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1.
Oxidation-reduction equilibrium experiments were conducted with Li2O-CaO-Al2O3-ZnO-SiO2-B2O3 melts containing small concentrations of either copper oxide or iron oxide. The results indicated that, for oxide melts containing relatively large proportions of amphoteric oxides, i.e., Al2O3 and ZnO, the ratios lcub;(Cu2+)/(Cu+)P O 2 1/4rcub; and lcub;(Fe3+)/(Fe2+)P O 2 1/4rcub; decreased with an increase in basicity. With further increase in basicity, however, these ratios became independent of basicity. For very basic melts, the ratios increased with an increase in basicity. These variations of lcub;(Cu2+)/(Cu+)P O 2 1/4rcub; and lcub;(Fe3+)/(Fe2+)P O 2 1/4rcub; can be interpreted in terms of the optical basicity of the oxide melts and are consistent with the following general expressions for the red-ox equilibria within acidic and relatively basic melts, respectively: M n++(1/4)O2=M(n+1)++(1/2)O2− M n++(1/4)O2+(3/2)O2−=MO2 (3−n) and M n++(1/4)O2=(3/4)M(n+1)++(1/4)MO2 (3−n)  相似文献   

2.
The solid electrolyte cell — Mo|Cr + Cr2O3‖ZrO2(MgO)‖{Cu-Cr}alloy + (Cr2O3)fluxes|Mo+ is used at 1673 K to determine Cr2O3 activities in MO-MX 2-Cr2O3 (M = Ca2+, Ba2−, X = F or Cl) ternary fluxes, which are in equilibrium with the copper-chromium binary alloy. The ternary isothermal phase diagrams of CaO-CaF2-Cr2O3 and BaO-BaCl2-Cr2O3 system fluxes are inferred on the basis of the experimental results and binary phase diagrams. The results indicate that Cr2O3 activities in all fluxes always decrease with the increase of the X MO /X MX2 ratio. Partial replacement of BaO in BaO-BaF2-Cr2O3 fluxes by CaO is acceptable for economy and efficiency considerations. At the same time, partial substitution of BaO for CaO in CaO-CaF2-Cr2O3 fluxes is advantageous for phosphorus removal and chromium retention as a result of the increased Cr2O3 activities, increased basicities, and widening of the liquid zones. Compared to those in BaO-BaF2-Cr2O3 fluxes, Cr2O3 activities in CaO-CaF2-Cr2O3 fluxes approximately follow the same curve as the former, although the position and the width of the liquid zones are considerably different, and activities in BaO-BaCl2-Cr2O3 fluxes are higher at the lower Cr2O3 content, or vice versa. The activity coefficients of Cr2O3 in the fluxes decrease with the increase of the X MO /X MX 2 ratios.  相似文献   

3.
The Er3+doped double perovskite Ba2 CaWO6 crystal is a promising ratiometric thermometer based on the fluorescence intensity ratio(FIR) of transitions from 2 H11/2 and 4 S3/2to the lowered 4 I15/2 level.However,the Ca2+vacancy defect caused by the charge difference between rare-earth ions and the substituted alkaline-earth ions gives rise to the non-radiative probability and limits the t...  相似文献   

4.
Directional melting and solidification of Ba2YCu3O6+8 in low oxygen partial pressures were investigated by the laser-heated floating zone (LHFZ) technique. The following reaction was observed on melting at Po2 > 8 Pa: Ba2YCu3O6+8→ BaY2CuO5 + L where BaY2CuO5 phase comprised equiaxed particles. At < 8 Pa < Po2 < 103 Pa, the preceding reaction occurred, and at higher temperatures, the following reaction also occurred to produce a rodlike BaY2O4 phase, oriented in the growth direction: BaY2Cu05 ar BaY2O4 + L At pressures below about 8 Pa, the low temperature reaction observed was Ba2YCu2O6+8 → BaY2O4 + L In this case, the oriented BaY2O4 phase formed directly from Ba2YCu2O6+8 and was platelike in morphology. Directional growth of the BaY2O4 phase from BaY2CuO5 was modeled in a simple way. The BaY2Cu05 particles ahead of the BaY2O4 interface dissolve in the superheated liquid, and solute transport for BaY2O2 growth is assumed to be limited by diffusion along the growth direction over distances equal to half the rod or plate spacing. A relation between supereating at the growth interface and growth rate was derived from the present model. Some possibilities for making use of such aligned structures in the growth of the superconducting compound Ba2YCu3O6+8 are discussed.  相似文献   

