Comparison of thermal ionization mass spectrometry and Multiple Collector Inductively Coupled Plasma Mass Spectrometry for cesium isotope ratio measurements

In the nuclear domain, precise and accurate isotopic composition determination of elements in spent nuclear fuels is mandatory to validate neutron calculation codes and for nuclear waste disposal. The present study presents the results obtained on Cs isotope ratio by mass spectrometric measurements. Natural cesium is monoisotopic (¹³³Cs) whereas cesium in spent fuels has 4 isotopes (¹³³Cs, ¹³⁴Cs, ¹³⁵Cs, and ¹³⁷Cs). As no standard reference material is available to evaluate the accuracy of Cs isotopic measurements, a comparison of cesium isotopic composition in spent nuclear fuels has been performed between Thermal Ionization Mass Spectrometry (TIMS) and a new method involving Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) measurements. For TIMS measurements, isotopic fractionation has been evaluated by studying the behavior of cesium isotope ratios (¹³³Cs/¹³⁷Cs and ¹³⁵Cs/¹³⁷Cs) during the analyses. For MC-ICPMS measurements, the mass bias effects have been corrected with an external mass bias correction using elements (Eu and Sb) close to cesium masses. The results obtained by the two techniques show good agreement: relative difference on ¹³³Cs/¹³⁷Cs and ¹³⁵Cs/¹³⁷Cs ratios for two nuclear samples, analyzed after chemical separation, ranges from 0.2% to 0.5% depending on the choice of reference value for mass bias correction by MC-ICPMS. Finally the quantification of the ¹³⁵Cs/²³⁸U ratio by the isotope dilution technique is presented in the case of a MOx (mixed oxide) spent fuel sample. Evaluation of the global uncertainties shows that this ratio could be defined at an uncertainty of 0.5% (k = 2). The intercomparison between two independent mass spectrometric techniques is fundamental for the evaluation of uncertainty when no isotopic standard is available.     

M(N3)2(L)]n: building 3-D MII-azido networks with new topologies

Novel 3D topologies combining diazine and azido bridges between MnII magnetic centres have been obtained and characterised by low-temperature magnetic measurements.     

Torsional stiffness of viscoelastic spheres in contact

The theory of elastic contact between two spherical bodies according to Hertz, Mindlin and others is used as a basis for an extension to include the contribution of the viscous effects to the total stress for viscoelastic spheres subjected to twisting moments. Expressions relating twisting moment to the radius of a stick region of the contact surface and the radius of the stick region to twist angle are derived. Two term power series truncations of the relations are then used to derive approximate expressions for torsional stiffness of the bodies. Validation of the model was by experiments utilising a rheometer device. Applications for the model in post-harvest agriculture include extraction of material surface properties for use in discrete element modelling of mechanical interactions of fruits and other spheroidal produce during machine handling.Received: 6 January 2004, Published online: 18 June 2004PACS: 46.35. + z Viscoelasticity, plasticity, viscoplasticity - 46.55. + d Tribology and mechanical contacts - 62.20.Dc Elasticity, elastic constants     

Sensitivity Analysis for Dynamic Spontaneous Imbibition with Variable Inlet Saturation and Interfacial Coupling Effects

Dynamic spontaneous imbibition (DSI) plays an important role in oil reservoir characterization. Conventional equations used to characterize DSI consider neither interfacial coupling effects (ICE) nor variable inlet saturation (S*) for DSI. Yazzan et?al. (Transp Porous Media 87(1):309?C333, 2011a; 86(3):705?C717, 2011b) developed a set of equations, and a numerical solution scheme, to take into account ICE and variable S* for DSI. Based on these, a graphical user interface (GUI) simulator was built. A sensitivity analysis has been conducted to study the effect of the fluid and rock properties on DSI. The results reveal that including a variable S* has no significant impact; however, neglecting ICE results in an overestimation of the imbibition flow rate. Moreover, it is shown that the capillary and relative permeability curves determine the type of frontal advance, and that the imbibition recovery is proportional to the square root of time.     

Microwave irradiation and COMU: a potent combination for solid-phase peptide synthesis

Here we demonstrate the compatibility of Oxyma-based uronium-type coupling reagent COMU with microwave-assisted peptide synthesizers. Consistent with previous reports, COMU displayed higher efficiency than benzotriazole classical immonium salts HATU and HBTU in the demanding synthesis of the Aib derivative of Leu-Enkephalin pentapeptide and did not yield Oxyma-based byproducts. Thus, the combination of microwave irradiation and COMU resulted in a similar performance in considerably shorter time to that achieved by manual synthesis.     

Synthesis,crystal structure and magnetic properties of the helical oxalate-bridged copper(II) chain {[(CH3)4N]2[Cu(C2O4)2] · H2O}n

The preparation, crystal structure and magnetic properties of a new oxalate-containing copper(II) chain of formula {[(CH₃)₄N]₂[Cu(C₂O₄)₂] · H₂O}_n (1) [(CH₃)₄N⁺ = tetramethylammonium cation] are reported. The structure of 1 consists of anionic oxalate-bridged copper(II) chains, tetramethylammoniun cations and crystallization water molecules. Each copper(II) ion in 1 is surrounded by three oxalate ligands, one being bidentate and the other two exhibiting bis-bidenate coordination modes. Although all the tris-chelated copper(II) units from a given chain exhibit the same helicity, adjacent chains have opposite helicities and then an achiral structure results. Variable-temperature magnetic susceptibility measurements of 1 show the occurrence of a weak ferromagnetic interaction through the oxalate bridge [J = +1.14(1) cm⁻¹, the Hamiltonian being defined as H = –J ∑_nmS_i · S_j]. This value is analyzed and discussed in the light of available magneto-structural data for oxalate-bridged copper(II) complexes with the same out-of-plane exchange pathway.