The reduction mechanism of a natural chromite at 1416 °C

The behavior of a natural chromite from the Bushveld Complex, Transvaal, South Africa, during reduction at 1416 °C by graphite was studied by means of thermogravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis. Experimental runs were allowed to proceed up to 120 minutes, resulting in 99 pct reduction. The specific objective of this study was to delineate the reduction mechanism of chromite by graphite. Zoning was observed in partially reduced chromites with degrees of reduction of up to about 70 pct. The inner cores were rich in iron, while the outer cores were depleted of iron. Energy-dispersive X-ray analysis revealed that Fe²⁺ and Cr³⁺ ions had diffused outward, whereas Cr²⁺, Al³⁺, and Mg²⁺ ions had diffused inward. The following mechanism of reduction, which is based on the assumption that the composition of the spinel phase remains stoichiometric with increasing degree of reduction, is proposed, (a) Initially, Fe³⁺ and Fe²⁺ ions at the surface of the chromite particle are reduced to the metallic state. This is followed immediately by the reduction of Cr³⁺ ions to the divalent state, (b) Cr²⁺ ions diffusing toward the center of the particle reduce the Fe³⁺ ions in the spinel under the surface of the particle to Fe²⁺ at the interface between the inner and outer cores. Fe²⁺ ions diffuse toward the surface, where they are reduced to metallic iron, (c) After the iron has been completely reduced, Cr³⁺ and any Cr²⁺ that is present are reduced to the metallic state, leaving an iron- and chromium-free spinel, MgAl₂O₄. Formerly Postgraduate Student, Department of Metallurgy and Materials Engineering, University of the Witwatersrand. Formerly with the Department of Metallurgy and Materials Engineering, University of the Witwatersrand.     

Energy transfer process of Nd3+/Ho3+ co-doped fluoride halide glasses with anion substituted multi-wavelength tunable mid-infrared luminescence

Ho³⁺ doped ZBLAN glass with 2.0 and 2.9 μm emission was prepared. In order to further improve the luminescence of Ho³⁺, halogen ions (Cl, Br, I) were introduced to reduce the maximum phonon energy and phonon state density of the sample. At the same time, Nd³⁺ was introduced to transfer the energy to Ho³⁺ pumped with a 793 nm laser (Nd³⁺:⁴F_5/2,⁴F_3/2→Ho³⁺:⁵I₆). The effect of different halogen ion on the luminescent properties of the fluoride halide glass was compared. The results show that the luminescent intensity of infrared increases with the introduction of different halogen ions. By comparison, it is found that the sample with I^– has the strongest luminescence of 1064 nm, 2.0 μm and 2.9 μm. This is consistent with the calculated J-O intensity parameters. In addition, the 2.0 and 2.9 μm emission of Ho³⁺ pumped with a 450 nm laser will not disappear. A mid-infrared sample with multi-wavelength excitation and multi-wavelength emission can be obtained. Nd³⁺/Ho³⁺ co-doped fluoride halide glasses with 1064 nm, 2.0 μm and 2.9 μm luminescence were prepared by melt quenching method. The luminescent mechanism and the energy transfer process between the two ions of Nd³⁺/Ho³⁺ co-doped fluoride halide glass were studied. The J-O parameters, luminescence lifetime and absorption emission cross-sectional area of Ho³⁺ and Nd³⁺ were calculated, respectively. It is found that the value of Ω₂ in the glass matrix increases with the introduction of different halogen ions, while Ω₄ and Ω₆ do not change obviously in different glass compositions. This is because the environment of the crystal field around the rare earth ions changes. The crystal phase and phonon energy of the sample were analyzed by X-ray diffraction pattern and a Fourier transform infrared spectrometer, respectively. Based on the above spectra and data (phonon energy is 634.71 cm⁻¹), it can be predicted that Nd³⁺/Ho³⁺ co-doped fluoride halide glass is a potential mid-infrared luminescent material.     

