Chemical potentials of oxygen for mixtures of CaO (s) + Ca4P2O9 (s) + {CaO + P2O5 + FexO} melts and Ca4P2O9 (s) + Ca3P2O8 (s) + {CaO + P2O5 + FexO} melts

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 + Fe_xO + P₂O₅. The results for the former are $$\log (P_{O_2 } /atm) = 6.22 - 27,900 (T/K)$$ while for the latter, $$\log (P_{O_2 } /atm) = 6.35 - 27,600 (T/K)$$      

Activities of FexO in CaO + CaF2 + SiO2 + FexO quaternary slags by disposable electrochemical oxygen probes

The activities of Fe_xO in CaO + CaF₂ + SiO₂ + Fe_xO quaternary slags were measured by means of solid-oxide galvanic cell. The Fe_xO activities in the slags are influenced by CaF₂ as well as SiO₂. At constant Fe_xO mole fractions, e.g., , at low SiO₂ mole fractions i.e., , the substitution of CaF₂ for CaO has an effect of raising the Fe_xO activity. At higher SiO₂ mole fractions, e.g., , however, such an effect becomes insignificant.     

Chemical potentials of components of the system CaO + P2O5 + FexO at 1673 K

Electromotive force (emf) measurements were conducted with a solid oxide galvanic cell of the type Mo/Mo + MoO₂/ZrO₂ (MgO)/Fe (s) + Fe_xO (in slag)/Ag/Fe at 1673 K in order to obtain the activities of Fe_xO in CaO + P₂O₅ + Fe_xO ternary slags. By using the Gibbs-Duhem integration, the activities of P₂O₅ and CaO were also obtained.     

Thermodynamics of iron oxide in FexO‐dilute CaO + Al2O3 + SiO2 + FexO slags at 1873 K

The ferrous and ferric ion capacities, and , for the slag of CaO + Al₂O₃ + SiO₂ are determined at 1873 K by means of the distribution equilibrium of iron between Fe_xO dilute slags of the system and Pt + Fe alloys under a controlled atmosphere. Compared with the values of for CaO + Al₂O₃ binary slag at a constant ratio of Al₂O₃ to decreases with an increase in SiO₂ content. Nearly linear relationships are observed between the logarithm of the ferrous and ferric ion capacities and the optical basicity. Applying these capacities, the relationship between (%Fe^T) and PO₂ under iron saturation, as well as the iron redox equilibrium in slag in relation to the optical basicity were discussed.     

A thermodynamic study of the system CaO + Al2O3 + FexO at 1673 K

Electrochemical measurements of the solid-oxide galvanic cell: Mo/Mo + MoO₂/ZrO₂(MgO)/(CaO + Al₂O₃ + Fe_xO) + Fe(s) + Ag/Fe have been conducted at 1673 K in order to obtain the activities of Fe_xO) in CaO + Al₂O₃ + Fe_xO slags. By using the activity data for Fe_xO, the isothermal section of the phase diagram for the system CaO + Al₂O₃ + Fe_xO was derived.     

The Activities of FexO in {CaO‐SiO2‐Al2O3‐MgO‐FexO} Slags at 1723 K

In Japanese steelworks, hot metal is now produced by scrap melting process. With this process removal of sulphur is very much handicapped because of very high sulphur levels (0.04 to 0.09 pct by weight) and relatively low tapping temperatures (1623 to 1723 K). In order to overcome such disadvantages, the authors explored on the phase diagrams of {CaO‐SiO₂‐Al₂O₃‐MgO} slags, and this research revealed that those slags at 35 wt%‐Al₂O₃ would be good candidates as reagents for the removal of sulphur from high sulphur hot metal at relatively low temperatures. For better understanding of the thermodynamic properties of the candidate slags, in this study, activities of Fe_xO were determined by using solid‐state electrochemical cells incorporating MgO‐stabilized zirconia and Mo + MoO₂ reference electrode.     

