Sol-gel synthesis and characterization of SiO2@CaWO4, SiO2@CaWO4 : Eu3+/Tb3+ core-shell structured spherical particles

Nanocrystalline CaWO4 and Eu3+ (Tb3+)-doped CaWO4 phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by the Pechini sol-gel method, resulting in the formation of SiO2@CaWO4, SiO2@CaWO4:Eu3+/Tb3+, core-shell structured particles. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), time-resolved PL spectra and lifetimes were used to characterize the core-shell structured materials. Both XRD and FT-IR indicate that CaWO4 layers have been successfully coated on the SiO2 particles, which can be further verified by the FESEM and TEM images. The PL and CL demonstrate that the SiO2@CaWO4 sample exhibits blue emission band WO42- with a maximum at 420 nm (lifetime = 12.8 mu s) originated from the 4 groups, while SiO2@CaWO4:Eu3+ and SiO2@CaWO4:Tb3+ show additional red emission dominated by 614 nm (Eu3+:D-5(0)-F-7(2) transition, lifetime = 1.04 ms) and green emission at 544 nm (Tb3+:D-5(4)-F-7(5) transition, lifetime = 1.38 ms), respectively.

Sol-gel synthesis and photoluminescence properties of spherical SiO2@LaPO4 : Ce3+/Tb3+ particles with a core-shell structure

LaPO4: Ce3+ and LaPO4: Ce3+, Tb3+ phosphor layers have been deposited successfully on monodispersed and spherical SiO2 particles of different sizes ( 300, 500, 900 and 1200 nm) through a sol - gel process, resulting in the formation of core - shell structured SiO2@ LaPO4: Ce3+/ Tb3+ particles. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microcopy (SEM), transmission electron microscopy (TEM), and general and time-resolved photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting SiO2@ LaPO4: Ce3+/ Tb3+ samples. The XRD results demonstrate that the LaPO4: Ce3+, Tb3+ layers begin to crystallize on the SiO2 templates after annealing at 700 degrees C, and the crystallinity increases on raising the annealing temperature. The obtained core - shell phosphors have perfectly spherical shape with a narrow size distribution, non-agglomeration, and a smooth surface. The doped rare-earth ions show their characteristic emission in the core - shell phosphors, i.e. Ce3+ 5d - 4f and Tb3+5D4 - F-7(J) (J = 6 - 3) transitions, respectively. The PL intensity of the Tb3+ increased on increasing the annealing temperature and the SiO2 core particle size.

Electrogenerated chemiluminescence biosensor based on Ru(bpy)(3)(2+) and dehydrogenase immobilized in sol-gel/chitosan/poly(sodium 4-styrene sulfonate) composite material

A new electrogenerated chemiluminescence biosensor was fabricated by immobilizing ECL reagent Ru(bPY)(3)(2+) and alcohol dehydrogenase in sol-gel/chitosan/poly(sodium 4-styrene sulfonate) (PSS) organically modified composite material. The component PSS was used to immobilize ECL reagent Ru(bpy)(3)(2+) by ion-exchange, while the addition of chitosan was to prevent the cracking of conventional sol-gel-derived glasses and provide biocompatible microenvironment for alcohol dehydrogenase. Such biosensor combined enzymatic selectivity with the sensitivity of ECL detection for quantification of enzyme substrate and it was much simpler than previous double-layer design. The detection limit was 9.3 x 10(-6) M for alcohol (S/N = 3) with a linear range from 2.79 x 10(-5) to 5.78 x 10(-2) M. With ECL detection, the biosensor exhibited wide linear range, high sensitivity and good stability.

Silica supported submicron SiO2@Y2SiO5 : Eu3+ and SiO2@Y2SiO5 : Ce3+/Tb3+ spherical particles with a core-shell structure: Sol-gel synthesis and characterization

X-1-y(2)SiO(5):Eu3+ and X-1-Y2SiO5:Ce3+ and/or Tb3+ phosphor layers have been coated on nonaggregated, monodisperse, submicron spherical SiO2 particles by a sol-gel process, followed by surface reaction at high temperature (1000 degrees C), to give core/shell structured SiO2@Y2SiO5:Eu3+ and SiO2@Y2SiO5:Ce3+/Tb3+ particles. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), TEM, photoluminescence (PL), low voltage cathodoluminescence (CL), and time-resolved PL spectra and lifetimes are used to characterize these materials. The XRD results indicate that X-1-Y2SiO5 layers have been successfully coated on the sur- face Of SiO2 particles, as further verified by the FESEM and TEM images. The PL and CL studies suggest that SiO2@Y2SiO5:Eu3+, SiO2@Y2SiO5:Tb3+ (or Ce3+/Tb3+), and SiO2@Y2SiO5:Ce3+ core/shell particles exhibit red (Eu3+, 613 rim: D-5(0)-F-7(2)), green (Tb3+, 542nm: D-5(4)-F-7(5)), or blue (Ce3+, 450nm: 5d-4f) luminescence, respectively. Pl, excitation, emission, and time-resolved spectra demonstrate that there is an energy transfer from Ce3+ to Tb3+ in the SiO2@Y2SiO5:Ce3+,Tb3+ core/shell particles.