Long afterglow yellow luminescence from Pr3+ doped SrSc2O4

A yellow emitting long afterglow luminescence material SrSc₂O₄:Pr³⁺ was successfully prepared by solid state reaction method. SrSc₂O₄:Pr³⁺ phosphor shows a long afterglow luminescence peak at about 495, 545, 621, 630 and 657 nm, respectively, corresponding to the f–f transitions of Pr³⁺. The afterglow chromaticity coordinates of SrSc₂O₄:1 at%Pr³⁺ were calculated to be (0.35, 0.41), indicating that the afterglow emission is close to the light of yellow region. And, the afterglow luminescence of the optimal sample doped by 1 at%Pr³⁺ can persist for over 3 h. The thermoluminescence results suggest that there are three types of traps with depth of 0.61, 0.69 and 0.78 eV exiting for all the samples, which are produced by the addition of Pr³⁺ ions. The trap density of SrSc₂O₄:1 at%Pr³⁺ is the maximum when the incorporation of Pr³⁺ ions reaches 1 at%, which thus results in the longest afterglow luminescence. All the results indicate that SrSc₂O₄:Pr³⁺ can be a potential candidate of novel long afterglow phosphors.     

Energy transfer and luminescent properties of Tb3+ and Tb3+, Yb3+ doped CNGG phosphors

In this work,calcium niobium gallium garnet(Ca₃ Nb_1.6875Ga_3.1875O₁₂-CNGG) ceramic samples singledoped with Tb³⁺ and co-doped with Tb³⁺ and Yb³⁺ ions were sintered by the solid-state reaction method.The structural characterization of the samples was carried out by X-ray diffraction measurements.The optimal concentration of Tb³⁺ ions corresponding to the maximum luminescence in the green spectral range in CNGG:...     

Electrical and electronic conductivity of CaO-SiO2-FeOx slags at various oxygen potentials: Part II. Mechanism and a model of electronic conduction

The experimental results obtained for ionic and electronic conductivity of ‘FeO’-CaO-SiO₂ melts have been analyzed considering the mechanism of each conduction process. The Nernst-Einstein equation was employed to calculate diffusion coefficients of Fe²⁺ and Ca²⁺ cations from ionic conductance. A “diffusion-assisted charge transfer” model was developed to explain the dependence of the electronic conductivity on the oxidation state of iron in the slag. The model considers the electronic conduction as a two-step process: in one step, ferrous ions diffuse from their initial position to a proper distance from ferric ions; in the next step, an electron is transferred between Fe²⁺ and Fe³⁺. The optimum distance of the iron ions for electron hopping was found to be approximately 4 Å, in great consistency with the values reported for electron transfer between Fe²⁺ and Fe³⁺ in aqueous solutions and solid glasses.     

Intense upconversion luminescence of Er3+/Yb3+ codoped oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals

Er3+/Yb3+-codoped transparent oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals were prepared and spectroscopic properties of rare earth ions were investigated.Fluoride nanocrystals Ba2GdF7 were successfully precipitated in glass matrix,which was confirmed by X-ray diffraction(XRD)and transmission electron microscopy(TEM)results.In comparison with the as-made precursor,significant enhancement ofupconversion luminescence was observed in the Er3+/Yb3+codoped oxyfluoride glass ceramics,which may be due to the variation of coordination environment around Er3+and Yb3+ions after crystallization.The transition mechanisms of the green and red upconversion luminescence were ascribed to a two-photon process,and that of the blue upconversion luminescence was a three-photon process.     

