Synthesis of high efficiency Zn2SiO4:Mn green phosphors using nano-particles

In this study, Zn₂SiO₄:Mn²⁺ luminescent phosphors were prepared by mixing nano-scale ZnO, SiO₂, and MnO₂ particles at the compositions corresponding to 2ZnO + SiO₂ + X mol% MnO₂ (Zn₂SiO₄–X-MnO₂, 0.02 ≤ X ≤ 0.05). The mixing powders were calcined from 900 °C to 1300 °C in air and in N₂ atmosphere. No matter calcined in air or in N₂ atmosphere, Zn₂SiO₄ was the mainly crystalline phase in particles calcined at 900 °C and was the only phase in particles calcined at 1000 °C and higher. The influences of MnO₂ concentration and calcining atmosphere and temperature on wavelength of luminescence peak and the emission intensity were further intensively investigated. We would show that the calcining atmosphere had no apparent influences on the physical and photoluminescence (PL) characteristics of Zn₂SiO₄:Mn²⁺ phosphors. The MnO₂ content and the calcining temperature were the main reasons to influence the physical and PL characteristics of Zn₂SiO₄:Mn²⁺ phosphors.     

Low temperature sintering and microwave dielectric properties of Ce2(WO4)3 ceramics

Ce₂(WO₄)₃ ceramics have been synthesized by the conventional solid-state ceramic route. Ce₂(WO₄)₃ ceramics sintered at 1000 °C exhibited ?_r = 12.4, Qxf = 10,500 GHz (at 4.8 GHz) and τ_f = −39 ppm/°C. The effects of B₂O₃, ZnO–B₂O₃, BaO–B₂O₃–SiO₂, ZnO–B₂O₃–SiO₂ and PbO–B₂O₃–SiO₂ glasses on the sintering temperature and microwave dielectric properties of Ce₂(WO₄)₃ were investigated. The Ce₂(WO₄)₃ + 0.2 wt% ZBS sintered at 900 °C/4 h has ?_r = 13.7, Qxf = 20,200 GHz and τ_f = −25 ppm/°C.     

Microwave dielectric properties of the (1 − x)Mg2TiO4-xCaTiO3-y wt.% ZnNb2O6 ceramics system

Composite ceramics based on (1 − x)Mg₂TiO₄-xCaTiO₃-y wt.% ZnNb₂O₆ (x = 0.12-0.16, y = 0-8) were prepared by a conventional mixed-oxide route. Zn²⁺ partially replaced Mg²⁺ in Mg₂TiO₄ and formed the spinel-structured (Mg_1−δZn_δ)₂TiO₄ phase. Nb²⁺, is known to be solid soluble in CaTiO₃, was found to change its shape from cubic to pliable. A bi-phase system (Mg_1−δZn_δ)₂TiO₄ and CaTiO₃ exhibited in all samples, where a small amount of second phase Mg_1−δZn_δTiO₃ was also detected. The microwave dielectric properties of specimens were strongly related to ZnNb₂O₆ and CaTiO₃ content. As y increased, ?_r and τ_f decreased, however, Q × f decreased to a minimum value and started to increase thereafter. It was also found that ?_r and τ_f increased and Q × f decreased with increasing x. The optimized microwave dielectric properties with ?_r = 18.37, Q × f = 31,027 GHz (at 6 GHz), and τ_f = 0.51 ppm/°C were achieved for (1 − x)Mg₂TiO₄-xCaTiO₃-y wt.% ZnNb₂O₆ (x = 0.12, y = 4) sintered at 1360 °C for 6 h.     