5.
By employing an electrochemical technique involving stabilized zirconia as solid electrolyte and Mo + MoO2 mixture as reference electrode, the equilibrium oxygen partial pressures for three-phase assemblages of CaSiO3(s) + Ca3Si2O7(s) + {CaO + SiO2 + FexO} melt and Ca3Si2O7(s) + Ca2SiO4(s) + {CaO + SiO2 + FexO} melt were determined as: - log {PO2 (CS + C3S2 + L)/bar} = - 3.22 13000/(T/K) ± 0.05 - log {PO2 (C3S2 + C2S + L)/bar} = - 0.92 16400/ (T/K) ± 0.04. respectively, where CS, C3S2 and C2S indicate CaSiO3(s), Ca3Si2O7(s). and Ca2SiO4(s), respectively.  相似文献   

6.
The standard Gibbs energies of formation of barium phosphide and barium orthophosphate were determined by a chemical equilibration technique yielding the following results: 3Ba(1)+P2(g)=Ba3P2 (s) Δ=−732,000+156.1T(±12,800) (J/mol) 3BaO (s)+P2(g)+5/2O2(g)=Ba3(PO4)2(s) Δ=−2,523,000+580.0T(±16,600) (J/mol) The stability and the thermodynamic behavior of barium compounds as reaction products of dephosphorization of steel were discussed in terms of the oxygen partial pressure and the activity coefficient of Ba1.5P in molten Ba saturated with CaO. D.J. MIN, formerly Graduate Student, Department of Metallurgy, The University of Tokyo, Bunkyo-ku, Tokyo 113, Japan  相似文献   

7.
The equilibrium oxygen pressure over the Cr-Y2O3-YCrO3 coexistence has been measured by the following cells: Cr, Y2O3, YCrO3∥ZrO2∥Cr, Cr2O3 [I] Mn, MnO∥ZrO2∥Cr, Y2O3, YCrO3 [II] Moreover, the partial electronic conduction parameter,P e, has been determined simultaneously, as the oxygen partial pressure where then-type electronic and ionic conductivities are equal in the stabilized ZrO2. The equilibrium oxygen pressure,P O 2, over the Cr-Y2O3-YCrO3 coexistence andP e are expressed as log (PO 2/atm) = 10.6 − 4.39 × 1041/T ± 0.1 (1385 to 1470 K) log ( Pe/atm = 8.86 − 4.21 x 104 1/T ± 0.3 (1385 to 1470 K) From the equilibrium oxygen pressure and the standard Gibbs energy of formation of Y2O3, the standard Gibbs energy of formation of YCrO3 is calculated as ΔG o f /J mol™1 = −1.58 x 106 + 2.93 x 102 T ± 7 × 103 (1385 to 1470 K)  相似文献   

8.
As a cyan-emitting oxonitridosilicate phosphor,BaSi2O2N2:Eu2+can be used as a competent cyan compensator to improve the color rendering index of white light-emitting diodes(WLEDs).However,low luminescence efficiency and poor thermal stability of this type of phosphor seriously suppress its actual application in full-spectrum lighting.The replacements of Ba2+by Lu3+and Ba2+-Si4+by Lu3+-Al3+can greatly increase the luminescence intensity and improve the thermal stability at the same time.With Lu3+doping,the internal quantum efficiencyηIQE Ba0.925Si2O2N2:0.03 Eu2+,0.045 Lu3+is 24.08%higher than that of Ba0.97Si2O2N2:0.03 Eu2+.After Al3+co-doping,theηIQE is further increased by 10.31%compared to Ba0.925Si2O2N2:0.03 Eu2+,0.045 Lu3+.When the temperature rises to 473 K,the luminescence intensity of Ba0.925Si2O2N2:0.03 Eu2+,0.045 Lu3+maintains 62.32%of that at room temperature,which increases by 17.35%in relative to the Ba0.97Si2O2N2:0.03 Eu2+,while the luminescence intensity of Ba0.925Si1.97O2N2:0.03 Eu2+,0.045 Lu3+,0.03 Al3+keeps 73.87%of the initial value,which increases by18.52%compared to Ba0.925Si2O2N2:0.03 Eu2+,0.045 Lu3+.The mechanisms for luminescence and thermal stability improvement are proposed.The Ba0.925Si1.97O2N2:0.03 Eu2+,0.045 Lu3+,0.03 Al3+cyan phosphor,Y3 Al5 O12:Ce3+yellow phosphor and CaAlSiN3:Eu2+red phosphor are mixed thoroughly and coated on a blue LED(450 nm)to assemble a WLED.The WLED demonstrates a color rendering index(Ra)of 97.1 at150 mA,and the R1-R15 values are all above 90.The results indicate that as an effective cyan compensator in WLED,the BaSi2O2N2:Eu2+,Lu3+,Al3+phosphor has great application prospect in the field of full-spectrum lighting.  相似文献   