火焰原子吸收光谱法测定火法冶炼镍基体料矿热炉渣中镍

通过对火法冶炼镍基体料矿热炉渣化学组成和性质的研究,确定了测定微、痕量镍的实验方法。由于样品中二氧化硅含量在40%～65%,样品的分解难度很大,且对镍的测定存在严重的负干扰,因此需在样品分解过程中加入足量氢氟酸与之反应生成SiF₄挥发除去。溶液中其余共存离子主要有Mg²⁺、Ca²⁺、Fe³⁺、Al³⁺、Cr⁶⁺等,其中Ca²⁺对测定存在严重的正干扰,通过向空白溶液中加入同量的钙可消除此干扰。高氯酸是最佳的分析介质,其浓度控制在3%～5%即可达到稳定分析。方法的检出限为0.001 2 mg/L。对4个火法冶炼镍基体料矿热炉渣实际样品中镍进行分析,回收率为99%～102%,相对标准偏差处于1.3%～2.9%范围内,与ICP-AES的分析结果相一致。     

High pressure luminescence studies of europium doped GaN

We reported on the high pressure luminescence spectra of polycrystalline Eu-doped GaN material synthesized in the reaction between alloys of gallium, bismuth and europium in ammonia atmosphere. The integrated luminescence intensity of the dominant Eu³⁺ ion transition (⁵D₀→⁷F₂) at 622 nm increased approximately one order of magnitude whereas its spectral position and line width did not change significantly between ambient and 6.8 GPa pressure, respectively. Moreover, material was characterized with photo- and cathodo-luminescence, and photoluminescence excitation spectra at different temperatures. It was found that the Eu³⁺ ions occupying substitutional Ga site created different centers which could be effectively excited with above band gap excitation and from excitons resonantly photoexcited at the I₂ bound exciton energy. Furthermore, the less efficient Eu³⁺ ions excitation path existed through intrinsic impurities and defects generating shallow energy levels in the forbidden gap. It was proposed that reduction of the thermal quenching and consequent enhancement of Eu³⁺ ion emission intensity resulted from stronger localization of bound exciton on RESI trap induced by applied pressure.     

Up-conversion luminescence properties of Yb^3＋ and Ho^3＋ co-doped Bi3.84W0.16O6.24 powder synthesized by hydrothermal method

Using polyethylene glycol (PEG) as the surfactant, Bi3.84W0.16O6.24 up-conversion luminescence nano-crystal co-doped with Yb3+ and Ho3+ ions was synthesized by the hydrothermal method. The structure and properties of luminescence powder were studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). It was of cubic system when the sample was synthesized at a low temperature and the particle size was about 30 nm. The results showed that adding surfactants was useful to improve the powder agglomeration and the grain crystal was spherical. The green emission peak at 546 nm and red emission peak at 655 nm, corresponding to the ( 5F4, 5S2)→ 5 I 8 and the 5 F 5 → 5 I 8 transitions of Ho 3+ , respectively, were simultaneously observed at room temperature under excitation of 980 nm semiconductor laser. The up-conversion luminescence intensity was the strongest when the concentration ratio of Yb3+ /Ho3+ was 6:1 and the concentration of Ho 3+ ion was 1.5 mol.%. The up-conversion mechanism was also studied. The green and red emission peaks were the two-photon absorption according to the relationship between the pump power and the luminescence intensity.     

Improving luminescence and thermometric performance of Ba2CaWO6:Er3+ by tri-doping with Yb3+ and Na+

The Er³⁺doped double perovskite Ba₂ CaWO₆ crystal is a promising ratiometric thermometer based on the fluorescence intensity ratio(FIR) of transitions from ² H_11/2 and ⁴ S_3/2to the lowered ⁴ I_15/2 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...     