Experimental liquidus in the PbO-ZnO-“Fe2O3”-(CaO + SiO2) System in Air,with CaO/SiO2 = 0.35 and PbO/(CaO + SiO2) = 3.2

Experimental studies on phase equilibria in the multicomponent system PbO-ZnO-CaO-SiO₂-FeO-Fe₂O₃ in air have been conducted to characterize the phase relations of a complex slag system used in lead and zinc smelting. The liquidus in the pseudoternary section ZnO-“Fe₂O₃”-(PbO + CaO + SiO₂) with a CaO/SiO₂ weight ratio of 0.35 and a PbO/(CaO + SiO₂) weight ratio of 3.2 has been constructed to describe liquidus temperatures as a function of composition in the range of commercial operating conditions employed by the Lead Isasmelt smelting process. The section contains the primary phase fields of spinel (zinc ferrite, Zn _x Fe_3−y O_4+z ), zincite (Zn _u Fe_1−u O), melilite (Pb _v Ca_2−v Zn _w Fe_1−w -Si₂O₇), hematite (Fe₂O₃), magnetoplumbite (PbFe₁₀O₁₆), and wollastonite (CaSiO₃).     

A thermodynamic study of the system FexO + AI2O3 + SiO2 at 1673 K

Electrochemical measurements of the solid-oxide galvanic cell Mo/Mo + MoO₂/ZrO₂(MgO)/Fe + (Fe_xO + A1₂O₃ + SiO₂)_slag/Ag/Fe have been made at 1673 K in order to obtain the activities of Fe_xO in Fe_xO + A1₂O₃ + SiO₂ slags. Activities of A1₂O₃ and SiO₂ were also determined by virtue of Gibbs-Duhem integration. By using the activity data, the free energies of formation of hercynite and mullite were also obtained. Leave of absence from the Steelmaking Research Section, Iron and Steel Research Laboratories, Kobe Steel Ltd.     

Acid dissolution of willemite (Zn,Mn)2 SiO4) and hemimorphite (Zn4Si2O7(OH)2 H2O)

The influence of temperature, pH, acid type, and surface area on the kinetics of the acid dissolution of natural and synthetic willemites and natural hemimorphites has been investigated. Specific rate constants, based upon areas determined by krypton adsorption measurements, were estimated from the experimental data obtained. For both willemite and hemimorphite, the rates of dissolution in different acids are shown to be related to the relative strengths of zinc-acid anion complexes. The reactivity of willemite toward acids increases with increasing replacement of zinc by manganese. Mixed chemical/diffusion control is responsible for the observed rates of willemite dissolution under the conditions studied (HNO₃, HCl, HClO₄, H₃PO₄, H₂SO₄, pH 0.31 to 3.00,T 21 to 94 °C). Estimates of the relative contributions of chemical and diffusional resistances to the overall rate have been made for the dissolution of manganese-free willemite in sulfuric acid solutions. The experimentally measured rates have been demonstrated to be in reasonable agreement with predicted overall dissolution rates. Proposals are made regarding the nature of the diffusion and chemical steps involved in the dissolution process. Hemimorphite was found to be considerably more reactive than willemite and its dissolution is primarily diffusion controlled under the conditions studied (T 20 to 76 °C, pH 2 to 3.5). Formerly a Postgraduate Research Student, Department of Metallurgy and Materials Science, Royal School of Mines, Imperial College, London     

Fabrication and Luminescence Properties of Ca2Gd8(SiO4)6O2:Er3+ Phosphors via Sol-Gel Process

Ca2RE8(SiO4)6O2 (RE=Y, Gd, La) is a kind of ternary rare-earth-metal silicate with the oxyapatite structure, which was used as host materials for the luminescence of various rare earth and mercury-like ions. Ca2Gd8(SiO4)6O2:Er3 phosphors were prepared through the sol-gel process. X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectra were used to characterize the resulting phosphors. The results of XRD indicate that the phosphors crystallized completely at 1000 ℃. SEM study reveals that the average grain size is 400～1000 nm. In Ca2Gd8(SiO4)6O2:Er3 phosphors, the Er3 shows its characteristic green emission at 528 nm (2H11/2-4I15/2) and 548 nm(4S3/2-4I15/2) upon excitation into 382 nm, with an optimum doping concentration of 5% (mole fraction) of Gd3 in the host lattices.     

