Luminescent properties of Gd2Ti2O7 : Eu3+ phosphor films prepared by sol-gel process

Gd2Ti2O7: Eu3+ thin film phosphors were fabricated by a sol-gel process. X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800 degreesC and the crystallinity increased with the elevation of annealing temperatures. Uniform and crack free phosphor films were obtained, which mainly consisted of grains with an average size of 70 nm. The doped Eu3+ showed orange-red emission in crystalline Gd2Ti2O7 phosphor films due to an energy transfer from Gd2Ti2O7 host to them. Both the lifetimes and PL intensity of the Eu3+ increased with increasing the annealing temperature from 800 to 1000 degreesC, and the optimum concentrations for Eu3+ were determined to be 9 at.%. of Gd3+ in Gd2Ti2O7 film host.

Luminescence and energy transfer properties of Ca2Gd8(SiO4)(6)O-2 : A(A = Pb2+, Tm3+) phosphors

Ca2Gd8(SiO4)(6)O-2: A(A = Ph2+, Tm3+) phosphors were prepared through the sol-gel process. X-ray diffraction (XRD), scanning electron microseopy(SEM) and photoluminescence spectra were used to characterize the resulting phosphors. The results of XRD indicate that the phosphors crystallized completely at 1000 degreesC. SEM study reveals that the average grain size is 300 similar to 1000 nm. In Ca2Gd8(SiO4)(6)O-2: Tm3+ phosphors, the Tm3+ shows its characteristic blue emission at 456 nm (D-1(2)-F-3(4)) upon excitation into its H-3(6)-D-1(2)(361 nm), with an optimum doping concentration of 1 mol% of Gd3+ in the host lattices. In Ca2Gd8(SiO4)(6)O-2: Pb2+, Tm3+ phosphors, excitation into the Ph2+ at 266 nm (S-1(0)-P-3(1)) yields the emissions of Gd3+ at 311 nm (P-6-S-8) and Tm3+ at 367 nm (D-1(2)-H-3(6)) and 456 our (D-1(2)-F-3(4)), indicating that energy transfer processes of Pb2+-Gd3+ and Ph2+-Tm3+ have occur-red in the host lattices.

Micellization and reversible pH-sensitive phase transfer of the hyperbranched multiarm PEI-PBLG copolymer

A novel, hyperbranched, amphiphilic multiarm biodegradable polyethylenimine-poly(gamma-benZyl-L-gluta- mate) (PEI-PBLG) copolymer was prepared by the ring-opening polymerization of gamma-benzyl-L-glutamate-N-car-boxyanhydride (BLG-NCA) with hyperbranched PEI as a macroinitiator. The copolymer could self-assemble into core-shell micelles in aqueous solution with highly hydrophobic micelle cores. As the PBLG content was increased, the size of the micelles increased and the critical micelle concentration (CMC) decreased. The surface of the micelles had a positive potential. The cationic micelles were capable of complexing with plasmid DNA (pDNA), which could be released subsequently by treatment with polyanions. The PEI-PBLG copolymer formed unimolecular micelles in chloroform solution. ne pH-sensitive phase-transfer behavior exhibited two critical pH points for triggering the encapsulation and release of guest molecules. Both the encapsulation and release processes were rapid and reversible. Under strong acidic or alkaline conditions, the release process became partially or completely irreversible.

A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

In the present work a nonmonotonic dependence of standard rate constant (k(0)) on reorganization energy (lambda) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k(0) on lambda is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of lambda, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the lambda dependence of k(0) for Process I is monotonic thoroughly, while for Process II on electrode surface the lambda dependence of k(0) could show a nonmonotonicity.

Stress transfer and damage evolution simulations of fiber-reinforced polymer-matrix composites

The stress transfer from broken fibers to unbroken fibers in fiber-reinforced thermosetting polymer-matrix composites and thermoplastic polymer-matrix composites was studied using a detailed finite element model. In order to check the validity of this approach, an epoxy-matrix monolayer composite was used as thermosetting polymer-matrix composite and a polypropylene (PP)-matrix monolayer composite was used as thermoplastic polymer-matrix composite, respectively. It is found that the stress concentrations near the broken fiber element cause damage to the neighboring epoxy matrix prior to the breakage of other fibers, whereas in the case of PP-matrix composites the fibers nearest to the broken fiber break prior to the PP matrix damage, because the PP matrix around the broken fiber element yields. In order to simulate composite damage evolution, a Monte Carlo technique based on a finite element method has been developed in the paper. The finite element code coupled with statistical model of fiber strength specifically written for this problem was used to determine the stress redistribution. Five hundred samples of numerical simulation were carried out to obtain statistical deformation and failure process of composites with fixed fiber volume fraction.