Luminescence properties of calcium tungstate activated by lanthanide(Ⅲ) ions

Calcium tungstate phosphors activated by the Ln3+ ions(Ln=Pr, Nd, Tb, Yb) were synthesized by a traditional high-temperature solid-state method. The crystal structures and morphologies of the products were characterized by scanning electron microscopy(SEM), X-ray powders diffraction(XRD) and infrared spectra(FT-IR). The samples were found to show luminescence properties(down-conversion, DC, at excitation wavelength 254 nm and up-conversion, UC, at excitation wavelength 980 nm). CaWO4 doped with Tb3+/Yb3+ showed green DC and UC luminescence characteristic of Tb(III) ion in the range of 470–660 nm, corresponding to the 5D4→7F6,5,4,3,2 electronic transition. CaWO4 doped with Pr3+/Yb3+ showed week blue, green and red(DC and UC) luminescence of Pr(III) ion, in the wavelength region of 450–700 nm. Emission peaks were ascribed to the 3P1→3H4,5,6, 3P0→3H4,5,6, 3P1→3F2 and 3P0→3F2 transitions, respectively. CaWO4 doped with Nd3+/Yb3+ phosphor emitted orange UC luminescence at 450–690 nm(2P3/2→4I15/2, 4G7/2→4I9/2,11/2,13/2) and strong near-infrared UC luminescence at 720–900 nm(4F7/2+4S3/2→4I9/2, 4F5/2+2H3/2→4I9/2, 4F3/2→4I9/2) which is the characteristic of Nd(III) ion.     

Rare earth double activated phosphors for different applications

For the purpose of development of highly energy-efficient light sources, one needs to design highly efficient green, red and yellow phosphors, which are able to absorb excitation energy and generate emissions. In this contribution, we present our results on producing some efficient phosphors with improved luminescence properties. Using double activation, energy could be transferred from one luminescent activator to the other one, resulting in more efficient or brighter device operation. Co-activators could be added to a host material to change the color of the emitted light. The incorporation of Eu³⁺ or Tb³⁺ ions into the CaWO₄ crystal lattice modified the luminescence spectrum due to the formation of the emission centers that generated the specific red and green light. Very efficient new red phosphors based on YNbO₄ and doped by Eu³⁺, Ga³⁺, Al³⁺ allowed recommending these materials as good candidates for different applications including LED and X-ray intensifying screens. For double activated TAG with Ce³⁺ and Eu³⁺ and for different mole ratios of Ce/Eu, the color temperature changed from 5500 K (0.331, 0.322) up to 4200 K (0.370, 0.381) and the light became “warmer”. Application of TAG: Ce, Eu in the light emitting device showed better chromaticity coordinates of luminescence and color rendering index of LEDs.     

A single-phase full-color phosphor Sr2Ca2La(PO4)3O:Eu2+,Tb3+,Mn2+: Photoluminescence and energy transfer

A single-phase full-color emitting phosphor Sr₂Ca₂La(PO₄)₃O:Eu²⁺,Tb³⁺,Mn²⁺ was synthesized by the high temperature solid-state method. The phase formation, luminescence properties, thermal stability, and energy transfer from Eu²⁺ to Tb³⁺ and Eu²⁺ to Mn²⁺ in Sr₂Ca₂La(PO₄)₃O were investigated in details. Tunable emission color from blue to blueish green or orange can be observed under 365 nm near-ultraviolet excitation based on the energy transfer from Eu²⁺ to Tb³⁺ or Mn²⁺ ions by varying the ratio of Eu²⁺/Tb³⁺ or Eu²⁺/Mn²⁺ ions. White light was obtained with chromaticity coordinates of (0.3558, 0.3500) in the Sr₂Ca₂La(PO₄)₃O:0.04Eu²⁺,0.08Tb³⁺,0.40Mn²⁺ phosphor, suggesting their potential applications in white light emitting diodes.     