Improvement of photoluminescence properties of Ce3+- doped CaSrAl2SiO7 phosphors by charge compensation with Li+ and Na+

In this work, we prepared CaSr_1-xAl₂SiO₇:xCe³⁺ (0.03 ≤ x ≤ 0.12) and CaSr_0.94Al₂SiO₇:0.03Ce³⁺,0.03 M⁺ (M⁺ = Li⁺ and Na⁺) phosphors via solid-state reaction method. Structural and photoluminescence (PL) properties of the phosphors were also investigated. The prepared phosphors formed an orthorhombic crystal structure with the P2₁2₁2₁ space group. CaSr_1-xAl₂SiO₇:xCe³⁺ phosphors were effectively excited by near-ultraviolet (UV) light (345 nm), which is suitable with the emission of near-UV light emitting diode chips. A broad blue emission (402 nm) was detected in CaSr_1-xAl₂SiO₇:xCe³⁺ and CaSr_0.94Al₂SiO₇:0.03Ce³⁺,0.03 M⁺ phosphors; this was attributed to the 4f⁰5d¹ → 4f¹ transition of Ce³⁺. To maintain charge equilibrium, charge compensators, such as monovalent Li⁺ and Na⁺ ions, were doped into the CaSr_0.97Al₂SiO₇:0.03Ce³⁺ phosphor, significantly improving its PL properties. The strongest emission intensity was achieved in CaSr_0.94Al₂SiO₇:0.03Ce³⁺,0.03Li⁺ phosphor. Addition of Li⁺ charge compensator was highly effective in improving PL properties of CaSr_0.97Al₂SiO₇:0.03Ce³⁺ phosphors.     

Experimental determination of the eutectic temperature in air of the CuO-TiO2 pseudobinary system

Eutectic temperature and composition in the CuO-TiO₂ pseudobinary system have been experimentally determined in air by means differential thermal analysis (DTA), thermogravimetry (TG) and hot-stage microscopy (HSM). Samples of the new eutectic composition treated at different temperatures have been characterized by X-ray diffraction (XRD) and X-ray absorption near-edge structural spectroscopy (XANES) to identify phases and to determine the Cu valence state, respectively. The results show that the eutectic temperature in air is higher by 100 °C (∼1000 °C) for a Ti-richer composition (XTiO₂=25 mol%) than the one calculated in the literature. The reduction of Cu²⁺ to Cu⁺ takes places at about 1030 °C. The existence of Cu₂TiO₃ and Cu₃TiO₄ has been confirmed by XRD in the temperature range between 1045 and 1200 °C.     

Sintering of glass-added BaZn1/3Nb2/3O3 ceramics

The complex perovskite oxide Ba(Zn_1/3Nb_2/3)O₃ (BZN) has been studied for its attractive dielectric properties which place this material interesting for applications as multilayer ceramics capacitors or hyperfrequency resonators. This material is sinterable at low temperature with combined glass phase–lithium salt additions, and exhibits, at 1 MHz very low dielectric losses combined with relatively high dielectric constant and a good stability of this later versus temperature. The 2 wt.% of ZnO–SiO₂–B₂O₃ glass phase and 1 wt.% of LiF-added BZN sample sintered at 900 °C exhibits a relative density higher than 95% and attractive dielectric properties: a dielectric constant ?_r of 39, low dielectrics losses (tan(δ) < 10⁻³) and a temperature coefficient of permittivity τ_? of 45 ppm/°C⁻¹. The 2 wt.% ZnO–SiO₂–B₂O₃ glass phase and 1 wt.% of B₂O₃-added BZN sintered at 930 °C exhibits also attractive dielectric properties (?_r = 38, tan(δ) < 10⁻³) and it is more interesting in terms of temperature coefficient of the permittivity (τ_? = −5 ppm/°C). Their good dielectric properties and their compatibility with Ag electrodes, make these ceramics suitable for L.T.C.C applications.     

Low temperature and microwave dielectric properties of TiO2/ZBS glass composites

TiO₂ based ceramic/glass composites were prepared by a non-reactive liquid phase sintering (NLPS) using zinc borosilicate (ZBS) glass having the deformation temperature of 588 °C. The compounds of Zn₂SiO₄ and Zn₄B₆O₁₃ were formed after the sintering process, indicating that the ZBS glass was a non-reactive one in this system. For TiO₂/50 vol% ZBS glass composite, the two-stage sintering behavior was conducted as the sintering temperature increased. The former might be correlated to the NLPS process and the latter appeared to be related to the crystallization. The dielectric constant (?_r) was mainly affected by the porosity and obeyed the logarithmic mixing rule. The quality factor (Q × f₀) showed an increase and then a steep decrease after the maximum at 850 °C. TiO₂/50 vol% ZBS glass composite sintered at 900 °C demonstrated 36 in the dielectric constant (?_r) and 7500 GHz in the quality factor (Q × f₀) for an application to LTCC filters.     

