3D molecular imaging SIMS

Thin monolayer and bilayer films of spin cast poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), poly(lactic) acid (PLA) and PLA doped with several pharmaceuticals have been analyzed by dynamic SIMS using SF₅⁺ polyatomic primary ion bombardment. Each of these systems exhibited minimal primary beam-induced degradation under cluster ion bombardment allowing molecular depth profiles to be obtained through the film. By combing secondary ion imaging with depth profiling, three-dimensional molecular image depth profiles have been obtained from these systems. In another approach, bevel cross-sections are cut in the samples with the SF₅⁺ primary ion beam to produce a laterally magnified cross-section of the sample that does not contain the beam-induced damage that would be induced by conventional focussed ion beam (FIB) cross-sectioning. The bevel surface can then be examined using cluster SIMS imaging or other appropriate microanalysis technique.     

Determination of Hydrogen Single Ion Activity Coefficients in Aqueous HCl Solutions at 25°C

The single ion activity coefficients of hydrogen and chloride ions in aqueous HCl solutions have been estimated at 25°C at concentrations up to 1 mol-kg^–1, using potentiometric measurements with ion-selective electrodes and appropriate calibration procedures. Two methods are described for an internal calibration of the electrodes in the extended Debye–Hückel concentration range. The results are compared to the conventional pH calibration with external buffer solutions. Since the latter calibration method does not account for the liquid junction potential E _J which arises at the reference electrode, the resulting activity coefficients are quite different in HCl solutions of higher concentration. These differences between internal and external calibration decrease significantly, when a correction for E _J is introduced into the conventional pH calibration. Hence, in solutions of higher ionic strength the accuracy of the conventional pH electrode calibration using buffer solutions is very limited, when exact H⁺ activities are required. The consistency of the results indicates that the liquid junction potentials in the examined systems calculated by the Henderson/Bates approximation are of reasonable precision.     

Time-scale and excitation energy partition in sequential binary decays induced by heavy-ion collisions at ≃6 MeV·A

We studied the sequential binary decay of the systems ³²S+⁴⁵Sc, ⁷⁶Ge, ⁸⁹Y, ⁵⁹Co, ⁶³Cu and ¹⁹F+⁶³Cu induced by collisions at ≃6 MeV·A. The two stages of the process have reaction-times compatible with the dynamics of different mechanisms. The study of the excitation energy partition shows that the reaction mechanism of the first step has influence on the de-excitation of the primary fragments producing two decay components which have different time scale. Received: 25 March 1997 / Revised version: 2 December 1997     

A193Ir Mössbauer study of Pt−Ir catalysts prepared by impregnantion of silica with H2MCl6

The state of iridium on Pt?Ir catalysts prepared by impregnation of amorphous silica with H₂IrCl₆ and H₂PtCl₆ was studied by¹⁹³Ir Mössbauer spectroscopy after different steps of preparation. The Ir is adsorbed in its trivalent state, presumably as [IrCl₆]^3?. Calcination in air at 450°C converts this to IrO₂. The metallic clusters formed by subsequent reduction in H₂ at 200°C show a strong tendency towards segregation of Ir and Pt and re-oxidize partially when exposed to air at ambient temperature. In both respects the behaviour is similar to that of samples prepared by co-exchange from [Ir(NH₃)₅Cl]Cl₂ and Pt(NH₃)₄Cl₂. H₂O.