Luminescence properties of sol-gel derived spherical SiO2@Gd-2(WO4)(3): Eu3+ particles with core-shell structure

Monodisperse, core-shell structured SiO2@Gd-2(WO4)(3):Eu3+ particles were prepared by the sol-gel method. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy, transmission electron microscopy, photoluminescence (PL) and low-voltage cathodoluntinescence (CL). PL and CL study revealed that the core-shell structured SiO2@Gd-2(WO4)(3):Eu3+ particles show strong red emission dominated by the D-5(0)-F-7(2) transition of Eu3+ at 615 nm with a lifetime of 0.89 ins. The PL and CL emission intensity can be tuned by the coating number of Gd-2(WO4)(3):Eu3+ phosphor layers on SiO2 particles, the size of the SiO2 core particles, and by accelerating voltage and the filament current, respectively.

Core-shell structured SiO2@YVO4 : Dy3+/Sm3+ phosphor particles: Sol-gel preparation and characterization

Spherical SiO2 particles have been coated with YVO4:Dy3+/Sm3+ phosphor layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO2@YVO4:Dy3+/Sm3+ particles. X-ray diffraction (XRD), Fourier-transform IR spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting SiO2 @YVO4:Dy3+/Sm3+ core-shell phosphors. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 300 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (20 nm for one deposition cycle). The core-shell particles show strong characteristic emission from Dy3+ for SiO2@YVO4:Dy3+ and from Sm3+ for SiO2@YVO4:Sm3+ due to an efficient energy transfer from YVO4 host to them. The PL intensity of Dy3+ and Sm3+ increases with raising the annealing temperature and the number of coating cycles.

Sol-gel fabrication and photoluminescence properties of SiO2@Gd2O3 : Eu3+ core-shell particles

A uniform nanolayer of europium-doped Gd2O3 was coated on the surface of preformed submicron silica spheres by a Pechini sol-gel process. The resulted SiO2@Gd2O3:Eu3+ core-shell structured phosphors were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays. The XRD results show that the Gd2O3:Eu3+ layers start to crystallize on the SiO2 spheres after annealing at 400 degrees C and the crystallinity increases with raising the annealing temperature. The core-shell phosphors possess perfect spherical shape with narrow size distribution (average size: 640 nm) and non-agglomeration. The thickness of the Gd2O3:Eu3+ shells on the SiO2 cores can be adjusted by changing the deposition cycles (70 nm for three deposition cycles). Under short UV excitation, the obtained SiO2@Gd2O3:Eu3+ particles show a strong red emission with D-5(0)-F-7(2) (610 nm) of Eu3+ as the most prominent group.The PL intensity of Eu3+ increases with increasing the annealing temperature and the number of coating cycles.

Sol-gel growth of Gd2MoO6 : Eu3+ nanocrystalline layers on SiO2 spheres (SiO2@Gd2MoO6 : Eu3+) and their luminescent properties

SiO2@Gd2MoO6:EU3+ core-shell phosphors were prepared by the sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy ITEM), photoluminescence (PL) spectra as well as kinetic decays were used to characterize the resulting SiO2@Gd2MoO6:Eu3+ core-shell phosphors. The XRD results demonstrate that the Gd2MoO6:Eu3+ layers on the SiO2 spheres begin to crystallize after annealing at 600 degrees C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 600 nm), are not agglomerated, and have a smooth surface. The thickness of the Gd2MoO6:Eu3+ shells on the SiO2 cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). The Eu3+ shows a strong PL luminescence (dominated by D-5(0)-F-7(2) red emission at 613 nm) under the excitation of 307 nm UV light.

Fabrication and optical properties of core-shell structured spherical SiO2@GdVO4 : Eu3+ phosphor via sol-gel process

Europium-doped nanocrystalline GdVO4 phosphor layers were coated on the surface of preformed submicron silica spheres by sol-gel method. The resulted SiO2@Gd0.95Eu0.05VO4 core-shell particles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra, low voltage cathodoluminescence (CL), time resolved PL spectra and kinetic decays. The XRD results demonstrate that the Gd0.95Eu0.05VO4 layers begin to crystallize on the SiO2 spheres after annealing at 600 C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have spherical shape, narrow size distribution (average size ca. 600 nm), non-agglomeration. The thickness of the Gd0.95Eu0.05VO4 shells on the SiO2 cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). PL and CL show that the emissions are dominated by D-5(0)-F-7(2) transition of Eu3+ (618 nm, red).