Optical spectroscopy properties of KMgF3 : Eu2+ nanocrystals and powder synthesized by microemulsion and solvothermal process

Nanocrystals and powders of KMgF3 doped with Eu2+ were synthesized by the microemulsion method and the solvothermal process, respectively. The emission and excitation spectra of KMgF3:Eu2+ phosphors were measured and compared with those of the samples synthesized through a solid. state reaction, Bridgman-Stockbarger method, and mild hydrothermal technique. The KMgF3: Eu2+ samples synthesized by means of the microemulsion method and the solvothermal process show only a sharp emission peak located at 360 nm, in the emission spectra, which arises from the f -> f(P-6(1/2)-> S-8(1/2)) transition of Eu2+. The broad emission bands appear at 420 nm,,which arises from Eu2+ <- O2- cannot be observed(in the mild hydrothermal and single crystal samples, the emission peak at 420 nm besides the emission of Eu2+ at 360 nm is observed). In the excitation spectrum of the KMgF3: Eu2+ samples synthesized by the microemulsion method and the solvothermal process, the excitation peaks show an intensive blue shift. The blue shift can he attributed to the lower oxygenic content in the KMgF3: Eu2+ samples synthesized by the microemulsion method and the solvothermal process.

Luminescent properties of rare-earth-doped CaWO4 phosphor films prepared by the Pechini sol-gel process

CaWO4 phosphor films doped with rare-earth ions (Eu3+, Dy-,(3+) Sm3+, Er3+) were prepared by the Pechini sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric and differential thermal analysis, atomic force microscopy, and photoluminescence spectra, as well as lifetimes, were used to characterize the resulting powders and films. The results of the XRD analysis indicated that the films began to crystallize at 400degreesC and that the crystallinity increased with elevation of the annealing temperature. The doped rare-earth ions showed their characteristic emissions in crystalline CaWO4 phosphor films due to energy transfer from WO42- groups to them. Both the lifetimes and PL intensities of the doped rare-earth ions increased with increasing annealing temperature, from 500 to 900degreesC, and the optimum concentrations for Eu3+, Dy3+, Sm3+, Er3+ were determined as 30, 1.5, 1.5, 0.5 at.% of Ca2+ in CaWO4 films annealed at 900degreesC, respectively.

Energy transfer and upconversion luminescence properties of Y2O3 : Sm and Gd2O3 : Sm phosphors

Y2O3:Sm and Gd2O3:Sm powder phosphors were prepared by carbonate coprecipitation method. The purified crystalline phases of Y2O3:Sm and Gd2O3:SM were obtained at 600degreesC, and the crystallinity increases with increase in annealing temperature. Both samples contain aggregated phosphor particles. An energy transfer (ET) from Y2O3 and Gd2O3 hosts to sm(3+) has been observed, and the ET efficiency in the latter is higher than that in the former because an energy migration process like Gd3+-(Gd3+)(n)-Sm3+ has occurred in the latter. Furthermore, an upconversion luminescence from the (4)G(5/2) level of Sm3+ has been observed in both Y2O3 and Gd2O3 under the excitation of 936 nm infrared, whose mechanisms are proposed. Both the up and downconversion emission intensities of Sm3+ in Gd2O3 are stronger than those in Y2O3.

Luminescence properties of RP1-xVxO4: A (R=Y, Gd, La; A=Sm3+Er3+ x=0, 0.5, 1) thin films prepared by pechini sol-gel process

Thin film phosphors with compositions of RP1-xVxO4: A (R = Y, Gd, La; A = Sm3+, Et3+; x = 0, 0.5, 1) have been prepared by a Pechini sol-gel process. X-Ray diffraction, atomic force microscopy (AFM), photoluminescence excitation and emission spectra were utilized to characterize the thin film phosphors. The results of XRD showed that a solid solution formed in YVxP1-xO4: A film series from x = 0 to x = 1 with zircon structure, which also held for GdVO4: A film. However, LaVO4: A film crystallized with a different structure, monazite. AFM study revealed that the phosphor films consisted of homogeneous particles ranging from 90 to 400 nm depending on the compositions. Upon short ultraviolet excitation, the films exhibit the characteristic Sm(3+ 4)G(5/2)-H-6(J) (J=5/2, 7/2, 9/2) emission in the red region and Er3+ H-2(11/2), S-4(3/2)-I-4(15/2) emission in the green region, respectively With the increase of x values in YVxP1-xO4: SM3+ (Er3+) films, the emission intensity Of SM3+ (Er3+) increases due to the increase of energy transfer probability from VO43- to Sm3+ (Er3+). Due to the structural effects, the Sm3+ (Er3+) shows similar spectral properties in YVO4 and GdVO4 films, which are much different from those in LaVO4 film.