Photoluminescent properties of Ca2Gd8(SiO4)6O2: Dy3+ phosphor films prepared by sol-gel process

There are growing interests on phosphor thin films owing to their potential application in high-resolution devices such as cathode ray tubes and flat panel display devices. The solution-based sol-gel method is one of the most important techniques for the synthesis of vari-ous functional coating films. Compounds with the apatite structure are very suitable host lattices for various luminescent ions. Ca2RE8(SiO4)6O2 ( RE=Y, Gd, La ) is a kind of ternary rare-earth-metal silicate with oxyapatite structure, which has been used as host mate-rial for the luminescence of various rare earth and mercury-like ions. In this article, Ca2Gd8(SiO4)6O2:Dy3 phosphor films were dip-coated on quartz glass substrates through the sol-gel process. X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL) spectra, as well as lifetimes were used to characterize the resulting films. AFM study revealed that the phosphor films consisted of homoge-neous particles. The Dy3 showed its characteristic emission in crystalline phosphor films, i.e., 4F9/2–6H15/2 and 4F9/2–6H13/2.     

Luminescent Properties of Ca2 Y8 ( SiO4 ) 6O2:Eu3 + Phosphors Prepared by Spray Pyrolysis Process

Using CaCO3, metal oxides (all dissolved by nitric acid) and tetraethoxysilane Si (OC2H5 )4 (TEOS) as the main starting materials, Ca2Y8 (SiO4 )6O2: Eu3 phosphors were synthesized by spray pyrolysis.X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting phosphors.The results of XRD indicated that the 1000 ℃ annealed powders crystallize with the silicate oxyapatite structure.SEM study revealed that the phosphors consist of spherical particles with an average size of about 1 ～ 3 μm.In the crystalline Ca2 Y8 (SiO4)6O2: Eu3 phosphor, the Eu3 shows its characteristic emission corresponding to 5 D0 - 7 FJ ( J = 0, 1,2, 3, 4) transitions, with 5D0 - 7 F2 red emission (613 nm) as the most prominent group, agreeing well with the structure of the host material.     

Determination of the standard gibbs energy for the reaction of 3BaO (s) + 2Cr (s) + 3/2O2 (g) = 3Ba0 · Cr2O3 (s)

The standard Gibbs energy of formation of 3BaO · Cr₂O₃ has been measured by a chemical equilibrium technique and is expressed as follows: 3BaO (s) + 2Cr (s) + 3/2 O₂ (g) = 3BaO · Cr₂O₃ (s) ΔG^o = -1,260,000 (±3000) + 282 (±24)r(J/mol) The activity coefficient of chromium in copper, which was needed for the foregoing measurement, may be expressed by the following equation: 5790 log γ _Cr ^{o =5790/T-2.10} The value of standard Gibbs energy at 1573 K was found to be close to that of reaction of formation of CaO · Cr₂O₃ expressed in the similar form. The BaO saturated BaF₂ flux is shown to be far more promising in the oxidative dephosphorization of chromium-containing hot metal in comparison with the CaO-SiO₂-CaF₂ flux doubly saturated with CaO and 3CaO-Cr₂O₃.     

Luminescence Properties of Eu~(2 ) and Mn~(2 ) Co-Doped Ca_8Mg(SiO_4)_4Cl_2

The green phosphor for white LED, Ca8Mg(SiO4)4Cl2∶Eu2+, Mn2+, was synthesized by high temperature solid state reaction under reducing atmosphere. During the process of the phosphor prepared, the excess CaCl2 can improve the intensity of emission. The experimental results indicate that there is an effective energy transfer from Eu2+ to Mn2+in Ca8Mg(SiO4)4Cl2 host. This kind of energy transfer may be due to resonance transfer, and this energy transfer is limited.     

