Fabrication and luminescent properties of rare earths-doped Gd-2(WO4)(3) thin film phosphors by Pechini sol-gel process

Rare earth ions (Eu3+ and Dy3+)-doped Gd-2(WO4)(3) phosphor films were prepared by a Pechini sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting powders and films. The results of XRD indicate that the films begin to crystallize at 600degreesC and the crystallinity increases with the elevation of annealing temperatures. The film is uniform and crack-free, WO(4)(2-)mainly consists of closely packed fine particles with an average grain size of 80 nm. Owing to an energy transfer from 4 groups, the rare earth ions show their characteristic emissions in crystalline Gd-2(WO4)(3) phosphor films, i.e., D-5(J) -F-7(J), (J = 0, 1, 2, 3; J' = 0 1, 2, 3, 4, not in all cases) transitions for Eu3+ and F-4(9/2)-H-6(J) (J = 13/2, 15/2) transitions for D Y3+, with the hypersensitive transitions D-5(0)-F-7(2) (Eu3+) and F-4(9/2) - H-6(13/2) (Dy3+) being the most prominent groups, respectively.

Long-lasting properties of rare earth-doped Y2O2S phosphors

The aim of this presentation is to report a new result of afterglow materials. The Y2OS: Ln(3+) (Ln = Sm, Tm) phosphors show bright reddish orange and orange-yellow colors when excited by UV or visible light. The main spectroscopic characterizations of Sin(3+) and Tin(3+) in yttrium oxysulfide and their long-lasting phosphorescence were measured and discussed in this presentation. Their long-lasting phosphorescence can be seen by the naked eyes clearly for about one hour in the dark room after the Irradiation light sources were removed. XRD and photoluminescence (PL) spectra as well as the luminance decay were used to characterize these long-lasting phosphorescence phosphors. The results of XRD indicate that the products synthesized through the flux fusion method tinder 1050 degreesC, for 6 It have a good crystallization without any detectable amount of impurity phase. Both the PL spectra and luminance decay results reveal that these phosphors have efficient luminescent and good long-lasting properties. We believe that the experimental data gathered in our present work will be. useful in finding some new long-lasting phosphors with different colors.

Extraction and separation of cerium(IV) from nitric acid solutions containing thorium(IV) and rare earths(III) by DEHEHP

The extraction behaviour of Ce(IV), Th(IV) and part of RE(III), viz., La, Ce, Nd and Yb, has been investigated using di(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP,B) in heptane as an extractant. Results show that extractability varies in the order: Ce(IV) > Th(IV) much greater than RE(III). Therefore, it is possible to find the appropriate conditions under which Ce(IV) can be effectively separated from Th(IV) and RE(III). Furthermore, stripping Ce(IV) from the loaded organic phase can be carried out by dilute H2SO4 with an aliquot of H2O2.Roasted bastnasite made in Baotou (China) by Na2CO3 and leached by HNO3, there is about 50% Ce mainly as tetravalent nitrate along with other RE(III) and Th(IV) in the leachings. Through fractional extraction, taking nitric acid leachings of roasted Bastnasite as feed and DEHEHP as an extractant, we can obtain the CeO2 products with high purity of 99.9-99.99%, with a yield of >85%, in which ThO2/CeO2 < 10(-4).

Separation of thorium(IV) and extracting rare earths from sulfuric and phosphoric acid solutions by solvent extraction method

The bastnasite of Baotou (China) was roasted in concentrated sulfuric acid at 250-300 degreesC and the calcined products were leached by water. Almost all rare earths (RE) were moved into solutions in trivalent along with some radioactive impurity thorium(IV) (Th(IV))which accounts for 0.4% of RE and other impurities such as Fe(III), Ca, F, P, etc. Through fractional extraction (seven stages for extraction and nine for scrubbing), the mass ratio of Th(IV) and RE (ThO2/REO) in solution has decreased to 5 x 10(-6). The purity of ThO2 product recovered from organic phase is above 99%. The iron(III) in solutions can be removed in the form of precipitation by adding some magnesia into the solutions. Then RE can be concentrated by solvent extraction with 2-ethylhexyl phosphinic acid 2-ethylhexylester (P-507). The results of fractional extraction show that the concentration of total RE in aqueous solutions stripped by hydrochloric acid is over 200 g REO/I with the yield of RE above 99%. Individual RE can be attained by solvent extraction with P507 in the following process.