Room temperature transesterification of soybean oil to biodiesel catalyzed by rod-like CaxSiOx + 2 solid base

Rod-like Ca_xSiO_x + 2 catalysts were synthesized by using one-pot hydrothermal method. Catalysts calcined at 550 °C were used in the transesterification reaction of soybean oil with methanol. Under methanol reflux condition, FAME yields of 82% and 95% were achieved on Ca₄SiO₆ in a reaction time of 1 and 2 h, separately. Also, the FAME yields on different Ca_xSiO_x + 2 catalysts were correlated with their basic properties. Besides, a FAME yield of ca. 80% can be achieved under room temperature over Ca₄SiO₆ catalyst.     

Enhanced luminescence of novel Ca3B2O6:Dy phosphors by Li-codoping for LED applications

The Ca_3−xB₂O₆:xDy³⁺ (0.0 ≤ x ≤ 0.105) and Ca_2.95−yDy_0.05B₂O₆:yLi⁺ (0 ≤ y ≤ 0.34) phosphors were synthesized at 1100 °C in air by solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), photoluminescence excitation (PLE) and photoluminescence (PL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm is due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions upon 350 nm excitation is observed at 480 nm (blue) due to the ⁴F_9/2 → ⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2 → ⁶H_13/2 transitions and a weak 660 nm (red) due to ⁴F_9/2 → ⁶H_11/2 emissions, respectively. The optimal PL intensity of the Ca_3−xB₂O₆:xDy³⁺ phosphors is found to be x = 0.05. Moreover, the PL results from Ca_2.95−yDy_0.05B₂O₆:yLi⁺ phosphors show that Dy³⁺ emissions can be enhanced with the increasing codopant Li⁺ content till y = 0.22. By simulation of white light, the CIE of the investigated phosphors can be tuned by varying the content of Li⁺ ions, and the optimal CIE value (0.300, 0.298) is realized when the content of Li⁺ ions is y = 0.22. All the results imply that the Ca_2.95−yDy_0.05B₂O₆:yLi⁺ phosphors could be potentially used as white LEDs.     

Calcination and sintering characteristics of limestone under O2/CO2 combustion atmosphere

The O₂/CO₂ coal combustion technology is an innovative combustion technology that can control CO₂, SO₂ and NO_x emissions simultaneously. Calcination and sintering characteristics of limestone under O₂/CO₂ atmosphere were investigated in this paper. The pore size, the specific pore volume and the specific surface area of CaO calcined were measured by N₂ adsorption method. The grain size of CaO calcined was determined by XRD analysis. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere are less than that of CaO calcined in air at the same temperature. And the pore diameter of CaO calcined in O₂/CO₂ atmosphere is larger than that in air. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere increase initially with temperature, and then decline as temperature exceeds 1000 °C. The peaks of the specific pore volume and the specific surface area appear at 1000 °C. The specific surface area decreases with increase in the grain size of CaO calcined. The correlations of the grain size with the specific surface area and the specific pore volume can be expressed as L = 744.67 + 464.64 lg(1 / S) and L = − 608.5 + 1342.42 lg(1 / ε), respectively. Sintering has influence on the pore structure of CaO calcined by means of influencing the grain size of CaO.     

