indicated that energy transfer from the host-lattice to the Eu³⁺ ions was efficient in Na₃Y₉O₃(BO₃)₈:Eu³⁺. These excellent VUV PL properties were revealed to be correlated with the unique isolated layer-type structure of Na₃Y₉O₃(BO₃)₈ host. The results showed that the Na₃Y₉O₃(BO₃)₈:Eu³⁺ would be a good candidate for VUV-excited red phosphor.     

Preparation of KMgF3 and Eu-doped KMgF3 nanocrystals in water-in-oil microemulsions

In this study, KMgF₃:Eu²⁺ luminescent nanocrystals (NCs) were prepared in water/cetyltrimethylammonium bromide (CTAB)/2-octanol microemulsions. The KMgF₃:Eu²⁺ NCs were characterized by transmission electron microscopy (TEM), X-ray diffractometer (XRD), fluorescence spectrum, infrared spectroscopy (IR) and elementary analysis. The results showed that the size of the KMgF₃:Eu²⁺ NCs was hardly affected by water content and surfactant (CTAB) concentration. The emission spectrum showed that the position of the 362 nm peak is due to the K⁺ sites substituted Eu²⁺. Two emission peaks located at 589 and 612 nm can be attributed to Eu³⁺, which exist at two different types of Eu³⁺ centers: one is Eu³⁺ at a K⁺ site, the other is clustering of Eu³⁺ ions in the interstices of KMgF₃ host lattice.     

Characterizations and properties of Eu-doped ZnWO4 prepared via a facile self-propagating combustion method

ZnWO₄ and Eu³⁺-doped ZnWO₄ were prepared for the first time via a facile self-propagating combustion method. The structure, morphology and luminescence of the as-prepared ZnWO₄ and Eu³⁺-doped ZnWO₄ were characterized. The photoluminescent property of Eu³⁺-doped ZnWO₄ complexes indicated an energy transfer from WO₄²⁻ groups to Eu³⁺ and suggested an effective doping of Eu³⁺ into the lattice of ZnWO₄. The photocatalytic activity of ZnWO₄ and Eu³⁺-doped ZnWO₄ was investigated by the photodegradation of rhodamine B (RhB). Eu³⁺-doped ZnWO₄ showed enhanced photocatalytic activity in the photodegradation of RhB.     

Synthesis and optical properties of (Gd1−x,Eux)2O2SO4 nano-phosphors by a novel co-precipitation method

(Gd_1−x,Eu_x)₂O₂SO₄ nano-phosphors were synthesized by a novel co-precipitation method from commercially available Gd₂O₃, Eu₂O₃, H₂SO₄ and NaOH starting materials. Composition of the precursor is greatly influenced by the molar ratio of NaOH to (Gd_1−x,Eu_x)₂(SO₄)₃ (the m value), and the optimal m value was found to be 4. Fourier transform infrared spectrum (FT-IR) and thermal analysis show that the precursor (m = 4) can be transformed into pure (Gd_1−x,Eu_x)₂O₂SO₄ nano-phosphor by calcining at 900 °C for 2 h in air. Transmission electron microscope (TEM) observation shows that the Gd₂O₂SO₄ phosphor particles (m = 4) are quasi-spherical in shape and well dispersed, with a mean particle size of about 30-50 nm. Photoluminescence (PL) spectroscopy reveals that the strongest emission peak is located at 617 nm under 271 nm light excitation, which corresponds to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The quenching concentration of Eu³⁺ ions is 10 mol% and the concentration quenching mechanism is exchange interaction among the Eu³⁺ ions. Decay study reveals that the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions has a single exponential decay behavior.     

The photoluminescence properties of Y2O3:Eu prepared by surfactant assisted co-precipitation-molten salt synthesis

Y₂O₃:Eu³⁺ red phosphors were prepared by surfactant assisted co-precipitation-molten salt synthesis method. The effects of surfactant content and annealing temperature on the structure and luminescence were investigated by X-ray diffraction and fluorescence spectrophotometer. The use of surfactant reduces the impurities on the surface of particles and promotes the reaction. The color purity of as-prepared Y₂O₃:Eu³⁺ red phosphors is improved with the presence of surfactant. In the excitation spectra, two strong bands at 394 and 466 nm are attributed to ⁷F_0,1-⁵L₆, ⁷F_0,1-⁵D₂ transitions of Eu³⁺ ions respectively. With the excitation of 394 or 466 nm, the as-fabricated samples reveal excellent red emission as high as that of samples monitored by 254 nm. Thus, the Y₂O₃:Eu³⁺ is a promising red phosphor for ultraviolet-visible light-emitting diodes.     

