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1.
We report on the luminescence quenching mechanism of Eu-doped GaN powder phosphor produced with a low-cost, high yield rapid-ammonothermal method. We have studied as-synthesized and acid rinsed Eu-doped GaN powders with the Eu concentration of ~0.5 at.%. The Eu-doped GaN photoluminescence (PL) was investigated with 325 nm excitation wavelength at hydrostatic pressures up to 7.7 GPa in temperature range between 12 K and 300 K. The room temperature integrated Eu3+ ion PL intensity from acid rinsed material is a few times stronger than from the as-synthesized material. The temperature dependent PL studies revealed that the thermal quenching of the dominant Eu3+ ion transition (5D0  7F2) at 622 nm is stronger in the chemically modified phosphor indicating more efficient coupling between the Eu3+ ion and passivated GaN powder grains. Furthermore, it was found that thermal quenching of Eu3+ ion emission intensity can be completely suppressed in studied materials by applied pressure. This is due to stronger localization of bound exciton on Eu3+ ion trap induced by hydrostatic pressure. Furthermore, the effect of 2 MeV oxygen irradiation on the PL properties has been investigated for highly efficient Eu-doped GaN phosphor embedded in KBr–GaN:Eu3+ composite. Fairly good radiation damage resistance was obtained for 1.7 × 1012 to 5 × 1013 cm?2 oxygen fluence. Preliminary data indicate that Eu-doped GaN powder phosphor can be considered for devices in a radiation environment.  相似文献   

2.
The hydrostatic pressure effect on the dielectric properties of (NH4)2H2P2O6 ferroelectric crystal was studied for pressures from 0.1 MPa to 360 MPa and for temperatures from 100 to 190 K. The pressure–temperature phase diagram obtained is linear with increasing pressure. The paraelectric–ferroelectric phase transition temperature decreases with increasing pressure with the pressure coefficient dTc/dp=?5.16×10?2 K MPa?1. Additionally, the pressure dependences of Curie–Weiss constants for the crystal in paraelectric (C+) and ferroelectric (C?) phases are evaluated and discussed. The possible mechanism of paraelectric–ferroelectric phase transition is also discussed.  相似文献   

3.
《Solid State Ionics》2006,177(9-10):893-900
M2Mn3O8 (M = Ca2+, Cu2+) compounds were synthesized and characterized in lithium cells. The M2+ cations, which reside in the van der Waals gaps between adjacent sheets of Mn3O84−, may be replaced chemically (by ion-exchange) or electrochemically with Li. More than 7 Li+/Cu2Mn3O8 may be inserted electrochemically, with concomitant reduction of Cu2+ to Cu metal, but less Li can be inserted into Ca2Mn3O8. In the case of Cu2+, this process is partially reversible when the cell is charged above 3.5 V vs. Li, but intercalation of Cu+ rather than Cu2+ and Li+/Cu+ exchange occurs during the subsequent discharge. If the cell potential is kept below 3.4 V, the Li in excess of 4 Li+/Cu2Mn3O8 can be cycled reversibly. The unusual mobility of + 2 cations in a layered structure has important implications both for the design of cathodes for Li batteries and for new systems that could be based on M2+ intercalation compounds.  相似文献   

4.
《Journal of luminescence》2003,65(2-4):127-133
BaMgAl10O17:Eu2+ (BAM) blue phosphor particles with improved photoluminescence (PL) intensity under vacuum ultraviolet (VUV) excitation were prepared by a spray pyrolysis process. In order to improve the PL intensity, Er3+ and Nd3+ ions were used as co-doping elements. The VUV characteristics of BAM:Eu2+, M+ (M=Er, Nd) were monitored with varying the Er3+ and Nd3+ content in order to find the optimal co-doping concentration when they were prepared by spray pyrolysis. It was found that doping Er3+ or Nd3+ enhances the PL intensity of BAM:Eu2+ blue phosphor particles. In particular, the M3+ doping effect on the PL intensity was pronounced when the prepared BAM:Eu2+, M3+ particles were excited by 172 nm VUV. The maximum intensity was obtained when the M3+ content was 1.0 at% with respect to Ba element. The PL intensity of BAM:Eu2+, M+ (M=Er3+, Nd3+) particles was also further improved by producing them in a spherical shape, which was successfully achieved by controlling the spray solution. The optimized BAM:Eu2+, M+ particles had about 10% higher PL intensity than that of the commercial particles, which are made by a conventional solid-state reaction.  相似文献   