Cr2O3 doping in ZnO–0.5 mol% V2O5 varistor ceramics

The effects of the amount of Cr₂O₃ (0.5–4 mol%) on the microstructure and the electrical properties have been studied in a binary ZnO–0.5 mol% V₂O₅ system. The microstructure of the samples consists mainly of ZnO grains with ZnCr₂O₄ and α-Zn₃(VO₄)₂ as the minority secondary phases. The addition of Cr₂O₃ is found to be effective in controlling the abnormal ZnO grain growth often found in V₂O₅-doped ZnO ceramic system, and a more uniform microstructure can be obtained. The varistor performance is also improved as observed from the increase in the non-linear coefficient α of the Cr₂O₃-doped ZnO–V₂O₅ samples. The α value is found to increase with the amount of Cr₂O₃ for up to 3 mol% Cr₂O₃ content. Further increase in Cr₂O₃ is found to cause a decrease in the α value. The highest α value of 28.9 is obtained for the ZnO–0.5 mol% V₂O₅–3 mol% Cr₂O₃ sample.     

Electrospinning amorphous SiO2-TiO2 and TiO2 nanofibers using sol-gel chemistry and its thermal conversion into anatase and rutile

SiO₂-TiO₂ nanofibers were electrospun from partially hydrolyzed tetraethyl orthosilicate, and titanium isopropoxide using sol-gel chemistry. SiO₂-TiO₂ sol phase diagrams were created summarizing the role of composition on solution homogeneity and electrospinnability. Inorganic nanofiber spinnability was studied without the addition of any organic polymer, oligomer, gelator, or binder. TiO₂ concentration within SiO₂-TiO₂ fibers ranged from 25 to 100 mol%. SiO₂, SiO₂-TiO₂, and TiO₂ nanofiber structures were investigated using scanning electron microscopy and transmission electron microscopy. Inorganic fiber spinning was highly dependent on sol reaction temperature, time, and solution composition. At high TiO₂ concentrations, twisted and ribbon-like nanofibers with dumbbell-shaped cross-sections were observed. This was attributed to jet branching and splitting during electrospinning. Electrospun fibers were amorphous at room temperature, but thermally converted into crystalline anatase, which underwent additional structural changes at higher temperatures into rutile. This anatase-rutile thermal phase transformation was highly dependent upon TiO₂ concentration. Nanofiber composition, thermal stability, and crystalline structures were characterized by energy-dispersive X-ray spectroscopy; Fourier transform infrared spectroscopy, thermal gravimetric analysis, and wide-angle X-ray diffraction.     

Factors influencing the structure of electrochemically prepared α-MnO2 and γ-MnO2 phases

The α- and γ-phases of MnO₂ prepared by electrolysis of MnSO₄ and M_xSO₄ (where M = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ or Mg²⁺) in aqueous solutions at various pH and voltage E_v values under ambient conditions have been systematically studied. The structures of powdery MnO₂ produced are found to depend on the radius of the M^z+ counter cation in addition to the pH and E_v conditions. In order to achieve the α-phase for MnO₂ formation under neutral pH condition, the radius of counter cation must be equal to or greater than 1.41 Å, the size of the K⁺ cation. The relative concentration ratio of [MnO₄⁻]_transient/[Mn²⁺], which is related to the pH-E_v conditions, also affects the structure of MnO₂ produced with counter ions smaller than K⁺. For samples prepared in acidified solution with the counter ions of Li⁺, Na⁺ or Mg²⁺ at 2.2 V, the electrolysis products display the γ-MnO₂ phase while those prepared at 2.8 V electrolysis produce a mixture of γ-MnO₂ and α-MnO₂ phases. Single phase of α-MnO₂ is identified in the 5 V electrolysis products. Furthermore, the valence state of manganese was found to decrease as the applied voltage was reduced from 5.0 to 2.2 V. This implies that the lower [MnO₄⁻]_transient/[Mn²⁺] ratio or the less oxidative condition is responsible for the non-stoichiometric MnO₂ structure with oxygen deficiency.     