Green emission from Eu/Dy codoped SrO-Al2O3-B2O3 glass-ceramic by ultraviolet light and femtosecond laser irradiation

A spectroscopic investigation of Eu²⁺/Dy³⁺ codoped SrO-Al₂O₃-B₂O₃ glass-ceramic is presented. The sample exhibits green emission excited by ultraviolet (UV) light and near-IR femtosecond (fs) laser. The emission profile obtained by near-IR fs laser irradiation is similar to that by UV excitation, indicating that both of the emissions come from 5d → 4f transition of the Eu²⁺ ions. The relationship between the upconversion luminescence (UCL) intensity and pump power reveals a two-photon process in the conversion of near-IR radiation to the green emission. The possible mechanism of UCL from such glass-ceramic is proposed.     

Gd2O3:Eu@mesoporous SiO2 bifunctional core-shell composites: Fluorescence label and drug release

A novel kind of core-shell nanocomposite Gd₂O₃:Eu³⁺@mesoporous SiO₂ was successfully fabricated, which consisted of a solvothermal synthesized Gd₂O₃:Eu³⁺ nanospheres core, a thin nonporous silica midterm layer and an ordered mesoporous silica shell. The XRD, SEM, TEM, FTIR, N₂ adsorption/desorption and PL spectra were employed to characterize the composites. The cytotoxicity of Gd₂O₃:Eu³⁺@mesoporous SiO₂ and Gd₂O₃:Eu³⁺ was assessed by the standard MTT assay. The composites had spherically monodisperse morphology and a narrow size distribution around 180 nm in diameter. Furthermore, they also demonstrated the strong photoluminescence of ⁵D₀-⁷F_J emissions. In addition, the composites exhibited good property of sustained drug release by using ibuprofen (IBU) as model drug in the drug delivery process. Therefore, the drug release process could be easily tracked and identified through photoluminescence. Overall, the present composites have potential significant biomedical application as ideal bifunctional materials.     

Dependence of photoluminescence (PL) emission intensity on Eu and ZnO concentrations in Y2O3:Eu and ZnO·Y2O3:Eu nanophosphors

Y₂O₃:Eu³⁺ and ZnO·Y₂O₃:Eu³⁺ nanophosphor powders with different concentrations of Eu³⁺ ions were synthesized by a sol-gel method and their luminescence properties were investigated. The red photoluminescence (PL) from Eu³⁺ ions with the main emission peak at 612 nm was observed to increase with Eu³⁺ concentration from 0.25 to 0.75 mol% and decreased notably when the concentration was increased to 1 mol%. The decrease in the PL intensity at higher Eu³⁺ concentrations can be associated with concentration quenching effects. The red emission at 612 nm was shown to increase considerable when ZnO nanoparticles were incorporated in Y₂O₃:Eu³⁺ while green emission from ZnO was suppressed. The increase is attributed to energy transfer from ZnO to Eu³⁺.     

Structure and magnetic properties of soft organic ZnAl-LDH/polyimide electromagnetic shielding composites

The imidization mechanism, structure, and magnetic properties of organic modified Zinc-aluminum layered double hydroxides/polyimide composites are investigated. During imidization, organic modified Zinc-aluminum layered double hydroxides lose the hydroxyl group and sodium dodecyl sulfate modifier decomposes partly resulting in a loose contact between PI and oxidized Zinc-aluminum layered double hydroxides. The thermal properties of composites are slightly decreased with increasing organic modified Zinc-aluminum layered double hydroxides but the wettability varies oppositely. Comparing to organic modified Zinc-aluminum layered double hydroxides, the saturated magnetization of heated organic modified Zinc-aluminum layered double hydroxides is enhanced slightly due to structural improvement in Fe₃O₄ crystalline domain. Therefore, the magnetic properties are not affected by imidization procedure. The soft magnetic composites have large potential in electromagnetic shielding.     

