Authors:Pedro Forster, Ademar Lugao, Hermi Brito, and Duclerc Parra
Polymers doped with rare earth complexes are advantaged in film production for many applications in the luminescent field.
In this luminescent polycarbonate (PC) films doped with diaquatris(thenoyltrifluoroacetonate)europium(III) complex [Eu(TTA)3(H2O)2] were prepared and their calorimetric and luminescent properties in the solid state are reported. The thermal behavior was
investigated by utilization of differential scanning calorimetry (DSC) and thermogravimetry (TG). Due of the addition of rare
earth [Eu(TTA)3(H2O)2] into PC matrix, changes were observed in the thermal behavior concerning the glass transition and thermal stability. Characteristic
broadened narrow bands arising from the 5D0 → 7FJ transitions (J = 4−0) of Eu3+ ion indicate the incorporation of the Eu3+ ions in the polymer. The luminescent films show enhancement emission intensity with an increase of rare earth concentration
in polymeric matrix accompanied by decrease in thermal stability.
Authors:I. Alimarin, Yu. Jakovlev, A. Miklishansky, N. Dogadkin, and O. Stepanets
Radioactivation analysis is the only method which allows the determination of individual rare earth element impurities in
rare earth elements of high purity. The determination of dysprosium, europium, samarium and gadolinium in yttrium oxide is
complicated by the short half-life of165Dy (138 min.) and by the difficulty of separating traces of these elements from the matrix. A chromatographic method has been
developed, for the separation of traces of Dy, Eu, Sm and Gd from ytrium, on a column packed with anion exchangerAV-17, by means of elution with 0.1N and 0.3M solutions of EDTA-sodium salt, followed by the separation of the mixture of the rare earth impurities on a microcolumn of
cation exchangerKU-2, using a 0.17M solution of ammonium α-hydroxyisobutyrate as the eluent. The sensitivity of the determination of Dy, in the case of irradiating
10 mg of Y2O3 with a flux of 1.2·1013 n·cm−2·sec−1 for 5 min. was 1·10−7%; the corresponding values for Sm, Eu and Gd, when irradiating a 100 mg sample of Y2O3 for 20 hours with the same flux, were 2·10−7%, 1·10−8% and 5·10−6%, respectively.
Authors:S. Chen, X. Meng, Q. Shuai, B. Jiao, S. Gao, and Q. Shi
solid complex Eu(C5H8NS2)3(C12H8N2) has been obtained from reaction of
hydrous europium chloride with ammonium pyrrolidinedithiocarbamate (APDC)
and 1,10-phenanthroline (o-phen⋅H2O)
in absolute ethanol. IR spectrum of the complex indicated that Eu3+
in the complex coordinated with sulfur atoms from the APDC and nitrogen atoms
from the o-phen. TG-DTG investigation provided
the evidence that the title complex was decomposed into EuS.
enthalpy change of the reaction of formation of the complex in ethanol, ΔrHmθ(l), as –22.2140.081 kJ mol–1,
and the molar heat capacity of the complex, cm,
as 61.6760.651 J mol–1 K–1,
at 298.15 K were determined by an RD-496 III type microcalorimeter. The enthalpy
change of the reaction of formation of the complex in solid, ΔrHmθ(s), was calculated as 54.5270.314 kJ mol–1
through a thermochemistry cycle. Based on the thermodynamics and kinetics
on the reaction of formation of the complex in ethanol at different temperatures,
fundamental parameters, including the activation enthalpy (ΔH≠θ),
the activation entropy (ΔS≠θ),
the activation free energy (ΔG≠θ),
the apparent reaction rate constant (k),
the apparent activation energy (E), the
pre-exponential constant (A) and the reaction
order (n), were obtained. The constant-volume
combustion energy of the complex, ΔcU,
was determined as –16937.889.79 kJ mol–1
by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy
of combustion, ΔcHmθ,
and standard enthalpy of formation, ΔfHmθ,
were calculated to be –16953.379.79 and –1708.2310.69
kJ mol–1, respectively.
The effect of Aldrich humic acid (HA) on the mobility of137Cs,85Sr,152Eu and239Pu radionuclides was studied in Ca-montmorillonite suspensions. Verified 2-sites-2-species (2s2s) models correspond to an
intensive interaction of all elements with humificated surface, what is in a remarkable contrast with the weak complexation
of cesium and even strontium in solutions — the neutral ligand interaction constants β (l/mol) are log β<−9.9 and 7.56±0.21
for Cs and Sr, respectively. The result for europium complexation in solution, log β=12.49±0.18 is in a good agreement with
literature data. For plutonium(IV) not only a high proton competitive constant in solution was obtained, log β β=(−0.67±0.32)+3pH,
but also a strong chemisorption, which at high concentrations of humic acid (above 0.05 g/l) indicates the formation of bridge
humate complexes of plutonium on the humificated surface. Logarithms of heterogeneous interaction constants (
24, l/g) for Pu(IV) −3.80±0.72. Distribution coefficients of humic acid and metal humates between 0.01 g HA/l solution and montmorillonite
were derived as logKd(AH)=−1.04±0.11, logKd(EuA)=1.56±0.11 and logKd(PuA)=2.25±0.04, while the values for Cs and Sr were obtained with very high uncertainty. Speciation of the elements on montmorillonite
surface is illustrated as a function of equilibrium concentration of humic acid in solution and of pH.
