Institutional results of the Argentine Graduate Programme in Radiochemistry

Summary The evolution of radiochemistry at the National Atomic Energy Commission (CNEA) in Argentina is analyzed. The antecedents of the establishment, in 1998, of the Master Programme in Radiochemistry, jointly organized by CNEA and the Buenos Aires Regional Faculty of the National Technological University are revised, and the structure of the Programme is described. On the basis of the thesis works, the initial trends are discussed. Finally, the institutional results of the Programme are described.     

Copper diffusion in Ti-Si-N layers formed by inductively coupled plasma implantation

Ternary Ti-Si-N refractory barrier films of 15 nm thick was prepared by low frequency, high density, inductively coupled plasma implantation of N into Ti_xSi_y substrate. This leads to the formation of Ti-N and Si-N compounds in the ternary film. Diffusion of copper in the barrier layer after annealing treatment at various temperatures was investigated using time-of-flight secondary ion mass spectrometer (ToF-SIMS) depth profiling, X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and sheet resistance measurement. The current study found that barrier failure did not occur until 650 °C annealing for 30 min. The failure occurs by the diffusion of copper into the Ti-Si-N film to form Cu-Ti and Cu-N compounds. FESEM surface morphology and EDX show that copper compounds were formed on the ridge areas of the Ti-Si-N film. The sheet resistance verifies the diffusion of Cu into the Ti-Si-N film; there is a sudden drop in the resistance with Cu compound formation. This finding provides a simple and effective method of monitoring Cu diffusion in TiN-based diffusion barriers.     

Volumetric and refractive properties of binary mixtures containing 1,3-dioxolane and isomeric chlorobutanes

The relation between refractive index deviations and excess volumes for binary mixtures formed by a cyclic ether and a haloalkane has been tested using several methods: refractive index mixing rules and equations of state. Refractive index deviations, excess volumes and molar refractions have been calculated from experimental data of refractive indices and densities at two temperatures 298.15 and 313.15 K. Results obtained have been discussed in terms of intermolecular interactions. Refractive indices were compared with those predicted by several mixing rules. Excess volumes have also been correlated using several cubic equations of state and finally a relation between parameter b from equations of state and molar refraction has been provided.     

Proton–proton bremsstrahlung towards the elastic limit at 190 MeV incident beam energy

A series of nucleon–nucleon bremsstrahlung (NNγ) experiments at 190 MeV incident beam energy have been performed at KVI in order to gain more insight into the dynamics governing the bremsstrahlung reaction. After initial measurements wherein the bremsstrahlung process was studied far away from the elastic limit, a new study was used to probe the process nearer to the elastic limit by measuring at lower photon energies. Measured cross sections and analyzing powers are compared with the predictions of a microscopic model and those of two soft-photon models. The theoretical calculations overestimate the data by up to ≈30%, for some kinematics.     

Methods in carbon K-edge NEXAFS: Experiment and analysis

Near-edge X-ray absorption spectroscopy (NEXAFS) is widely used to probe the chemistry and structure of surface layers. Moreover, using ultra-high brilliance polarised synchrotron light sources, it is possible to determine the molecular alignment of ultra-thin surface films. However, the quantitative analysis of NEXAFS data is complicated by many experimental factors and, historically, the essential methods of calibration, normalisation and artefact removal are presented in the literature in a somewhat fragmented manner, thus hindering their integrated implementation as well as their further development. This paper outlines a unified, systematic approach to the collection and quantitative analysis of NEXAFS data with a particular focus upon carbon K-edge spectra. As a consequence, we show that current methods neglect several important aspects of the data analysis process, which we address with a combination of novel and adapted techniques. We discuss multiple approaches in solving the issues commonly encountered in the analysis of NEXAFS data, revealing the inherent assumptions of each approach and providing guidelines for assessing their appropriateness in a broad range of experimental situations.     