9.
Oxygen permeability of commercial calcia-stabilized zirconia has been measured at 1673 to 1823 K by the following cell; O2 ZrO2(CaO) N2 - O2 (P’tO2 = 1 atm) solid electrolyte (P″O2 = 0.39 - 1010-3 atm). Oxygen permeability of calcia-stabilized zirconia is proportional to (1 - P″O2 1/4). From the permeability measurement, the conduction properties of the electrolyte were log σ- b+ = 0.28- 5100/T and logPb+ =-0.87 + 15,400/T where σ- b+ is the t-@#@ type electronic conductivity at PO 2 = 1 atm, and Pb+ is the oxygen activity at which the t-@#@ type electronic conductivity and the ionic conductivity are equal.  相似文献   

10.
A novel green-emitting phosphor,Eu2+-doped Ca2-x/2 Si1-x Px O4(0.25≤x≤0.30),was prepared through a conventional solidstate reaction.X-ray diffraction(XRD),photoluminescence(PL) and decay studies were employed to characterize the sample,which was assigned to P63mc space group in the hexagonal system.The effect of P-doping on the α-Ca2 SiO4 was studied and P2 O5 broken down by the raw material of(NH4)2 HPO4 played an important role in stabilizing α-Ca2 SiO4 which can only be stable at high temperature.The XRD patterns of the Ca2-x/2 Si1-x Px O4 host were found pure and optimized when the mole fraction of P2 O5 was 14.5%.The diffuse reflectance spectra of the Ca1.855 Si0.71 P0.29 O4 and Ca1.845 Si0.71 P0.29 O4 :0.01Eu2+covered the spectral region of 230-400 nm,implying that the phosphor was suitable for UV or near-UV LED excitation.The phosphor could be effectively excited in the near UV region with the maximum at 372 nm.The emission spectrum of the Ca1.845 Si0.71 P0.29 O4 :0.01Eu2+phosphor showed an asymmetrical single intensive band centered at 513 nm,which corresponded to the 4f65d1→4f7transition of Eu2+.Eu2+ions might occupy two types of Ca2+sites in the Ca1.855 Si0.71 P0.29 O4 lattice and form two corresponding emission centers,which led to the asymmetrical emission of Eu2+in Ca1.855 Si0.71 P0.29 O4.The effects of Eu2+-doped concentration in Ca1.855-x Si0.71 P0.29 O4 :xEu2+on the PL were also discussed,the optimum doping concentration of Eu2+was 1 mol.% and the critical distance of the energy transfer was also calculated by the concentration-quenching method.The non-radiative energy transfer between Eu2+seemed to be caused by the multipole-multipole interaction.The fluorescence lifetime of Eu2+was found to be 0.55711 μs.The results suggested that these phosphors might be promising candidates used for near UV light excited white LEDs.  相似文献   

11.
In this paper,luminescence thermal quenching of M_2SiO_4:Eu~(2+)(M=Sr,Ba) orthosilicate phosphors and mechanisms for thermal quenching proposed by different authors are briefly reviewed.Depending on preparation conditions and/or Eu~(2+)-doping concentrations,the quenching temperature(T_(1/2)) and activation energy for thermal quenching of the same orthosilicate phosphor reported by different authors are inconsistent.The common conclusion is that T_(1/2) of the intermediate compound(Ba_(1-x)Sr_x)_2 SiO_4:Eu~(2+)(x≈0.5) is higher than that of either Sr_2So_4;Eu~(2+)or Ba_2SiO_4;Eu~(2+)end-member.Moreover,T_(1/2) of the best-performing SrBaSiO_4:Eu~(2+)is evidently lower than that of YAG:Ce~(3+)and some Eu~(2+)-doped nitride phosphors.Rega rding the quenching mechanism,most of the investigators attributed thermal quenching to a thermally assisted 4f-5d cross-over in the configuration coordinate diagram.Only a few authors ascribed thermal quenching to a thermally assisted photoionization of 5 d electron to conduction band of the host.Nonetheless,a close inspection of T_(1/2) and Stokes shift derived from the vibrational spectra of the intermediate compound and end-member phosphors indicates that the 5d electron photo ionization model instead of the 4f-5d crossing decay model should be the genuine mechanism for the thermal quenching of M_2 SiO_4:Eu~(2+)(M=Sr,Ba) phosphors.Since the relationship between T_(1/2) and Stokes shift of the phosphors does not support the 4 f-5 d crossing decay model.The ionization probability of the 5 d electron depends on the energy gap(E_(dC)) between 5 d_1 level of the Eu~(2+)and conduction band minimum(CBM) of the host at higher temperatures.Lattice thermal expansion would result in an elevating 5 d_1 level of the Eu~(2+)along with a diminishing CBM of the host and as a consequence a reduction in E_(dC) and an enhanced photo ionization probability at elevated temperatures.A less rigid lattice and hence a larger coefficient of thermal expansion of M_2SiO_4 hosts should be the physical origin of poorer thermal quenching properties of the orthosilicate phosphors.  相似文献   