Studies of electron-transfer and charge-transfer coupling processes at a liquid/liquid interface by double-barrel micropipet technique

Investigation of a heterogeneous electron-transfer (ET) reaction at the water/1,2-dichloroethane interface employing a double-barrel micropipet technique is reported. The chosen system was the reaction between Fe(CN)(6)(3-) in the aqueous phase (W) and ferrocene in 1,2-dichloroethane (DCE). According to the generation and the collection currents as well as collection efficiency, the ET-ion-transfer (IT) coupling process at such an interface and competing reactions with the organic supporting electrolyte in the organic phase can be studied. In addition, this technique has been found to be an efficient method to distinguish and measure the charge-transfer coupling reaction between two ions (IT-IT) processes occurring simultaneously at a liquid/liquid interface. On this basis, the formal Gibbs energies of transfer of some ions across the W/DCE interface, such as NO3-, NO2-, Cl-, COO-, TBA(+), IPAs+, Cs+, Rb+, K+, Na+, and Li+, for which their direct transfers are usually difficult to obtain because of the IT-IT coupling processes, were quantitatively evaluated.

Facilitated ion transfer across the micro-liquid /liquid interface supported at the tip of a silanized micropipette

Glass micropipettes with silanized inner walls can be filled with an organic solvent for voltammetric measurements in an aqueous solution. This arrangement was employed to investigate systematically the mechanism of facilitated potassium ion transfer by an ionophore dibenzo-18-crown-6 (DB18C6) across a micro-water/1.2-dichloroethane(W/DCE) interface supported at the tip of a silanized micropipette. Our experimental results verify that this facilitated ion transfer across the liquid/liquid interface did occur by an interfacial complexation-dissociation process (TIC-TID mechanism). The ratio of the diffusion coefficient of DB18C6 to that of its complexed ion in the DCE phase was calculated to be 1.74 +/- 0.07.

Synthesis of the complex fluoride LiBaF3 and optical spectroscopy properties of LiBaF3 : M(M = Eu,Ce) through a solvothermal process

The complex fluoride LiBaF3 and LiBaF3:M(M = Eu, Ce) is solvothermally synthesized at 180 degreesC and characterized by means of X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis and infrared spectroscopy. In the solvothermal process, the solvents, molar ratios of initial mixtures and reaction temperature play important roles in the formation of products. The excitation and emission spectra of the LiBaF3:M(M= Eu,Ce) have been measured by fluorescence spectrophotometer. In the LiBaF3: Eu emission spectra, there is one sharp line emission located at 360 nm arising from f --> f transition of Eu2+ in the host lattice, and typical doublet 5d-4f emission of Ce3+ in LiBaF3 powder is shown.

Luminescence properties of rare earth-polyoxometalate thin film deposited by sol-gel process

The rare earth (Eu3+, Dy3+)-polyoxometalate thin films were fabricated on quartz plate by the sol-gel method. The thin films were demonstrated by the luminescence spectra. The thin films exhibit the characteristic emission bands of the rare-earth ions. It is noticed that the yellow to blue intensity ratio (Y:B) of Dy3+ and the red to orange ratio (R:O) of Eu3+ in the films are different from that of the corresponding solids. Furthermore, the thin films present shorter fluorescence lifetime than the pure complexes. The reasons that were responsible for these results were also discussed.

Mechanisms of sodium and potassium ions transfer facilitated by dibenzo-15-crown-5 across the water /1,2-dichloroethane interface using micropipettes

The transfer of sodium and potassium ions facilitated by dibenzo-15-crown-5 (DB15C5) has been studied at the micro-water/1,2-dichloroethane (water/DCE) interface supported at the tip of a micropipette. Cyclic volt-ammetric measurements were performed in two limiting conditions: the bulk concentration of Na+ or K+ in the aqueous phase is much higher than that of DB15C5 in the organic phase (DB15C5 diffusion controlled process) and the reverse condition (metal ion diffusion controlled process). The mechanisms of the facilitated Na+ transfer by DB15C5 are both transfer by interfacial complexation (TIC) with 1 : 1 stoichiometry under these two conditions, and the corresponding association constants were determined at log beta(1) = 8.97 +/- 0.05 or log beta(1) = 8.63 +/- 0.03. However, the transfers of K+ facilitated by DB15C5 show different behavior. In the former case it is a TIC process and its stoichiometry is 1 : 2, whereas in the latter case two peaks during the forward scan were observed, the first of which was confirmed as the formation of K (DB15C5)(2) at the interface by a TIC mechanism, while the second one may be another TIC process with 1 : 1 stoichiometry in the more positive potential. The relevant association constants calculated for the complexed ion, K+(DB15C5)(2), in the organic phase in two cases, logbeta(2), are 13.64 +/- 0.03 and 11.34 +/- 0.24, respectively.

Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.