Comparative study of dewatering characteristics of metal precipitates generated during treatment of monometallic solutions

The sludge dewatering properties (settling, filtration and centrifugation) of metal precipitates generated during treatment of monometallic solutions (0.020 mol/L) have been evaluated in this research. The precipitation tests carried out on 15 different metals gave metal removal yields generally similar to those predicted by MINEQL+ software, with the exception that kinetic aspects should be considered during precipitation of metal sulphides and phosphates. Hydroxides precipitation at pH 10.0 was the most efficient technique for the removal of eight metallic ions (Al³⁺, Cd²⁺, Co²⁺, Fe²⁺, Fe³⁺, Mg²⁺, Mn²⁺, Ni²⁺), whereas phosphates precipitation (at pH 6.0 with an addition of 0.0133 mol PO₄^3?/L) gave highest removal yields for Ba²⁺, Ca²⁺, Cr³⁺. Sulphides precipitation (at pH 7.0 and using, 0.020 mol S^2?/L) has been found the most efficient technique only for Cu²⁺ and Sn²⁺ precipitation, whereas carbonates precipitation (at pH 8.0 and using 0.020 mol CO₃^2?/L) gave better removal yield only for Pb²⁺. Results have also shown that metal phosphates have generally better dewatering characteristics (SVI, filtration capacity, SRF, sludge solids content) than metal carbonates, sulphides and hydroxides. In fact, considering only the sludge dewatering characteristics, phosphates precipitation appears the most appropriate technique for the precipitation of many metals (Al³⁺, Ba²⁺, Cd²⁺, Co²⁺, Cr³⁺, Fe²⁺, Fe³⁺, Ni²⁺ and Zn²⁺). Metal hydroxides formation constitutes the best option for Ca²⁺, Cu²⁺, Mg²⁺ and Sn²⁺ removal, whereas precipitation of metal carbonates is particularly interesting for treatment of Mn²⁺ and Pb²⁺ containing solutions.     

Local vibration around rare earth ions in alkaline earth fluorosilicate transparent glass and glass ceramics using Eu probe

By heat treating the alkaline earth fluorosilicate glass, transparent glass ceramics containing alkaline earth fluoride nanocrystallites were prepared. The luminescence spectra and phonon sideband associated with the Eu^3＋：^5D2→^7F0 in glass and glass ceramics were investigated to analyze the local environment around Eu^3＋. Judd-Ofelt parameters were also calculated from emission spectra, which indicated that the Eu^3＋ ions entered the precipitated CaF2, SrF2, and BaF2 nanocrystallites. Heat treating could not pledge Eu^3＋ ions to coordinate with F^- in the precipitated MgF2 nanocrystallites, owing to the smaller radius of Mg^2＋ than that of Eu^3＋.     

Zirconium metal organic framework for design of tetragonal rare earth-doped zirconia nanoparticles

Zirconium metal–organic frameworks ZrOBDC (where BDC = C₆H₄(COOH)₂, terephthalic acid) doped and co-doped with rare earth ions Ln (ZrOBDC:Ln³⁺, where Ln³⁺ = Eu³⁺ and Tb³⁺ as well as Er³⁺ and Yb³⁺) were used as precursors for the design of tetragonal rare earth doped zirconia nanoparticles (t-ZrO₂:Ln³⁺ NPs) through annealing process. Preparation, characterization and luminescence properties of ZrOBDC:Ln³⁺ and ZrO₂:Ln³⁺ NPs were investigated. The as-obtained t-ZrO₂:Ln³⁺ NPs have high purity with an average size of 20–30 nm. The luminescence spectra of ZrOBDC:Tb³⁺ and ZrOBDC:Eu³⁺ display strong green and red emission at around 544 and 611 nm which correspond to ⁵D₄ → ⁷F₅ and ⁵D₀ → ⁷F₂ transitions of Tb³⁺ and Eu³⁺ ions, respectively. The green and red up-conversion emissions of ZrO₂:Er³⁺,Yb³⁺ NPs due to ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions are observed under 976 nm laser excitation.     