Study on Ca8Mg(SiO4)4Cl2:Eu2+ Doped with Sr2+

Ca8Mg(SiO4)4Cl2:Eu2 phosphor doped with Sr2 cation for Ca2 partially, was synthesized by solid-state reaction at high temperature under reducing atmosphere, and its luminescent properties were investigated. The experimental results indicate that the emission intensity of the phosphor increases after being doped with a few amount of Sr2 ion. The emission peak of the phosphor blue shift to about 464 nm when the phosphor is doped with large quantity of Sr2 ions. The excitation spectrum indicates that the phosphor can be well excited by UV and blue light from 300 to 460 nm, and the phosphor was fitted well for the excitation by UV or blue-LED.     

Combustion synthesis and luminescence properties of Ca4Y6(SiO4)6O:Eu3+red phosphor for white LEDs

Eu3+activated Ca4Y6(SiO4)6O phosphors were prepared by combustion synthesis method, and their morphologies and lu-minescent properties were investigated. Field scanning electron microscopy (FSEM) confi...     

Experimental study of phase equilibria in the PbO-ZnO-“Fe2O3”-CaO-SiO2 system in air for high lead smelting slags (CaO/SiO2=0.35 and PbO/(CaO + SiO2)=5.0 by weight)

Experimental studies on phase equilibria in the multicomponent system PbO-ZnO-CaO-SiO₂-FeO-Fe₂O₃ in air have been conducted to characterize the phase relations of a complex slag system used in commercial lead oxidation smelting. The liquidus in the pseudo-ternary section ZnO-“Fe₂O₃”-(PbO + CaO + SiO₂) with the CaO/SiO₂ weight ratio of 0.35 and the PbO/(CaO + SiO₂) weight ratio of 5.0 has been constructed using results of over 100 high-temperature equilibration and quenching experiments followed by electron probe X-ray microanalysis. The liquidus in this pseudoternary section contains primary phase fields of spinel (zinc ferrite) Zn _x Fe_3−x O_4+y , zincite Zn _u Fe_1−u O, melilite Pb _v Ca_2−v Zn _w Fe_1−w Si₂O₇, hematite Fe₂O₃, magneto-plumbite PbFe₁₀O₁₆, and dicalcium silicate Ca_2−t Pb _t SiO₄. The laboratory results are compared with the slags obtained from an industrial reactor.     

Vacuum Ultraviolet Spectral Investigations on Green-Emitting Ca(La,Gd)4Si3O13:Tb3+ Phosphors for PDP Applications

In an effort to develop new green-emitting PDP phosphors with high efficiency, investigated were the synthesis, VUV photoluminescence (PL) spectra, optical properties, and chromaticity of Ca(La1-x-yTbxGdy)4Si3O13 phosphors by using synchrotron radiation. Upon analysis of the VUV spectroscopic and chromaticity investigations on the new green-emitting VUV phosphors, were an optimized composition achieved. The PLE spectral studies show that Ca(La1-x-yTbxGdy)4Si3O13 exhibit significant absorption in the VUV range. The VUV PL intensity was found to enhance with Gd3 -doping. Furthermore, the 1931 CIE chromaticity coordinates of Ca(La,Gd)4Si3O13:Tb were found to be (0.286, 0.548), as compared to (0.230, 0.712) for Zn2SiO4:Mn2 as a reference. The potential application of Ca(La,Gd)4Si3O13:Tb as a new green-emitting PDP phosphor are being currently improving and evaluating.     

Luminescence and Preparation of LED Phosphor Ca8Mg(SiO4)4Cl2:Eu2+

Calcium magnesium chlorosilicate doped by europium, Ca8Mg(SiO4)4Cl2:Eu2 , was prepared by the solid state reaction at high temperature. The compound obtained is pure Ca8Mg(SiO4)4Cl2 phase with cubic structure. Its average particle size is 5 μm, and it has good dispersity and morphological form. The excitation spectrum of Ca8Mg(SiO4)4Cl2:Eu2 is a wide band, which covers from 270 to 480 nm. The emission spectrum is also a wide band peaked at 510 nm. The luminescent intensity reaches to the maximum when the concentration of Eu2 is 2%. The wavelength of emission and excitation of the phosphor with various Eu2 contents keeps constant. This spectrum range matches violet and blue LED chips very well, and its strong luminescence intensity is suitable for a green phosphor of tricolor phosphor of white light LED.