12.
White light-emitting diodes (WLEDs) fabricated by single-phase full color emitting phosphor are an emerging solution for health lighting. The crystallographic site occupation of activators in a proper host lattice is crucial for sophisticated design of such phosphor. Here, we report a high quality white light-emitting phosphor Ba2Ca(BO3)2:Ce3+(K+),Eu2+,Mn2+ with spectral distribution covering whole visible region. Blue light emission originates from Ce3+ ions occupying preferentially Ba2+ site by controlling synthesis conditions. Green and red lights are obtained from Eu2+ occupying Ba2+ (and Ca2+) site and Mn2+ occupying Ca2+ site, respectively. In this triple-doped phosphor, strong red emission with a low concentration of Mn2+ is realized by the efficient energy transfer from Ce3+ and Eu2+ to Mn2+. Furthermore, high quality white light is accomplished by properly tuning the relative doping amount of Ce3+(K+)/Eu2+/Mn2+ based on efficient simultaneous energy transfer. The results indicate that Ba2Ca(BO3)2:Ce3+(K+),Eu2+,Mn2+ is a promising white light-emitting phosphor in WLEDs application.  相似文献   

13.
In this work,through a facile method of low-temperature(only 350 ℃) self-reduction,1D nano-sized M2B5O9CI:Eu2+(M=Sr,Ca) blue phosphors with highly efficient performance can be obtained.The crystal structure,morphology and photoluminescence(PL) properties including thermal stability of M2B5O9CI:Eu2+(M=Sr,Ca) phosphors were investigated.The M2B5O9CI:Eu2+(M=Sr,Ca) phos...  相似文献   

14.
A green long persistent luminescence (LPL) phosphor Ca3Ga4O9:Tb3+/Zn2+ was prepared. Ca3Ga4O9 matrix exhibits blue self-activated LPL due to the creation of intrinsic traps. When Tb3+ is doped, the photoluminescence (PL) and LPL colors change from blue to green with their intensities significantly enhanced. The doping of Zn2+ evidently improves the PL and LPL performances of the Ca3Ga4O9 matrix and Ca3Ga4O9:Tb3+. The thermoluminescence (TL) spectra show that a successive trap distribution is formed by multiple intrinsic traps with different depths in the Ca3Ga4O9 matrix, and the incorporation of Tb3+ and Zn2+ effectively increases the densities of these intrinsic traps. The existence of a successive trap distribution makes the Ca3Ga4O9:Tb3+/Zn2+ phosphor exhibit thermally stable PL and LPL. It is indicated that this phosphor shows great promise for the application such as high-temperature LPL phosphor.  相似文献   

15.
The ab initio self-consistent DV-Xα (discrete variational Xα) method was used in its relativistic and spin-polarized model to investigate the ground-state electronic structures of the crystal YPO4 and YPO4:RE3+ (RE=Ce, Pr and Sm) and f-d transition energies of the lattice. The calculation was performed on the clusters Y5P10O32 and REY4P10O32 embedded in a microcrystal containing about 1500 ions, respectively. The ground-state calculation provided the locations of the 4f and 5d crystal-field one-electron levels of RE3+ relative to the valence and conduction bands of host, the curve of total and the partial density of states, and the corresponding occupation numbers, etc. Especially, the transition-state calculation was performed to obtain the 4f → 5d transition energies of RE3+ in comparison to the experimental observations. The lattice relaxation caused by the dopant ion RE3+ was discussed based on the total energy calculation and the transition-state calculation of the f-d transition energies.  相似文献   