Enhanced emission from CaSi2O2N2:Eu phosphors by doping with Y ions

Yttrium doped CaSi₂O₂N₂:Eu²⁺ phosphors were prepared by the solid state reaction method. Large increases in the emission have been achieved by adding Y³⁺ ions in the host. XRD data revealed that the lattice expanded as doping Y³⁺ ions. XPS results suggested that there were more Eu²⁺ ions incorporated into the lattice of Y³⁺ doped samples than that of undoped samples. The doping effect of Y³⁺ ions has been discussed systematically. By using this novel Y³⁺ doped CaSi₂O₂N₂:Eu²⁺ phosphor, bright daylight emission with luminous efficiency (η_L) of 44 lm/W, color rendering index (CRI) of 82 and correlated color temperature (CCT) of 5300 K can be generated from white LED.     

Preparation and intercalation chemistry of magnesium-iron(III) layered double hydroxides containing exchangeable interlayer chloride and nitrate ions

Layered double hydroxides (LDHs) with Mg²⁺ and Fe³⁺ cations in the brucite-like layers and having chloride or nitrate ions in the interlayer region have been prepared and characterized by powder X-ray diffraction (PXRD), elemental analysis and thermal analysis. Thermal decomposition of the LDH-nitrate occurs in two steps, with loss of water followed by simultaneous dehydroxylation of the layers and loss of NO_x/O₂ arising from the nitrate anions. Thermal decomposition of the LDH-chloride involves an additional step, with chloride ions becoming grafted to the layers, prior to loss of HCl. The interlayer anions may be readily replaced by sulfate, thiosulfate, tartrate and vinylbenzenesulfonate ions suggesting that these materials may be useful precursors to Mg-Fe(III) LDHs intercalated with a variety of inorganic and organic anions.     

Etude des solutions solides entre le sesquioxyde de fer cubique γ-Fe2O3 et le ferrite de zinc ZnFe2O4

The authors have prepared metastable solid solutions between cubic iron sesquioxide γ-Fe₂O₃ and zinc ferrite ZnFe₂O₄. They give the main characteristics of these defect spinels. Fe³⁺ ions and vacancies are replaced by Zn²⁺ ions on tetrahedral sites. The lattice parameter and the thermal stability increase with the substitution rate. The magnetic behavior is comparable to that observed for solid solutions M_1?yZn_yFe₂O₄.     

Oxygen ionic conduction in brownmillerite CaAl0.5Fe0.5O2.5+δ

The oxygen permeability of CaAl_0.5Fe_0.5O_2.5+δ brownmillerite membranes at 1123-1273 K was found to be limited by the bulk ionic conduction, with an activation energy of 170 kJ/mol. The ion transference numbers in air are in the range 2×10⁻³ to 5×10⁻³. The analysis of structural parameters showed that the ionic transport in the CaAl_0.5Fe_0.5O_2.5+δ lattice is essentially along the c axis. The largest ion-migration channels are found in the perovskite-type layers formed by iron-oxygen octahedra, though diffusion in tetrahedral layers of the brownmillerite structure is also possible. Heating up to 700-800 K in air leads to losses of hyperstoichiometric oxygen, accompanied with a drastic expansion and, probably, partial disordering of the CaAl_0.5Fe_0.5O_2.5+δ lattice. The average thermal expansion coefficients of CaAl_0.5Fe_0.5O_2.5+δ ceramics in air are 16.7×10⁻⁶ and 12.6×10⁻⁶ K⁻¹ at 370-850 and 930-1300 K, respectively.     

The magnetic properties of Bi0.9Ba0.1Fe0.81M0.09Ti0.1O3 solid solutions (M = Co, Mn, Sc, Al)

Solid solutions with general formula Bi_0.9Ba_0.1Fe_0.81M_0.09Ti_0.1O₃ (M = Co, Mn, Sc, Al) together with parental Bi_0.9Ba_0.1Fe_0.9Ti_0.1O₃ were prepared by the traditional solid state reaction method. Their structural, room temperature magnetic, and dielectric properties were investigated. X-ray diffraction analysis indicated that all samples maintained original R3c space group. M–H hysteresis loop of Co³⁺ doped sample saturated at an applied field of 1 T with spontaneous magnetization of 1.735 emu/g, while Mn⁴⁺ substitution enhanced the magnetization of Bi_0.9Ba_0.1Fe_0.9Ti_0.1O₃ less strongly; addition of Sc³⁺ helped decrease magnetic coercive field while Al³⁺ modified sample exhibited paramagnetic M–H hysteresis loop. Differential scanning calorimetry was applied to determine the Neel temperature (T_N) and the T_N for undoped, Co³⁺, Mn⁴⁺, Sc³⁺, Al³⁺ doped solid solutions were 318.1, 324.3, 335.7, 293.9 and 295.8 respectively. Sc³⁺ substitution had little influence on the dielectric properties of Bi_0.9Ba_0.1Fe_0.9Ti_0.1O₃ while Al³⁺ doping improved its dielectric constant. In contrast, Co³⁺, Mn⁴⁺ doped samples showed decreased permittivity but inhibited tan δ at frequencies larger than 30 kHz.     

