Recent achievements in the development of partitioning processes of minor actinides from nuclear wastes obtained in the frame of the NEWPART European programme (1996–1999)

Partitioning of long-lived minor actinides (americium and curium) from the nuclear wastes issuing the reprocessing of nuclear spent fuels, in order to transmute them into short-lived nuclides or to condition them into stable crystalline matrices, was the subject of intense research within the NEWPART research program of the European 4^th Frame Work Program, FWP (1996–1999). The target waste considered was the acidic raffinate (HAR) issuing the reprocessing of the used nuclear fuels by the PUREX process. A two step separation process based on liquid-liquid extraction was designed. The first step consists in the co-separation of the mixture of trivalent actinides and lanthanides from the HAR by extraction with a malonamide extractant (DIAMEX process), while the second step concerns the actinides(III)/lanthanides(III) group separation (SANEX process). Several DIAMEX and SANEX processes were developed and successfully tested with cold, spiked and genuine high active effluents. The research carried out also included basic and fundamental works in order to better understand the relationships between the structures of the extractants and their affinities for the target metal ions. The lecture highlighted both the basic and applied aspects of the research. This work will be pursued (PARTNEW program) within the 5^th FWP of the European Union during the period 2000–2003.     

Cohesion energy densities and solubility parameters for the n-alkanes expressed as a new homomorph equation

A new correlation formula for the calculation of the cohesive energy density for n-alkanes and the corresponding homomorphs for polar solvents has been developed. Constants of the Antoine equation and literature values of heat of vaporisation at the boiling point and at 25°C were used. For the C₂-C₁₆ n-alkanes the new correlation equation describes the cohesion energy density as a function of molal volume and reduced temperature within the accuracy of experimental data. In the range of reduced temperatures 0.4 < T_r < 0.7 and molal volumes 50 < V <300 cm³ the maximum deviation for this fit is less than ± 0.05 J^1/2 cm^?3/2. In the region of T_r and V for polar homomorphs to the n-alkanes at 25°C the deviations are typically less than half this value.     

On the Synergy Effect in MoO3–Fe2(MoO4)3 Catalysts for Methanol Oxidation to Formaldehyde

Methanol oxidation to formaldehyde was studied over a series of Fe–Mo–O catalysts with various Mo/Fe atomic ratio and the end compositions Fe₂O₃ and MoO₃. The activity data show that the specific activity passes through a maximum with increase of the Mo content and is the highest for Fe₂(MoO₄)₃. The selectivity to formaldehyde, on the other hand, increases with the Mo content in the catalyst. A synergy effect is observed in that a catalyst with the Mo/Fe ratio 2.2 is almost as active as Fe₂(MoO₄)₃ and as selective as MoO₃. Imaging of a MoO₃/Fe₂(MoO₄)₃ catalyst by SEM and TEM shows that the two phases form separate crystals, and HRTEM reveals the presence of an amorphous overlayer on the Fe₂(MoO₄)₃ crystals. EDS line-scan analysis in STEM mode demonstrates that the Mo/Fe ratio in the amorphous layer is ~2.1 in the fresh catalyst and ~1.7 in the aged catalyst. The enrichment of Mo at the catalyst surface is confirmed by XPS data. Raman spectra give evidence for the Mo in the amorphous material being in octahedral coordination, which is in contrast to the crystalline Fe₂(MoO₄)₃ bulk structure where Mo has tetrahedral coordination. X-ray diffraction (XRD) analysis gives no support for the formation of a defective molybdate bulk structure. The results presented give strong support for the Mo rich amorphous structure being observed on the Fe₂(MoO₄)₃ crystal surfaces being the active phase for methanol oxidation to formaldehyde.     

Development of a correlation between the non-polar solubility parameter,refractive index and molecular structure. I. Aliphatic hydrocarbons

For non-polar liquids (e.g. the alkanes) the cohesion energy density (λ²) can be shown to be a function of the refractive index (nD ), molal volume (V) and molecular structure according to: where Δ is the non-polar solubility parameter and the increments g_ij are determined from molecular structure. The difference between values of Δ calculated by this formula and experimental data is <0.1% for the C₅–C₁₆ n-alkanes and <0.8% for the C₅–C₈ branched isomers. The main object of this correlation was to provide a method for estimating the London dispersion force contribution to the cohesive energy of branched polar liquids.     

The Influence of Entrainment on Distribution Ratios in Complexation Studies

ABSTRACT

Entrainment of a small amount of one phase in the other after phase separation is almost impossible to avoid in solvent extraction. The effect on distribution ratios, D-values, is that the measurement at high D-values results in lower values than the true D-value. The opposite happens with the aqueous phase. Entrainment reduces the maximum effective separation of two substances using countercurrent solvent extraction in mixer-settlers, pulsed columns, and centrifugal extractors. When solvent extraction is used to study the complex formation, the entrainment of a small amount of the organic phase in the aqueous phase reduces the limiting slope observed at low D-values and sometimes makes the accurate determination of one or more of the stability constants impossible.

On the other hand, the reduction of the expected limiting slope yields a tool for estimation of the entrainment in the specific case and hence makes it possible to get entrainment data that can be used in comparisons of the efficiencies of different phase separation techniques and equipment.

In this work, the effect of entrainment on “effective” D-values is derived in a quantitative way, yielding equations that can be either used to predict “effective” D-values from any given relative entrainment in any phase or used to estimate entrainment by comparing measured “effective” D-values and the corresponding data from test tube experiments with no entrainment.     