Thermodynamic aspects of the selection of sulfur-containing collectors during flotation of sulfide ores

Investigations into the complexing ability of sulfur-containing collectors relative to metal ions (Cu²⁺, Ni²⁺, Fe²⁺, Co²⁺) at 298 K and an ion force of 0.075–0.75 mol/L (NaNO₃) are carried out. It is established that potassium dibutyl dithiophosphate possesses the largest affinity to metal ions among phosphorus-containing collectors, while the maximal complexing ability is characteristic of the Co²⁺ ion. Series of thermal stability are found; the variations in enthalpy, entropy, and the Gibbs energy, as well as temperature-dependent and temperature-independent contributions of complexes of metal ions with collector anions into ΔG ⁰, are calculated.     

Hierarchical porous cellulose/lanthanide hybrid materials as luminescent sensor

Photoluminescent hybrid materials containing carboxymethyl cellulose and lanthanide ions (Eu³⁺, Tb³⁺) were prepared by a facile method under ambient conditions. Lanthanide ions were covalently grafted to the cellulose framework through coordination with the carboxylic groups of the cellulose. Hybrid materials were fabricated as hydrogel and aerogel. As shown by SEM and pore parameters, aerogel materials which were obtained by supercritical CO₂ drying show hierarchical porous structure. The photoluminescence spectrum of the hybrid materials shows the characteristic red emission of Eu³⁺ ion and green emission of Tb³⁺. Further luminescent investigations reveal that these hybrid materials can detect Fe³⁺ with relative selectivity and high sensitivity, which suggests that the hybrid materials could be a promising luminescent probe for selectively sensing Fe³⁺ ion.     

Magnetoelectric,Raman, and XPS Properties of Pb0.7Sr0.3[(Fe2/3Ce1/3)0.012Ti0.988]O3 and Pb0.7Sr0.3[(Fe2/3La1/3)0.012Ti0.988]O3 Nanoparticles

The Pb_0.7Sr_0.3[(Fe_2/3Ce_1/3)_0.012Ti_0.988]O₃ (PSFCT) and Pb_0.7Sr_0.3[(Fe_2/3La_1/3)_0.012Ti_0.988]O₃ nanoparticles were prepared by chemical synthesis route using polyvinyl alcohol as surfactant. X-ray diffraction pattern has been used to analyze the phase structure and average particles size. The phase structure is also confirmed by Raman spectra. The chemical states of Pb²⁺, Sr²⁺, Fe³⁺; Ti⁴⁺, Ce³⁺, La³⁺, and oxygen ions have been analyzed by X-ray photoelectron spectroscopy. The magnetoelectric coupling effect is confirmed by magnetic phase transition near ferroelectric phase-transition temperature. The magnetoelectric effect is also confirmed by measuring the value of magnetoelectric coefficient (α _E) as the function of applied dc magnetizing field under the influence of ac magnetic field of 10 Oe and frequencies of 847 and 997 Hz. The higher value of α _E is observed in PSFCT sample.     

硫酸铵-碘化钾-十二烷基三甲基氯化铵微晶吸附体系浮选分离镉(Ⅱ)

研究了硫酸铵-碘化钾-十二烷基三甲基氯化铵微晶吸附体系浮选分离镉(Ⅱ)的行为及其与常见离子定量分离的条件。结果表明,在0.5 g (NH₄)₂SO₄的存在下,当体系中Cd²⁺、KI、DTMAC同时存在时,体系中形成的三元缔合物(DTMAC)₂(CdI₄) 沉淀被定量吸附在DTMAC ⁺·I^-微晶物质表面而被浮选至盐水相上,Cd²⁺被定量浮选,Co²⁺、Ni²⁺、Zn²⁺、Mn²⁺、Fe³⁺、Al³⁺等离子留在水相中而不被浮选,实现了Cd²⁺与这些离子的定量分离,据此建立了一种微晶吸附体系浮选分离Cd²⁺的新方法。通过扫描电镜图片确证了DTMAC ⁺·I^-微晶物质的产生,探讨了Cd²⁺的浮选分离机理。方法成功用于合成水样中Cd²⁺的定量浮选分离,浮选率为95.4%～105.3%。