Solvent extraction of65zinc,60cobalt and152+154europium from aqueous buffers into benzene containing 4-thiobenzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one (SBMPP)
has been investigated in detail (μ=0.1, T=26±1°C). The species extracted and the values of log Kex, where Kex refers to the extraction equilibrium, are ZnL2 (−2.68) CoL2(−3.08) and EuL3(−7.08), where L is the anion of the ligand. The sulfur analog appears to be more effective than the parent ligand 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one
in the extraction of zinc(II) and cobalt(II), whereas the reverse is true with europium(III).
Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B−) in the presence of diphenyl-N-butylcarbamoylmethyl phosphine oxide (DPBCMPO, L) has been investigated. The equilibrium data
have been explained assuming that the complexes HL+, HL2+, ML23+, ML33+ and ML43+ (M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated
with water have been determined. It has been found that the stability constants of the corresponding complexes EuLn3+ and AmLn3+, where n = 2, 3, 4 and L is DPBCMPO, in water saturated nitrobenzene are comparable.
Authors:P. Ruikar, M. Nagar, M. Subramanian, K. Gupta, N. Varadarajan, and R. Singh
The extraction of plutonium(IV), uranium(VI), zirconium(IV), europium(III) and ruthenium(III) with -pre-irradiated n-dodecane solutions of methylbutyl substituted hexanamide (MBHA), octanamide (MBOA) and decanamide (MBDA) from 3.5M HNO3 has been studied as a function of absorbed dose up to 184×104 Gray. The distribution ratios (Kd) of uranium(VI) decreased gradually up to a dose of 50×104 Gray and became almost constant thereafter, while ruthenium(III) and europium(III) were not extracted in the entire dose range studied. The Kd values of Pu(IV) decreased gradually up to 10×104 Gray, for MBOA, and 30×104 Gray for MBHA and MBDA and then increased up to a dose of 72×104 Gray, indicating the synergistic effect of radiolytic products at higher doses. The extraction of zirconium(IV) was found to increase gradually up to 72×104 Gray. However, the steep fall in Kd values of plutonium(IV), zirconium(IV) beyond a dose of 72×104 Gray was atrributed to third phase formation. The radiolytic degradation of amides was monitored by quantitative IR spectroscopy and was found to follow the order MBOA>MBDA>MBHA at 184×104 Gray having the amines and carboxylic acids as the main radiolytic products.
Authors:I. Nowik, Y. Levi, I. Felner, E. Bauminger, and C. Mermelstein
Mössbauer studies of dilute57Fe and151Eu in RMn2Si2-xGex (R=La, Sm, Eu and Gd) at temperatures 4.2 K to 480 K have been performed. The diamagnetic iron and europium reveal the magnetic order of the Mn and rare earth sublattices through transferred hyperfine interactions. The57Fe studies show that in LaMn2Si2, LaMn2Ge2, and SmMn2Ge2 the Mn is magnetically ordered above the known Curie temperatures, and the compounds are antiferromagnets up to TN=470 K, 415 K and 385 K respectively. Studies of151Eu in R1-xEuxMn2Si2, (R=La, Gd) display Eu subspectra corresponding to Eu2+, Eu3+ and intermediate valant Eu. All display large magnetic hyperfine fields.
Authors:E. Makrlík, P. Vaňura, P. Selucký, V. Babain, and I. Smirnov
Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B−) in the presence of N,N,N′,N′-tetraethyl-2,6-dipicolinamide (TEtDPA, L) has been investigated. The equilibrium data have
been explained assuming that the cations HL+, HL23+, ML23+ and ML33+ (M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated
with water have been determined. It has been found that the stability constants of the corresponding complexes EuLn,org3+ and AmLn,org3+, where n = 2, 3 and L is TEtDPA, in the mentioned medium are comparable.
Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B−1) in the presence of N,N′-dibutyl-N,N′-dimethyl-2-(2-dodecyloxyethyl)-malonamide (DBDMDDOEMA, L) has been investigated. The
equilibrium data have been explained assuming that the cations HL2+, ML23+ and ML33+ (M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated
with water have been determined. It has been found that the stability constants of the corresponding complexes EuLn3+ and AmLn3+, where n = 2,3 and L is DBDMDDOEMA, in water saturated nitrobenzene are comparable.