Synergistic extraction of rare earths by mixture of bis(2,4,4-trimethylpentyl)phosphinic acid and Sec-nonylphenoxy acetic acid

Synergistic extraction of trivalent rare earths (RE=Sc, Y, La, Gd, Yb) from hydrochloride medium using mixture of bis(2,4,4-trimethylpentyl)phosphinic acid (HL, Cyanex272) and Sec-nonylphenoxy acetic acid (HA, CA-100) in n-heptane has been studied. The synergistic enhancement coefficients were observed for La (1.30), Gd (1.97), Y (3.59), Yb (8.21) and Sc (14.41). The results indicated yttrium was extracted into n-heptane as YH(5)A(4)L(4) mixed species instead of Y(HL2)(3), Y(OH)(2)A(HA)(3) which were extracted by Cyanex272 and CA-100, respectively. A cation exchange mechanism was proposed and further clarified by IR spectra. The equilibrium constants, formation constants and thermodynamic functions such as Delta G, Delta H and Delta S were determined. The Cyanex272 + CA-100 system not only enhanced the extraction efficiency of RE but also improved the selectivities significantly. The mutual separation factors of these ions suggested the mixture system would be of practical value in extraction and separation of rare earths.

A new hydrometallurgical process for extracting rare earths from apatite using solvent extraction with P-350

In this paper, a new process is proposed to recover rare earths from nitric acid leaching of apatite without interfering with the normal route for fertilizer production using solvent extraction with dimethyl heptyl methyl phosphonate CH3P(O)(OC8H17)(2) (P-350, B). In the present work, the leaching conditions are studied. In selected condition, apatite was dissolved in 20% (v/v) nitric acid solution at 60-70 degrees C while agitating. The most suitable acidity for extraction is 0.4 M HNO3. More than 98% of rare earths in apatite can be recovered using countercurrent extraction process with six stages when phase ratio = 0.5, and defluorination is unnecessary. The influences of phase ratio, stage number, acidity and salting-out agent on extractabilities Of P-350 are studied. The results show that rare earths can be separated with P-350 from Ca, P, Fe and other impurities. Mixed rare earth oxides (REO) of which purity is more than 95% with yield over 98% can be obtained.

The extraction of rare earths using mixtures of acidic phosphorus-based reagents or their thio-analogues

The solvent extraction of rare earths from chloride solution has been investigated using mixtures of 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (HEHEHP, P507) and organophosphorus acids [di-(2-ethylhexyl)phosphoric acid (HDEHP, P204), isopropylphosphonic acid 1-hexyl-4-ethylocryl ester (HHEOIPP), bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272), bis(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex 302), and bis(2,4,4-trimethypentyl)dithiophosphinic acid (Cyanex 301)]. Results show that the extractability of the selected extractants for rare earths decreases in the order: HEHEHP/HDEHP > HEHEHP/Cyanex 301 > HEHEHP/HHEOIPP > HEHEHP/Cyanex 302 > HEHEHP/Cyanex 272. A possible explanation of the different extractabilities is given based on the structure of the extractants. Furthermore, the possibilities of the separation of adjacent rare earths with these mixtures were investigated according to the extractabilities; the results show the possibility of separating the rare earths.

Studies on the synergistic extraction of rare earths with a combination of 2-ethylhexylphosphonic mono-2-ethylhexyl ester and trialkylphosphine oxide

The synergistic extraction of rare earths (La, Nd, Gd, Y and Yb) with a mixture of 2-ethylhexyl 2-ethylhexylphosphonate (EHEHPA) (HA) and trialkylphosphine oxide (Cyanex 923) (B) from a hydrochloride medium was investigated. The mixed system significantly enhances the extraction efficiency for lighter lanthanides and the synergistic enhancement coefficients for La (4.52), Nd (3.35), Gd (2.08), Y (1.31) and Yb (1.08) decrease with decreasing ionic radius of the rare earths. The extraction equilibrium of La, Nd and Gd indicate that La and Nd were extracted as MA(3)(.)B, whereas Gd was extracted as Gd(OH)A(2)(HA)(2)B-.. The equilibrium constants, thermodynamic functions such as Delta G, Delta H and Delta S and formation constants of the extracted species were determined. The stripping properties were also studied.

Synergistic extraction of rare earths(III) from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and di-(2-ethylhexyl)-2-ethylhexylphosphonate

The synergistic effect of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 (HPMBP, HA) and di-(2ethylhexyl)-2-ethylhexylphosphonate (DEHEHP, B) in the extraction of rare earths (RE) from chloride solutions has been investigated. Under the experimental conditions used, there was no detectable extraction when DEHEHP was used as a single extractant while the amount of RE(III) extracted by HPMBP alone was also low. But mixtures of the two extractants at a certain ratio had very high extractability for all the RE (III). For example, the synergistic enhancement coefficient was calculated to be 9.35 for Y3+, and taking Yb3+ and Y3+ as examples, RE3+ is extracted as RE(OH)A(2).B. The stoichiometry, extraction constants and thermodynamic functions such as Gibbs free energy change Delta G (-17.06kJmol(-1)), enthalpy change Delta H (-35.08kjmol(-1)) and entropy change Delta S (-60.47JK(-1)mol(-1)) for Y3+ at 298 K were determined. The separation factors (SF) for adjacent pairs of rare earths were calculated. Studies show that the binary extraction system not only enhances the extraction efficiency of RE(III) but also improves the selectivity, especially between La(III) and the other rare earth elements.