Enhanced thermal stability of zinc-based titanate (dielectric) ceramics prepared by the modified sol-gel route

A multi-component substitution of Co and Ni was incorporated into ZnTiO3 to form pure hexagonal Zn1-x(Co1/2Ni1/2)xTiO(3) (x = 0,0.8,0.9,1.0) dielectric ceramic powders by a modified sol-gel route, following heat treatments at 600 degrees C for 3 h and at 800 degrees C for 6 h. Differential scanning calorimetry measurements revealed that the order of increasing thermal stability of solid solution compound Zn1-x(Co1/2Ni1/2)(x)TiO3 was ZnTiO3 (945 degrees C), Zn0.1Ni0.9TiO3 (1346 degrees C), Zn-0.1(Co1/2Ni1/2)(0.9)TiO3 (1390 degrees C), and Zn0.1Co0.9TiO3 (> 1400 degrees C). Both the dielectric constant and loss tangent reached a maximum at x = 0.8 and then decreased with solubility, x, and measurement frequency.

Synthesis of nanocrystalline Ba(CoxZn1-x)(2)Fe16O27 by sol-gel auto-combustion method

The synthesis of nanocrystalline W-type hexaferrites Ba(CoxZn1-x)(2)Fe16O27 powders by sol-gel auto-combustion method has been investigated. The thermal decomposition process of dried gel was studied by thermogravimetry (TG), differential thermal analysis (DTA) and infrared spectra (IR). The structural and magnetic properties of resultant particles were investigated by X-ray diffraction (XRD), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM). The results reveal that the dried gel exhibits auto-combustion behavior. After combustion, pure nanocrystalline W-type hexaferrite phase starts to appear at the calcination temperature of 800 degrees C. The crystallinity and the grain size increase at higher temperature. The saturation magnetization and coercivity clearly depend on calcination temperature and Co content X.

Structure and properties of the ordered double perovskites Sr2MWO6 (M = Co, Ni) by sol-gel route

The single-phase double perovskites Sr2MWO6 (M=Co, Ni) were prepared by sol-gel method. Crystal Structure, magnetic properties and the morphology of Sr2CoWO6 and Sr2NiWO6 were investigated. X-ray powder diffraction (XRD) analysis shows single phase structure for Sr2MWO6 (M=Co, Ni) without any traces of impurities and the crystal structure of all the samples belongs to the tetragonal I4/m space group. SEM image for Sr2MWO6 (M=Co, Ni) indicate that the grains are homogeneous and connect each other very well. The Neel temperature for Sr2CoWO6 and Sr2NiWO6 are 23 K and 59 K, respectively. Magnetic measurements showed that the magnetic moment in these double perovskites originates mainly from the interactions between Ni ions and Co ions.

Photoluminescent properties of sol-gel derived (La, Gd)MgB5O10 : Ce3+/Tb3+ nanocrystalline thin films

Ce3+ and/or Tb3+-doped (La,Gd)MgB5O10 nanocrystalline thin films were deposited on silica glass substrates by a sol-gel dip-coating process using triethyl borate B(OC2H5)(3) as the boron source. The results of XRD indicated that the films have fully crystallized after annealing at 800 degrees C. The films are transparent, uniform and crack free with a thickness of about 300 nm, consisting of particles with an average grain size of 50 nm. The luminescence and energy transfer properties of Ce3+ and Tb3+ have been studied in the films. It is confirmed that the excitation energy of Ce3+ transfers to the Gd3+, migrates over the Gd3+ sublattices, trapped by the Tb3+ and resulted in its characteristic green emission (D-5(4)-F-7(5) at 543 nm) in GdMgB5O10 nanocrystalline films as in the powder phosphors.

Fabrication and luminescence properties of Y2SiWO8 : Dy3+ phosphors via sol-gel process

(YSiWO8)-Si-2:Dy3+ phosphors were prepared through a sol-gel process. XRD and photoluminespectra were used to characterize the resulting phosphors. The results indicated that the phosphors crystallized completely at 1000 degrees C. In Y2SiWO8:Dy3+ phosphors, the Dy3+ showed its characteristic yellow emission at 483nm (F-4(9/2)-H-6(5/2)) and 575nm (F-4(9/2)-H-6(13/2)) upon excitation into 275nm.

Study on the origin of inverted phase in drying solution-cast block copolymer films

In a previous study, we reported observation of the novel inverted phase (the minority blocks comprising the continuum phase) in kinetically controlled phase separating solution-cast poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer films [Zhang et al. Macromolecules 2000, 33, 9561-7]. In this study, we adopt the same approach to investigate the formation of inverted phase in a series of solution-cast poly(styrene-b-butadiene) (SB) asymmetric diblock copolymers having nearly equal polystyrene (PS) weight fraction (about 30 wt %) but different molecular weights. The microstructure of the solution-cast block copolymer films resulting from different solvent evaporation rates, R, was inspected, from which the kinetically frozen-in phase structures at qualitatively different block copolymer concentrations and correspondingly different effective interaction parameter, chieff, can be deduced. Our result shows that there is a threshold molecular weight or range of molecular weight below which the unusual inverted phase is accessible by controlling the solvent evaporation rate. In comparing the present result with that of our previous study on the SBS triblock copolymer, we find that the formation of the inverted phase has little bearing on the chain architecture. We performed numerical calculations for the free energy of block copolymer cylinders and found that the normal phase is always preferred irrespective of the interaction parameter and molecular weight, which suggests the formation of the inverted phase to have a kinetic origin.