5.
《Solid State Ionics》2006,177(15-16):1381-1388
In this work, we have studied the multilayered polypyrrole(PPy)/oxide composite electrode on glassy carbon (GC) having the structure GC/PPy/PPy(Cu1.4Mn1.6O4)/PPy using X-ray Photoelectron Spectroscopy and Mn K-edge and Cu K-edge XANES and EXAFS. The mixed oxide particles have been incorporated into the PPy matrix simultaneously to the electropolymerization of Py from a solution containing 0.1 M Py + 0.15 M KCl + Cu1.4Mn1.6O4. The XPS data have shown that, prior to the incorporation of the oxide into the PPy matrix, it contains Cu+, Cu2+, Mn3+ and Mn4+. The XPS, XANES and EXAFS results have shown that when the oxide is incorporated into the PPy matrix, the Cu+ present in the original oxide suffers dismutation to give Cu2+ and metallic Cu. The metallic Cu is segregated out of the spinel structure. The Mn K-edge XANES and EXAFS data show that, after the incorporation into the PPy matrix, Mn is present as Mn3+ and Mn4+ occupying octahedral sites in a spinel-related structure while the Cu K-edge XANES and EXAFS data indicate that copper occupies tetrahedral sites predominantly in that structure but having a large degree of disorder in the second and higher coordination shells.  相似文献   

6.
《Current Applied Physics》2010,10(3):825-827
Zn(OH)2 is a kind of amphoteric compound. Therefore, for chemical coprecipitation method, the precipitation of Zn2+ ions may be incomplete if using NaOH as precipitator. In this study, single-phase powder specimens with a nominal composition Ni0.2Zn0.6Cu0.2Fe2O4 were prepared with chemical coprecipitation method, and the effects of excessive Zn2+ content (x, x = 3%, 5%, 7%, 9%) in working solution on intrinsic magnetic and structural properties were studied by vibrating sample magnetometer and X-ray diffractometer, respectively. It was found that the magnetization when Hm = 398 kA/m (5000 Oe) reached a maximum when x = 5%, and then decreased with the increase of x, which was attributed to the effect of different amount of Zn2+ in A sites on the A–B and B–B exchange interaction. Moreover, it was found that the lattice parameter was affected by the Zn2+ and Fe3+ ions due to their different ion radius to a certain extent.  相似文献   

7.
Ultrasound coupled with supercritical CO2 has become an important method for exfoliation of graphene, but behind which a peeling mechanism is unclear. In this work, CFD simulation and experiment were both investigated to elucidate the mechanism and the effects of the process parameters on the exfoliation yield. The experiments and the CFD simulation were conducted under pressure ranging from 8 MPa to 16 MPa, the ultrasonic power ranging from 12 W to 240 W and the frequency of 20 kHz. The numerical analysis of fluid flow patterns and pressure distributions revealed that the fluid shear stress and the periodical pressure fluctuation generated by ultrasound were primary factors in exfoliating graphene. The distribution of the fluid shear stress decided the effective exfoliation area, which, in turn, affected the yield. The effective area increased from 5.339 cm3 to 8.074 cm3 with increasing ultrasonic power from 12 W to 240 W, corresponding to the yield increasing from 5.2% to 21.5%. The pressure fluctuation would cause the expansion of the interlayers of graphite. The degree of the expansion increased with the increase of the operating pressure but decreased beyond 12 MPa. Thus, the maximum yield was obtained at 12 MPa. The cavitation might be generated by ultrasound in supercritical CO2. But it is too weak to exfoliate graphite into graphene. These results provide a strategy in optimizing and scaling up the ultrasound-assisted supercritical CO2 technique for producing graphene.  相似文献   