Utilizing nanofabrication to construct strong, luminescent materials

Luminescent materials have been utilized widely in applications from lighting to sensing. The new development of technologies based on luminescence requires the materials to have high luminescence efficiency and mechanical strength. In this paper, we report the fabrication of luminescent materials possessing high mechanical strength by nanofabrication with polyvinyl alcohol used as a stabilizer or coupling agent. X-ray diffraction and high-resolution transmission microscope observations reveal that the nanocomposite sample contains ZnS and ZnO nanoparticles as well as kozoite and sodium nitrate. The mechanical strength and hardness of these nanocomposites are reasonably high, higher than polycarbonate and some carbon nanotube reinforced nanocomposites. Strong luminescence is observed in the new nanocomposites and the luminescence intensity does not degrade following up to 30?min of x-ray irradiation. Our results indicate that nanofabrication may provide a good method to improve the mechanical strength of luminescent materials for some applications in which high-strength luminescent materials are needed.     

Self-healing and self-organized gold nanoparticle films at a water/organic solvent interface

Gold nanoparticles (5 nm and 20 nm) have been synthesized and stabilized with mercaptoundecanol. These particles, although insoluble in water or common organic solvents, spread as a thin film at the liquid-liquid interface between a water phase and an organic phase. Films of these gold nanoparticles have been observed both by conventional transmission electron microscopy of deposited samples and by cryo-transmission electron microscopy of plunge-frozen samples. The film can be monolayered and extend over centimeter-sized areas. The particle films spontaneously re-assemble and self-organize at the interface when disrupted. This self-healing capacity of the film should make it possible to build a device for continuous production and deposition of the film.     

Evaluation of impact dynamics and contact forces in a hydropower rotor due to variations in damping and lateral fluid forces

Damages due to contact between the runner and the discharge ring have been observed in several hydroelectric power units. The damage can cause high repair costs of the runner and the discharge ring as well as considerable production losses.In this paper a rotor model of a 45 MW hydropower unit is used for the analysis of the rotor dynamical phenomena occurring due to contact between the runner and the discharge ring for different grades of lateral force on the turbine and bearing damping. The rotor model consists of a generator rotor and a turbine, which is connected to an elastic shaft supported by three isotropic bearings. The discrete representation of rotor model consists of 32 degrees of freedom; to increase the speed of the analysis, the size of the model was reduced with the IRS method to a system with 8 degrees of freedom.Results are presented in bifurcation diagrams, maximum contact force, Poincaré map and phase portrait. Simulations indicate that the contact forces between the turbine and the discharge ring are large, with considerable risks for serious damage as a consequence. The analysis shows that the risk for contact and damage are large for relatively small lateral turbine loads when the gap between the turbine and the discharge ring is small and the contact stiffness is high.     

Milling machine spindle analysis using FEM and non-contact spindle excitation and response measurement

In this paper a method for analysing lateral vibrations in a milling machine spindle is presented including finite-element modelling (FEM), magnetic excitation and inductive displacement measurements of the spindle response. The measurements can be conducted repeatedly without compromising safety procedures regarding human interaction with rotating high speed spindles. The measurements were analysed and compared with the FEM simulations which incorporated a spindle speed sensitive bearing stiffness, a separate mass and stiffness radius and a stiffness radius sensitive shear deformation factor. The effect of the gyroscopic moment and the speed dependent bearing stiffness on the system dynamics were studied for different spindle speeds. Simulated mode shapes were experimentally verified by a scanning laser doppler vibrometer. With increased spindle speed, a substantial change of the eigenfrequencies of the bearing-related eigenmodes was detected both in the simulations and in the measurements. The centrifugal force that acted on the bearing balls resulted in a softening of the bearing stiffness. This softening was shown to be more influential on the system dynamics than the gyroscopic moment of the rotor. The study performed indicates that predictions of high speed milling stability based on 0 rpm tap-test can be inadequate.     

Selenolthiol and dithiol C-terminal tetrapeptide motifs for one-step purification and labeling of recombinant proteins produced in E. coli

We have previously shown that a redox-active selenocysteine-containing tetrapeptide-Sel-tag (Gly-Cys-Sec-Gly)-can be used as a C-terminal fusion motif for recombinant proteins produced in Escherichia coli. This Sel-tag allows selenolate-targeted one-step purification, as well as fluorescent labeling or radiolabeling either with gamma emitters (75Se) or with positron-emitting radionuclides (11C). Here we have analyzed four different redox-active C-terminal motifs, carrying either dithiol (Gly-Cys-Cys-Gly or Ser-Cys-Cys-Ser) or selenolthiol (Gly-Cys-Sec-Gly or Ser-Cys-Sec-Ser) motifs. Utilizing these different functional motifs with the same recombinant protein (Fel d 1), we were able to assess their relative reactivities and potential usefulness for biotechnological applications. We found that all four redox-active tags could be utilized for efficient one-step purification to provide pure protein from a crude bacterial lysate through reversible binding to phenylarsine oxide sepharose, with yields and purities comparable to those obtained for a His-tagged protein purified by the more common approach with use of a Ni2+ column. For labeling with electrophilic fluorescent or radioactive compounds, however, the selenolthiol motifs were considerably more efficient than their dithiol counterparts. The results thus show that both the selenolthiol- and the dithiol-containing tags can serve as efficient alternatives to His-tags for protein purification, while the selenolthiol motifs offer additional and unique potential for Sec-targeted labeling. It should therefore be possible to utilize these multifunctional tetrapeptide motifs to develop a wide range of novel biotechnological applications based on Sec targeting with electrophilic compounds.