Extraction of rare earths(III) from nitrate medium with di-(2-ethylhexyl) 2-ethylhexyl phosphonate and synergistic extraction combined with 1-phenyl-3-methyl-4-benzoy l-pyrazolone-5

The extraction of trivalent rare earths ( RE) from nitrate solutions with di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP, B) and synergistic extraction combined with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP, HA) were investigated. The extraction distribution ratios demonstrate a distinct "tetra effect," and Y lies between Tb and Dy when DEHEHP is used as a single extractant for RE. According to the corresponding separation factors (SF12) for adjacent pairs of rare earths, it could be concluded that DEHEHP could be employed for the separation of La from the other rare earths, and Y from light rare earths. The present work has also found that mixtures of HPMBP and DEHEHP have an evident synergistic effect for RE(III). Taking Y( III) as an example, a possible synergistic extraction mechanism is proposed. The enhancement of extraction in the binary system can be explained due to the species Y(NO3) (.) A(2) (.) HA (.) B formed. The synergistic enhancement coefficients ( R), extraction constants, formation constants and thermodynamic functions of the reaction were calculated.

Mechanism of phase transformation and formation of barium hexaferrite doped with rare-earths in sol-gel process

The phase-transformation in sol-gel preparation of barium hexaferrite and the formation of barium hexaferrite doped with La3+ Were studied by chemical phase analysis, X-ray diffraction and infrared spectrometry analysis. The experimental results show that phase transformation reactions of FeCO3, Fe2O3 and BaFe2O4, barium hexaferrite and gamma-Fe2O3 take place in the heat treatment of gel. While the doping lanthanide ion replace barium ion, an equivalent quantity of Fe3+ are reduced to Fe2+ to maintain the charge equilibrium.

Extraction mechanism of rare earths with sec-octylphenoxy acetic acid by two-phase titration technique

The compositions of the extracted complexes of La, Gd, Er and Y with sec-octyl-phenoxy acetic acid in heptane and the related apparent extraction equilibrium constants K-M were determined using two-phase titration technique. The stoichiometric compounds for La, Gd, Er and Y should be LaA(3) . 2.5HA, GdA(3) . 3HA, ErA(3) . 3.1HA and YA(3) . 4.3HA respectively. And their pK(M) are 3.43, 3.46, 3.08 and 2.58 respectively.

Recovery of Ce(IV) and Th(IV) from rare earths(III) with Cyanex 923

Solvent extraction of Ce(IV), Th(IV) with Cyanex 923 in n-hexane from sulphuric acid medium was studied with the dependence of the extraction on acidity and temperature being investigated. The Ce(IV) and Th(IV) extraction mechanism was proposed by slope analysis and the IR spectra of purified Cyanex 923 saturated with Ce(IV) were employed to determine the composition of the Ce(IV) complex. The equilibrium constant and thermodynamic functions of Th(IV) extraction were calculated and the characteristics of the stripping of Ce(IV), Th(IV) from the loaded organic phase were studied. (C) 1998 Elsevier Science B.V. All rights reserved.

Synthesis, luminescence, energy transfer and Langmuir-Blodgett films of amphiphilic complexes of rare earths with monooctadecyl phthalate

Three new amphiphilic rare earth complexes with only two organic long chains Ln (MOP)(2)Cl (MOP=monooctadecyl phthalate, Ln=Eu, Tb, Gd) were synthesized and characterized by elemental analysis. The complexes (Eu, Tb) showed good luminescence property with long fluorescence lifetime, whereas the intensity and lifetime of Tb complex are greater than those of Eu complex, By measuring the triplet energy levels of ligand based on energy transfer mechanism, above phenomena have been well explained. The Langmuir films of the complexes on the air/water interface were also studied and the results show that all of them have good film-forming property.

pH-potentiometric study on rare earths and calcium binary and ternary complexes with DL-malic acid and L-hydroxyproline

The stability constants of M-L binary system and M-L-L' (M = La3+ similar to Yb3+, Y3+ and Ca2+; L= DL-malic aicd, L' = L-hydroxyproline) ternary system were determined by pH-(0)-tentiometric method under the simulating physiological condition(37 degrees C, I=0.15 mol/L NaCl). The complex species MpLqLr'H-s(abbr as pqrs) in the sytems were ascertained by program COMPLEX. The results show that there are three species(1101, 1100 and 1200) in M-L binary system and one species(1010) in M-L' binary system. In addition to the above four species, a new species, 1112 was found in the M-L-L' ternary system, which is the only species of mixed ligands. Rare earth ions form more stable complexes than calcium ion does and the stability differences between their complexes in the ternary system are less than that in the binary system. The distributions of all the species in La-L-L' ternary system vs pH are discussed.