8.
Cd0.9−xZn0.1CuxS (0≤x≤0.06) nanoparticles were successfully synthesized by a conventional chemical co-precipitation method at room temperature. Crystalline phases and optical absorption of the nanoparticles have been studied by X-ray diffraction (XRD) and UV–visible spectrophotometer. XRD confirms the phase singularity of the synthesized material, which also confirmed the formation of Cd–Zn–Cu–S alloy nanocrystals rather than separate nucleation or phase formation. Elemental composition was examined by the energy dispersive X-ray analysis and the microstructure was examined by scanning electron microscope. The blue shift of absorption edge below Cu=2% is responsible for dominance of Cu+ while at higher Cu concentration dominated Cu2+, d–d transition may exist. It is suggested that the addition of third metal ion (Cu2+/Cu+) is an effective way to improve the optical property and stability of the Cd0.9Zn0.1S solid solutions. When Cu is introduced, stretching of Cd–Zn–Cu–S bond is shifted lower wave number side from 678 cm−1 (Cu=0%) to 671 cm−1 (Cu=6%) due to the presence of Cu in Cd–Zn–S lattice and also the size effect. The variation in blue band emission peak from 456 nm (∼2.72 eV) to 482 nm (∼2.58 eV) by Cu-doping is corresponding to the inter-band radiation combination of photo-generated electrons and holes. Intensity of red band emission centered at 656 nm significantly increased up to Cu=4%; beyond 4% it is decreased due to the quenching of Cu concentration.  相似文献   

9.
Nanoparticles of Mg2SiO4:Eu3+ have been prepared by the solution combustion technique and the grain size estimated by PXRD is found to be in the range 40–50 nm. Ionoluminescence (IL) studies of Mg2SiO4:Eu3+ pellets bombarded with 100 MeV Si8+ ions with fluences in the range 1.124–22.48×1012 ions cm?2 are carried out at IUAC, New Delhi, India. Five prominent IL bands with peaks at 580 nm, 590 nm, 612 nm, 655 nm and 705 nm are recorded. These characteristic emissions are attributed to the luminescence centers activated by Eu3+ cations. It is found that IL intensity decreases rapidly in the beginning. Later on, the intensity decreases slowly with further increase of ion fluence. The reduction in the ionoluminescence intensity with increase of ion fluence might be attributed to degradation of Si–O (ν3) and Si–O (2ν3) bonds present on the surface of the sample. The red emission with peak at 612 nm is due to characteristic emission of 5D07F2 of the Eu3+ cations. Thermoluminescence (TL) studies of Mg2SiO4:Eu3+ pellets bombarded with 100 MeV Si8+ cations with fluences in the range 5×1011 ions cm?2 to 5×1013 ions cm?2 are made at RT. Two prominent and well resolved TL glows with peaks at ~220 °C and ~370 °C are observed. It is observed that TL intensity increases with increase of ion fluence. This might be due to creation of new traps during swift heavy ion irradiation.  相似文献   

10.
This paper reports on the thermo (TL), iono (IL) and photoluminescence (PL) properties of nanocrystalline CaSiO3:Eu3+ (1–5 mol %) bombarded with 100 MeV Si7+ ions for the first time. The effect of different dopant concentrations and influence of ion fluence has been discussed. The characteristic emission peaks 5D07FJ (J=0, 1, 2, 3, 4) of Eu3+ ions was recorded in both PL (1×1011–1×1013 ions cm?2) and IL (4.16×1012–6.77×1012 ions cm?2) spectra. It is observed that PL intensity increases with ion fluence, whereas in IL the peaks intensity increases up to fluence 5.20×1012 ions cm?2, then it decreases. A well resolved TL glow peak at ~304 °C was recorded in all the ion bombarded samples at a warming rate of 5 °C s?1. The TL intensity is found to be maximum at 5 mol% Eu3+ concentration. Further, TL intensity increases sub linearly with shifting of glow peak towards lower temperature with ion fluence.  相似文献   