Effect of Ta2O5 in (Ca,Si, Ta)-doped TiO2 ceramic varistors

TiO₂ varistors doped with 0.2 mol% Ca, 0.4 mol% Si and different concentrations of Ta were obtained by ceramic sintering processing at 1350 °C. The effect of Ta on the microstructures, nonlinear electrical behavior and dielectric properties of the (Ca, Si, Ta)-doped TiO₂ ceramics were investigated. The ceramics have nonlinear coefficients of α = 3.0–5.0 and ultrahigh relative dielectric constants which is up to 10⁴. Experimental evidence shows that small quantities of Ta₂O₅ improve the nonlinear properties of the samples significantly. It was found that an optimal doping composition of 0.8 mol% Ta₂O₅ leads to a low breakdown voltage of 14.7 V/mm, a high nonlinear constant of 4.8 and an ultrahigh electrical permittivity of 5.0 × 10⁴ and tg δ = 0.66 (measured at 1 kHz), which is consistent with the highest and narrowest grain boundary barriers of the ceramics. In view of these electrical characteristics, the TiO₂–0.8 mol% Ta₂O₅ ceramic is a viable candidate for capacitor–varistor functional devices. The characteristics of the ceramics can be explained by the effect and the maximum of the substitution of Ta⁵⁺ for Ti⁴⁺.     

Preparation and microwave dielectric properties of 3ZnO·B2O3 ceramics with low sintering temperature

The preparation and dielectric properties of 3ZnO·B₂O₃ ceramics were investigated. Dense 3ZnO·B₂O₃ ceramics were obtained as sintered in the temperature range from 950 to 1000 °C for 3 h. The X-ray diffraction showed that the obtained ceramics were of a monoclinic 3ZnO·B₂O₃ structure. The ceramic specimens fired at 955 °C for 1 h exhibited excellent microwave dielectric properties: ?_r ∼ 6.9, Q × f ∼ 20,647 GHz (@6.35 GHz), and τ_f ∼ −80 ppm/°C. The dependences of relative density, ?_r, and Q × f of ceramics sintered at 955 °C on sintering soaking time showed that they all reached their plateaus as the soaking time was up to 60 min. Meanwhile, 3ZnO·B₂O₃ ceramics had no reaction with silver during cofiring, indicating it is a potential candidate for low-temperature cofired ceramic (LTCC) substrate.     

Preparation of MnOx/TiO2 ultrafine nanocomposite with large surface area and its enhanced toluene oxidation at low temperature

The TiO₂ support materials were synthesized by a chemical vapor condensation (CVC) method and the subsequent MnO_x/TiO₂ catalysts were prepared by an impregnation method. Catalytic oxidation of toluene on the MnO_x/TiO₂ catalysts was examined with ozone. These catalysts had a smaller particle size (9.1 nm) and a higher surface area (299.5 m² g⁻¹) compared to MnO_x/P25-TiO₂ catalysts. The catalysts show high catalytic activity with the ozone oxidation of toluene even at low temperature. As a result, the synthesized support material by the CVC method gave more active catalyst.     

Morphological characteristics of mechanically processed ZnO and MnO2 powder mixtures

The evolution of structural-morphological characteristics of ZnO + 1 wt.% MnO₂ and ZnO + 10 wt.% MnO₂ samples during prolonged mechanical treatment (MT) was investigated by X-ray, AFM, LPS, SEM and IR methods. Changes in crystallite size due to mechanical activation were determined from X-ray measurements. These results were correlated with changes in particle size followed by SEM and AFM. Particle and aggregate size distributions were determined from LPS measurements. Interpretation of the evolution of IR-absorption peaks during mechanical activation using the theory of average dielectric constants enabled analysis of changes of particle and agglomerate shapes. All these results enabled establishment of a relationship between crystallites, particles, aggregates of particles, and superficial processes that occur during mechanical activation.     