A procedure for measuring the flexibility of single wood-pulp fibres

A way of determining the flexibility of wood-pulp fibres is developed, which involves i) a precise measurement of the topology of single-fibres by using a confocal laser scanning microscope and ii) the measurement of the elastic modulus of the fibres by using a single-fibre fatigue cell. Reported in this paper are the initial results of tests carried out on black spruce fibres, which have been subjected to three different levels of mechanical refining energy, namely ∼1100, 2300, and 3500 kWh/t. It is found that the fibre flexibility rises significantly between the first and second energy levels, but it does not change to the same degree between the second and third ones. The described procedure of measuring the flexibility of fibres may be used to establish the appropriate refiner energy necessary for the production of a specific grade of paper. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 42, No. 1, pp. 115–128, January–February, 2006.     

Structural characterisation of Sb-based heterostructures by X-ray scattering methods

Antimonide-based superlattices dedicated to the elaboration of opto-electronic devices have been studied by X-ray scattering techniques. In particular, specular and non-specular X-ray reflectometry experiments have been performed on two MBE-samples elaborated with different shutter sequences at the interfaces. The results have shown a limitation of the incorporation of Sb species in the subsequent InAs layer for one of the samples, as expected.Then, a study on a InGaAs-cap layer/(InGaAs/AlAsSb)_N superlattice grown on a InGaAs/InP buffer layer by both specular X-ray reflectometry and High resolution X-ray diffraction is reported. In particular, the results have revealed the presence of a highly disturbed thin-layer on top of the MOVPE-made GaInAs, whose presence has been explained by In-concentration modification during the desoxidation procedure at the surface of the MOVPE-made GaInAs.Beside the results on the Sb-based heterostructures, the use of X-ray scattering metrology as a routinely working non-destructive testing method has been emphasized.     

Interactions of xanthines with activated carbon: II. The adsorption equilibrium

In the present work, we have studied the adsorption of xanthine derivatives by activated carbon sorbents in aqueous solutions. The study comprised both kinetic, equilibrium and thermodynamic aspects. The kinetic results were reported in a previous paper; the equilibrium-related results are discussed here. The two types of carbon used exhibit some differences but the equilibrium isotherms obtained are all of the H-3 type in the classification of Giles. This suggests a high affinity of the sorbents for the sorbates. We also found that the overall adsorption process comprises more than one individual adsorption-desorption process of which one leads to the formation of a “monolayer” and the other to the “precipitation” of the sorbate on the sorbent surface (multilayer adsorption); the amount of sorbate adsorbed in monolayer form was seemingly greater in C-A14.     

Energy level alignment between C60 and Al using ultraviolet photoelectron spectroscopy

The energy level alignment between C₆₀ and Al has been investigated by using ultraviolet photoelectron spectroscopy. To obtain the interfacial electronic structure between C₆₀ and Al, C₆₀ was deposited on a clean Al substrate in a stepwise manner. The valence-band spectra were measured immediately after each step of C₆₀ deposition without breaking the vacuum. The measured onset of the highest occupied molecular orbital energy level was located at 1.59 eV from the Fermi level of Al. The vacuum level was shifted 0.68 eV toward lower binding energy with additional C₆₀ layers. The observed vacuum level shift means that the interface dipole exists at the interface between C₆₀ and Al. The barrier height of electron injection from Al to C₆₀ is 0.11 eV, which is smaller value than that of hole injection.     

Aluminum(III) complexes containing O,O chelating ligand

The stoichiometric reactions of trimethylaluminum with 2,6‐(MeOCH₂)₂C₆H₃OH (LH) revealed compounds L₃Al ( 1 ) and L₂AlMe ( 2 ). On the other hand reaction of 1 equiv. of LH with trimethylaluminum did not lead to the formation of complex LAlMe₂ ( 3 ), rather 2 together with Me₃Al were observed as a result of a disproportionation of 3 . Compounds 1 and 2 were characterized by elemental analysis, ¹H and ¹³C NMR spectroscopy and in the case of 1 by X‐ray diffraction. Derivative 2 underwent transmetalation with Ph₃SnOH, giving LSnPh₃ ( 4 ) as the result of a migration of ligand L from the aluminum to the tin atom. The identity of 4 was established by elemental analysis, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy and ¹H, ¹¹⁹Sn HMBC experiments. The system 2 and B(C₆F₅)₃ in a 1:1 molar ratio was shown to be active in the polymerization of propylene oxide and ε‐caprolactone. Copyright © 2007 John Wiley & Sons, Ltd.