11.
A multi-switchable poly(NIPAM-co-SPO-co-D-π-A dye) hydrogel with a photochromic spironaphthoxazine and an electron donor-π-conjugated-electron acceptor (D-π-A) type dye was prepared by typical radical copolymerization. The low critical solution temperature (LCST) behavior was investigated by UV–vis spectroscopy, which allows the measurement of the phase transition from 20 to 40 °C in aqueous solution. The fluorescence intensity of the poly(NIPAM-co-SPO-co-D-π-A dye) was temperature-dependent. Reversible modulation of fluorescence intensity was achieved using alternating irradiation with UV and visible light. Prepared polymer hydrogel also exhibited spectra change when not only used Cu2+ cation but also an acid unit.  相似文献   

12.
《Solid State Ionics》2006,177(5-6):549-558
Perovskite-type LaGa0.65Mg0.15Ni0.20O3−δ exhibiting oxygen transport comparable to that in K2NiF4-type nickelates was characterized as a model material for ceramic membrane reactors, employing mechanical tests, dilatometry, oxygen permeability and faradaic efficiency measurements, thermogravimetry (TG), and determination of the total conductivity and Seebeck coefficient in the oxygen partial pressure range from 10 15 Pa to 40 kPa. Within the phase stability domain which is similar to La2NiO4+δ, the defect chemistry of LaGa0.65Mg0.15Ni0.20O3−δ can be adequately described by the ideal solution model with oxygen vacancies and electron holes to be the only mobile defects, assuming that Ni2+ may provide two energetically equivalent sites for hole location. This assumption is in agreement with the density of states, estimated from thermopower, and the coulometric titration and TG data suggesting Ni4+ formation in air at T < 1150 K. The hole conductivity prevailing under oxidizing conditions occurs via small-polaron mechanism as indicated by relatively low, temperature-activated mobility. The ionic transport increases with vacancy concentration on reducing p(O2) and becomes dominant at oxygen pressures below 10 7–10 5 Pa. The average thermal expansion coefficients in air are 11.9 × 10 6 and 18.4 × 10 6 K 1 at 370–850 and 850–1270 K, respectively. The chemical strain of LaGa0.65Mg0.15Ni0.20O3−δ ceramics at 1073–1123 K, induced by the oxygen partial pressure variations, is substantially lower compared to perovskite ferrites. The flexural strength determined by 3-point and 4-point bending tests is 167–189 MPa at room temperature and 85–97 MPa at 773–1173 K. The mechanical properties are almost independent of temperature and oxygen pressure at p(O2) = 1–2.1 × 104 Pa and 773–1173 K.  相似文献   

13.
A simple and sensitive spectrofluorimetric method was developed to determine trace amounts of bilirubin (BR) using yttrium (Y3+)–norfloxacin (NFLX) complex as a fluorescence (FL) probe. NFLX can form a stable binary complex with Y3+ and markedly enhances the weak FL signal of the NFLX. The FL intensity of the Y3+–NFLX complex decreased significantly in the presence of BR in a buffer solution at pH=7.2. Under optimal conditions, the FL intensity decreased according to the BR concentration and showed a good linear relationship in the range of 0.03–2.3 μg mL?1 of BR with a correlation coefficient of 0.9988. The limit of detection for the determination of BR was 2.8 ng mL?1 with a relative standard deviation (RSD) of 1.55% for five replicate determination of 0.05 μg mL-1 BR. The presented method offers higher sensitivity with simple instrumentation and was applied successfully in detecting BR at low concentrations.  相似文献   