16.
Electrochemical measurements involving stabilized zirconia as solid electrode and Mo + MoO2 as reference electrode were conducted in order to determine the chemical potentials of oxygen for threephase assemblages of CaO (s) + Ca4P2O9 (s) + liquid and Ca4P2O9 + Ca3P2O8 + liquid within the system CaO + FexO + P2O5. The results for the former are $$\log (P_{O_2 } /atm) = 6.22 - 27,900 (T/K)$$ while for the latter, $$\log (P_{O_2 } /atm) = 6.35 - 27,600 (T/K)$$   相似文献   

17.
Commercial phosphors always require fewer impurities and higher crystallinity, but sometimes it is difficult or strict to synthesize a pure phase compound. Indeed, if the practical application is not influenced, it is acceptable to synthesize a kind of phosphors with diphase matrix that have similar structure and photoluminescence properties. In present work, we designed and synthesized a series of(1-x)BaMSiO_4·xBa_2 MSi_2 O_7:Eu(M = Zn~(2+), Mg~(2+)) diphase phosphors which contained two phases BaMSiO_4(hexagonal, P63) and Ba2 MSi_2 O_7(monoclinic, C2/c) by a high temperature solid-state reaction in air condition. The structures and luminescence properties related to the phase transform from BaMSiO_4 to Ba_2 MSi_2 O_7 were analyzed carefully. The results show that the self-reduction ability of Eu~(3+) is not the best in above four compounds, respectively. But it reaches the maximum and gets the green emission under the UV lamp when the matrix is in a proper ratio of two phases, which suggests that the heterostructure between the two crystals(BaMSiO_4 and Ba_2 MSi_2 O_7) improves the self-reduction process of the diphase.The possible mechanism of the tunable europium valence and the luminescent properties in(1-x)BaMSiO_4·xBa2 MSi_2 O_7:Eu phosphors were discussed in detail.  相似文献   

18.
The hardystonite phosphors of Eu2+ activated M2ZnSi2O7 (M=Sr, Ba) were synthesized by combustion-assisted method. They were systematically characterized by photoluminescence excitation and emission spectra. The emission spectra of these two phosphors showed that the main emission peaks are at 475 and 503 nm due to 4f65d1→4f7 transition of Eu2+. Both phosphors could be efficiently excited in the wavelength range of 250-425 nm where the near ultraviolet light-emitting diode was well matched. The (x, y) color coordinates were determined with the emission values (x, y)=(0.41, 0.21) and (0.16, 0.45) for the M2ZnSi2O7: Eu2+ (M=Sr, Ba) phosphors.  相似文献   

19.
A novel orange-red emitting Ba3Y4O9:Sm3+ phosphors were prepared by a high temperature solid-state reaction in air. X-ray diffraction (XRD), photoluminescence spectra, fluorescence decay and temperature-dependent emission spectra were utilized to characterize the structure and luminescence properties. The results show that the excitation spectrum includes a series of linear peaks at 350, 367, 382, 410, 424, 445, 470 and 495 nm, respectively. Under 410 nm excitation, the emission peaks were located at 574 nm (4G5/26H5/2), 608 nm (4G5/26H7/2), 659 nm (4G5/26H9/2) and 722 nm (4G5/26H11/2), respectively. The concentration quenching occurs when x equals 0.08 for Ba3Y4–xO9:xSm3+ phosphor and its mechanism is ascribed to the dipole–dipole interaction. The chromaticity coordinates of Ba3Y3.92O9:0.08Sm3+ phosphor are in the orange-red region. The temperature-dependent study shows that this phosphor has excellent luminescence thermal-stability. And the luminescence intensity of Ba3Y3.92O9:0.08Sm3+ phosphor at 473 K only declines by about 25.75% of its initial intensity. The experimental data indicate that Ba3Y4O9:Sm3+ phosphor may be promising as an orange-red emitting phosphor for white light emitting diodes.  相似文献   

20.
The oxygen adsorption/desorption properties of double perovskite structure oxides PrBaCo2O5+δ,GdBaCo2O5+δ,and YBaCo2O5+δ were investigated by the thermogravimetry(TG)method in the temperature range of 400~900 ℃.The calculated oxygen adsorption/desorption surface reaction rate constants ka and kd of these double perovskite structure oxides were larger than the commonly used cubic perovskite oxides,such as Ba0.95Ca0.05Co0.8Fe0.2O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ,whereas,the oxygen permeation flux was comparable to that of the latter,which was attributed to the smaller difference of oxygen vacancy in oxygen and nitrogen atmosphere(Δδ/Vmol)in these double perovskite structure oxides.The large oxygen adsorption/desorption rate constants of GdBaCo2O5+δ and PrBaCo2O5+δ made them nice catalyst coating materials,on other membrane surfaces,to improve the oxygen permeability.  相似文献   

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