Neutron powder diffraction and magnetic study of perovskites Pb(Mn1/2Nb1/2)O3 and Pb(Mn1/4Fe1/4Nb1/2)O3

The structural and magnetic properties of the complex metal oxides Pb(Mn_1/2Nb_1/2)O₃ (PMNO) and Pb(Mn_1/4Fe_1/4Nb_1/2)O₃ (PMFNO), which belong to a class of disordered perovskites have been studied. The magnetic susceptibilities of PMNO showed hysteresis between field cooled and zero-field cooled conditions below the transition of 15 K, suggesting that the material has a spin-glass feature. Neutron diffraction patterns of PMNO showed no evidence of a long-range magnetic ordering at 1.5 K, which is consistent with spin-glass behavior. Rietveld refinements of neutron powder diffraction data collected at different temperatures between 1.5 and 700 K have been carried out in order to extract structural information. The crystal structure of this compound is cubic (space group Pmm) within the whole temperature interval. The Mn and Nb ions were found to be disordered over the perovskite B-sites. The main feature of this structure is the positional disorder at the Pb site, the importance of which in connection with the ferroic transitions is briefly discussed. The Pb cations show a positional disorder shifting from their high-symmetry positions along the [1 1 1] direction. The effect of Fe-doping on PMNO has been studied. The substitution of Fe at the Mn site in PMFNO results in a small changes of the magnetic properties without significant differences in the crystal structures. The factors governing the observed structural and magnetic properties of PMNO and PMFNO are discussed and compared with those of other quaternary Mn-containing perovskites. For the PbB³⁺_1/2Nb_1/2O₃ series with the isomorphous substitution B³⁺, graphs of average lattice parameters of the perovskite phase and the temperatures of ferroelectric and magnetic phase transitions as functions of the B³⁺ cation radius were constructed and are discussed. Influence of A-cation sublattice on magnetic properties is also considered.     

Preparation, characterization and luminescence of La2TeO6 phosphor doped with Eu

Phosphors of La₂TeO₆ doped with Eu³⁺ ions have been synthesized by the oxidation of the corresponding rare-earths oxytellurides of formula La_2−xEu_xO₂Te (x = 0.02, 0.06, and 0.1) at 1050 K. Powder X-ray diffraction confirms that the as prepared materials consist of the orthorhombic La₂TeO₆ as main phase. The photoluminescence (PL) of red-emitting La_2−xEu_xTeO₆ powder phosphors is reported. The emission spectrum, exhibits an intense emission peak due to ⁵D₀ → ⁷F₂ transition at 616 nm, which indicates that the Eu³⁺ ion occupies a non-centrosymmetric site in the host lattice. These materials could find application for use as lamp phosphors in the red region.     

Growth morphology study of cathodically electrodeposited Fe3O4 thin films at elevated temperatures

We investigated the electrodeposition of Fe₃O₄ thin films in the Fe³⁺-triethanolamine system by galvanostatic deposition at elevated temperatures. It was found that with a fixed current density, the concentration of Fe³⁺ ions had a significant impact on the electrodeposition rate, while the deposition temperature and time strongly affected the morphology of the Fe₃O₄ thin films. Fe₃O₄ thin films deposited in electrolyte with high Fe³⁺ concentration and at high temperature (>80 °C) exhibited a dense and uniform morphology and were composed of globular or polyhedral crystallites, while the Fe₃O₄ thin films deposited at low temperatures (<70 °C) were loose and flake-like. Based on the empirical observations, a hypothetical growth model for the electrodeposition of Fe₃O₄ at elevated temperatures was proposed.