14.
The degradation of a reactive azo dye, Direct Red 81 (DR81), by Fenton process and in conjunction with sonolysis (SonoFenton) was studied. The synergistic effect of Fenton process and sonolysis enhanced the degradation of Direct Red 81 in aqueous solutions and the reaction followed the mechanism of hydroxyl radical (HO) oxidation. The influence of the initial substrate concentration, pH and catalyst loading on the rate of decolorisation were studied. The dye decolorisation followed apparent first order kinetics. The optimum conditions for decolorisation were pH = 3.0, [Fe2+] = 0.2 g/l, [H2O2] = 5.1 × 10−3 mol/l and ultrasonic frequency = 120 kHz, 60 W. These conditions yielded 99% decolorisation of DR81 within 75 min. The sonolytic degradation products of DR81 were identified using Electrospray Ionization-Mass Spectrometry (ESI-MS). The presence of CO32−, HCO3, Cl, NO3, and SO42− ions in the dye solution did not have a considerable effect on the decolorisation efficiency. This study demonstrates that Fenton and SonoFenton methods can effectively decolorize DR81 dye in waste water. The dye concentration used in this study is higher compared to earlier studies illustrating the effective mineralization by the SonoFenton process. The mechanism of dye degradation is also proposed.  相似文献   

15.
We report on studies of the structure and dynamics of the (0 0 1) surface of single crystal LiCu2O2, investigated by He beam scattering at room temperature, and with lattice-dynamical models. The best fit surface corrugation to measured diffraction patterns shows that the surface termination is exclusively a Li1+Cu2+O2? plane. Lattice dynamics fits to inelastic He scattering spectra reveal the presence of two low-lying surface phonon modes, identified with the motion of Cu2+, Li1+ surface ions normal to the surface.  相似文献   

16.
Ionoluminescence (IL) and photoluminescence (PL) spectra for different rare earth ions (Sm3+ and Dy3+) activated YAlO3 single crystals have been induced with 100 MeV Si7+ ions with fluence of 7.81×1012 ions cm?2. Prominent IL and PL emission peaks in the range 550–725 nm in Sm3+ and 482–574 nm in Dy3+ were recorded. Variation of IL intensity in Dy3+ doped YAlO3 single crystals was studied in the fluence range 7.81×1012–11.71×1012 ions cm?2. IL intensity is found to be high in lower ion fluences and it decreases with increase in ion fluence due to thermal quenching as a result of an increase in the sample temperature caused by ion beam irradiation. Thermoluminescence (TL) spectra were recorded for fluence of 5.2×1012 ions cm?2 on pure and doped crystals at a warming rate of 5 °C s?1 at room temperature. Pure crystals show two glow peaks at 232 (Tg1) and 328 °C (Tg2). However, in Sm3+ doped crystals three glow peaks at 278 (Tg1), 332 (Tg2) and 384 °C (Tg3) and two glow peaks at 278 (Tg1) and 331 °C (Tg2) in Dy3+ was recorded. The kinetic parameters (E, b s) were estimated using glow peak shape method. The decay of IL intensity was explained by excitation spike model.  相似文献   

17.
A comparative study was carried out of sonochemical (SCh), electrochemical (ECh) and sonoelectrochemical (SECh) strategies for the degradation of the fungicide thiram in dilute aqueous solution. The SCh and SECh studies were performed using a sonicator equipped with an 11 mm titanium-alloy probe and operated at 20 kHz with a power intensity of 523 W cm−2. In the ECh and SECh investigations, galvanostatic electrolyses were implemented using a single compartment electrochemical cell with a boron-doped diamond electrode as anode and applied current densities in the range 10–50 mA cm−2. For these processes, the decrease in concentration of thiram was monitored by high performance liquid chromatographic (HPLC) analysis and values of current efficiency and energy consumption were determined. The results showed that the rate of degradation of thiram and the amount of energy consumed were directly proportional to the applied current density, while current efficiency was inversely related to current density. The kinetics of thiram degradation followed a pseudo first order model with apparent rate constants in the region of 10−3 min−1. Thiram in aqueous solution was subjected to “exhaustive” degradation by ECh and SECh processes for 5 h at applied current densities of 35 mA cm−2 and the intermediates/byproducts so-formed were identified by HPLC–mass spectrometry. Mechanisms of the degradation reactions have been proposed on the basis of the results obtained.  相似文献   