Preparation and electrochemical properties of LiCoO2-LiNi0.5Mn0.5O2-Li2MnO3 solid solutions with high Mn contents

The solid solutions LiCoO₂-LiNi_1/2Mn_1/2O₂-Li₂MnO₃ with higher Mn content have been prepared by a spray drying method between 750 and 950 °C and their electrochemical performances have also been characterized. The effects of the Li content on the structure and electrochemical performance of the samples have been studied. It was found that their lattice parameters a, c and V increase with the increase in Ni content and the decrease in Co content. The solid solutions xLiCoO₂-yLiNi_1/2Mn_1/2O₂-(1−x−y)Li₂MnO₃ with x = 0.18, 0.27 and y = 0.2 have the largest discharge capacity, which is more than 200 mAh/g in the voltages of 3.0-4.6 V. It is believed that the optimum Co content x in xLiCoO₂-yLiNi_1/2Mn_1/2O₂-(1−x−y)Li₂MnO₃ is between 0.2 and 0.3 in the charge-discharge voltage range of 3.0-4.6 V. The solid solutions xLiCoO₂-yLiNi_1/2Mn_1/2O₂-(1−x−y)Li₂MnO₃ with x = 0.18-0.36 and y = 0.2 have the excellent cycling performance and the capacity retention attains to almost 100% after 50 cycles. Moreover, it is found that the discharge capacity gradually increases with the increment of cycle number especially in the initial 10 cycles. XRD showed that the layered structure has been kept all the time in 20 cycles, which is perhaps the reason why the sample has the excellent cycling performance.     

Fluorescence improvement of Ba1.3Ca0.7SiO4:Eu,Mn phosphors via Dy addition and their color-tunable properties

A series of novel single-phase white phosphors Ba_1.3Ca_0.69−x−ySiO₄:0.01Eu²⁺,xMn²⁺, yDy³⁺ were synthesized by the solid-state method. The excitation spectra of these phosphors exhibit a broad band in the range of 260–410 nm, which can meet the application requirements for near-UV LED chips (excited at 350–410 nm). The emission spectra consist of two broad bands positioned around 455 nm and 596 nm, which are assigned to 5d→4f transition of Eu²⁺, and ⁴T₁→⁶A₁ transition of Mn²⁺, respectively. The luminescence intensity of phosphors enhances obviously by doping Dy³⁺ ions, and the intensity of two bands reaches an optimum when Dy³⁺ amounts to 2 mol%. In addition, thermoluminescence investigation of phosphor was conducted, getting two shallow trap defects with activation energy of 0.43 eV and 0.45 eV, which demonstrates the energy transfer mechanism of Dy–Eu through the process of hole and electron traps. By precisely tuning the Mn²⁺ content, an optimized white light with color rendering index (CRI) of R_a=84.3%, correlated color temperature (CCT) of T_c=8416 K and CIE chromaticity coordinates of (0.2941, 0.2937) is generated. The phosphor could be a potential white phosphors for near-UV light emitting diodes.     

Structural and magnetic characterization of MnxZn1 − xFe2O4 (x = 0.2; 0.35; 0.65; 0.8; 1.0) ferrites obtained by the citrate precursor method

In this work the microstructure and magnetic properties of Mn-Zn ferrites powders were investigated. Mn_xZn1 _− xFe₂O₄ powders where x = 0.2; 0.35; 0.5; 0.65; 0.8 and 1.0 were obtained by citrate precursor method. Citrate resin precursor was burned on air atmosphere at 400 °C for 3 h. Mn-Zn powders were calcined at 950 °C during 150 min under inert atmospheres: N₂ and rarefied atmosphere. Thermal analysis of precursor resin, phase evolution and microstructure of Mn-Zn ferrites powders were investigated by TG, DTA, XRD and SEM techniques. The powders calcined under rarefied atmosphere show spinel cubic structure and contamination of α-Fe₂O₃, while powders calcined under N₂ presents only the spinel cubic structure. Particle size was observed by SEM ranging from 80 to 150 nm. The magnetic properties were measured employing a vibrating sample magnetometer (VSM). It was observed that the saturation magnetization M_s increased with the increase of Mn content. The M_s of Mn_0.8Zn_0.2Fe₂O₄ calcined on rarefied atmosphere and Mn_0.8Zn_0.2Fe₂O₄ calcined on N₂ was 23.31 emu g⁻¹ and 56.23 emu g⁻¹, respectively.