Inductively coupled plasma compared with direct current arc spectrometry for analysis of minor elements in aluminium baths

A validation study was carried out in order to evaluate the efficiency of inductively coupled plasma-optical emission spectrometry (ICP-OES) for the analysis of minor elements (manganese, chromium, copper, iron, and titanium) in aluminium alloys. Aluminium casting samples were obtained by adding compressed powder compacts of each alloying element and aluminium (minitablets) to aluminum baths in a laboratory crucible furnace. Digestion of solid samples was performed using concentrated HCI and H202 35% (v/v) previous to analysis by ICP-OES without any matrix separation. This solution-based method was validated considering direct current arc spectrometry as the reference method based on direct analysis without any pretreatment of the solid samples considered. Univariate statistical procedures were carried out, for which precision <3% and trueness of the analytical results were taken into account.     

Ambiphilic boryl groups in a neutral Ni(ii) complex: a new activation mode of H2

The concept of metal–ligand cooperation opens new avenues for the design of catalytic systems that may offer alternative reactivity patterns to the existing ones. Investigations of this concept with ligands bearing a boron center in their skeleton established mechanistic pathways for the activation of small molecules in which the boron atom usually performs as an electrophile. Here, we show how this electrophilic behavior can be modified by the ligand trans to the boron center, evincing its ambiphilic nature. Treatment of diphosphinoboryl (PBP) nickel–methyl complex 1 with bis(catecholato)diboron (B₂Cat₂) allows for the synthesis of nickel(ii) bis-boryl complex 3 that promotes the clean and reversible heterolytic cleavage of dihydrogen leading to the formation of dihydroborate nickel complex 4. Density functional theory analysis of this reaction revealed that the heterolytic activation of H₂ is facilitated by the cooperation of both boryl moieties and the metal atom in a concerted mechanism that involves a Ni(ii)/Ni(0)/Ni(ii) process. Contrary to 1, the boron atom from the PBP ligand in 3 behaves as a nucleophile, accepting a formally protic hydrogen, whereas the catecholboryl moiety acts as an electrophile, receiving the attack from the hydride-like fragment. This manifests the dramatic change in the electronic properties of a ligand by tuning the substituent trans to it and constitutes an unprecedented cooperative mechanism that involves two boryl ligands in the same molecule operating differently, one as a Lewis acid and the other one as a Lewis base, in cooperation with the metal. In addition, reactivity towards different nucleophiles such as amines or ammonia confirmed the electrophilic nature of the Bcat moiety, allowing the formation of aminoboranes.

A bis(boryl)nickel complex promotes the facile and reversible activation of H₂ through a cooperative mechanism that involves the metal and both boryl moieties in a concerted five-center process.     

Selenium in electrolytic manganese as a reference material for the quality control of aluminium melts

Electrolytic manganese is an important alloying element for aluminium and steel melts. It is mainly added to melts of aluminium in the holding furnace as tablets or minitablets (compressed compacts of manganese and aluminium powders). Selenium derivates are usually added during the production of electrolytic manganese, so some selenium is present in the alloys produced when electrolytic manganese is added to the aluminium furnace. Since the selenium contents of many alloys are of concern from health and environmental perspectives, their values should be provided. In this work, a laboratory reference material (LRM) based on electrolytic manganese was produced to assure our routine quality control method, where selenium is analysed by hydride generation followed by optical emission spectrometry with inductively coupled plasma (HG–ICP–OES). Therefore, the present paper describes in detail the preparation procedure for and the results from homogeneity and stability studies performed on electrolytic manganese LRM. For this purpose, a commercial electrolytic manganese lot was selected and the main factors involved in the preparation of the material (pretreatment step, homogenization, bottling and storage) were carefully studied and established in order to guarantee the long-term stability of the LRM. The results obtained showed that the LRM developed was a fit-for-purpose material for the quality control of the routine analysis of selenium.     

The N = Z nucleus 76 Sr: Gamow-Teller strength and nuclear deformation

Challenged by recent theoretical work, a study of the -EC decay of the N = Z even-even nucleus ⁷⁶ Sr has been undertaken in order to assign the parent ground-state deformation. In this study 13 levels with have been located in ⁷⁶ Rb. The beta-delayed proton emission has been observed for the first time in an N = Z even-even nucleus. The p branching ratio has been determined to be . The ⁷⁶ Sr half-life has been remeasured and a more precise value of s has been obtained. On the basis of the comparison of measured Gamow-Teller strength with calculated strength distributions for both oblate and prolate deformation, it is concluded that the ⁷⁶ Sr has strong prolate deformation in the ground state.Received: 26 June 2003, Revised: 5 November 2003, Published online: 18 June 2004PACS: 21.10.Hw Spin, parity, and isobaric spin - 23.20.Lv transitions and level energies - 23.40.Hc Relation with nuclear matrix elements and nuclear structure - 27.50. + e J. Giovinazzo: Present address: Centre d Etudes Nucléaires de Bordeaux-Gradignan, Le Haut Vigneau, F-33175 Gradignan Cedex, France.M. Ramdhane: Present address: University Mentouri, 25000 Constantine, Algeria.     

The t+n+n system and 5H

The one-proton knockout channel from 6He (240 MeV/u) impinging on a carbon target has been investigated. The triton fragments originating from this channel were detected in coincidence with the two neutrons. A broad structure, peaked at 3 MeV above the t+2n threshold, is observed in the t+n+n-relative energy spectrum. It is shown that this structure is mainly due to a I(pi)=1/2(+) resonance as expected for the 5H ground state, and from the observed angular and energy correlations, being used for the first time in 5H studies, that the neutrons to a large extent occupy the p shell.     

Halo structure of (14)Be

The two-neutron halo nucleus (14)Be has been investigated in a kinematically complete measurement of the fragments ((12)Be and neutrons) produced in dissociation at 35 MeV/nucleon on C and Pb targets. Two-neutron removal cross sections, neutron angular distributions, and invariant mass spectra were measured, and the contributions from electromagnetic dissociation (EMD) were deduced. Comparison with three-body model calculations suggests that the halo wave function contains a large nu(2s(1/2))(2) admixture. The EMD invariant mass spectrum exhibited enhanced strength near threshold consistent with a nonresonant soft-dipole excitation.     

Structure of 231Ac: Measurements of level half-lives

There is lack of knowledge of the structure of the ²³¹Ac nucleus located in the upper border of the island of octupole deformation centered around A = 225. We have populated the excited states in ²³¹Ac by beta-decay from the parent ²³¹Ra produced at ISOLDE, CERN. The low-energy structure of ²³¹Ac has been investigated by means of γ, conversion electrons, γ-γ and γ-e^- spectroscopy. We report here in the precise determination in ²³¹Ac of the half-life of the most intensively populated states by the Advanced Time Delayed ββγ(t) technique.