18.
This work aims at investigating for the first time the key sonication (US) parameters: power density (DUS), intensity (IUS), and frequency (FS) – down to audible range, under varied hydrostatic pressure (Ph) and low temperature isothermal conditions (to avoid any thermal effect).The selected application was activated sludge disintegration, a major industrial US process. For a rational approach all comparisons were made at same specific energy input (ES, US energy per solid weight) which is also the relevant economic criterion.The decoupling of power density and intensity was obtained by either changing the sludge volume or most often by changing probe diameter, all other characteristics being unchanged. Comprehensive results were obtained by varying the hydrostatic pressure at given power density and intensity. In all cases marked maxima of sludge disintegration appeared at optimum pressures, which values increased at increasing power intensity and density. Such optimum was expected due to opposite effects of increasing hydrostatic pressure: higher cavitation threshold then smaller and fewer bubbles, but higher temperature and pressure at the end of collapse.In addition the first attempt to lower US frequency down to audible range was very successful: at any operation condition (DUS, IUS, Ph, sludge concentration and type) higher sludge disintegration was obtained at 12 kHz than at 20 kHz. The same values of optimum pressure were observed at 12 and 20 kHz.At same energy consumption the best conditions – obtained at 12 kHz, maximum power density 720 W/L and 3.25 bar – provided about 100% improvement with respect to usual conditions (1 bar, 20 kHz). Important energy savings and equipment size reduction may then be expected.  相似文献   

19.
《Solid State Ionics》2006,177(9-10):885-892
Tri block-copolymer poly(iminoethylene)-b-poly(oxyethylene)-b-poly(iminoethylene) with a poly(oxyethylene) central block (PEI-b-PEO-b-PEI) were used as a “dual” matrix for polymer electrolytes having selectivity for hard cations (Li+/PEO) in one phase and for soft cations (Cu2+/PEI) in the other. Conductivity measurements were recorded for 20:1, 12:1 and 8:1 coordinating atom (O or/and N) to cation (Li+, Cu2+) ratios, for each of the three complexes studied: PEI-b-PEO-LiTFSI-b-PEI, PEI-Cu(TFSI)2-b-PEO-b-PEI-Cu(TFSI)2 and PEI-Cu(TFSI)2-b-PEO-LiTFSI-b-PEI-Cu(TFSI)2. For either low (20 °C) or high temperature (80 °C) the highest conductivity was given by the polymer electrolyte based on Cu(TFSI)2 with N/Cu2+ = 20:1 (10 6, respectively 2 × 10 4 S cm 1). In the present paper, the conductivity evolution is discussed in relation with the polymer structure, the type and the concentration of the salt and the thermal behavior of our systems.  相似文献   

20.
UV excited photo luminescence from Li2B4O7:Cu and Li2B4O7:Cu, Ag single crystals has been investigated in the temperature range from 77 K to 300 K. An excitation band having a doublet structure at 240 nm and 262 nm was observed for the emission at 370 nm that corresponds to 1A1g1Eg and 1A1g1T2g crystal field components of the 3d10→3d94s1 transition of Cu+. The relative intensity of these components and their temperature dependence provide a measure of the off-center displacement of the Cu+ ground state in the crystal lattice site. The co-doped Ag plays a role of a sensitizer when doped with Cu and increases the overall emission as the emission between Ag states lies in the excitation region of Cu states. The 370 nm emission in both the crystals slightly decreases with temperature; however a sudden increase in the intensity around 264 K was observed.  相似文献   

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