F. Lo Celso

Composition and corrosion phases of Etruscan Bronzes from Villanovan Age

A neutron diffraction (ND) and neutron tomography (NT) study of laminated ancient bronzes was performed at the ISIS (Rutherford Appleton Laboratory, UK) neutron source and at the BENSC reactor (Hahn-Meitner Institut, Germany). The samples are part of an 8th century BC Etruscan collection discovered in the necropolises of Osteria-Poggio Mengarelli and Cavalupo in the Vulci area (Viterbo, Italy). The study allowed us to derive—in a totally non-destructive manner—information related to the main composition of the objects, possible presence of alterations and their nature, crusts and inclusions, as well as structure of the bulk. The presence of some components is linked to a variety of questions such as the correct determination of the historical and cultural timeframe, place and method of production, technologies adopted and conditions for restoration and preservation. Moreover, the data analysis of corrosion products provides information about the past environments and the physical/chemical events that transformed the objects into a partially corroded matrix.

Study of percolation and clustering in supercritical water-CO2 mixtures

The microscopic structure of supercritical water-CO(2) mixture is investigated by neutron diffraction experiments exploiting the isotopic HD substitution. The investigated water reach mixtures are in the liquidlike region of the phase diagram, according to the behavior of the radial distribution functions, yet a reduction of the average number of hydrogen bonds, compared to equivalent states of pure water, is found. As a consequence, the average dimension of water clusters is reduced and the system stays below the percolation threshold. These results, along with the shift of the main peaks of the site-site radial distribution functions, suggest that the excess volume in these supercritical mixtures is likely associated with the CO(2) solvation shell.

Structural and dynamical characterization of melt PEO–salt mixtures

Salt doped poly ethylene oxide (PEO) mixtures were investigated by means of both small angle neutron scattering and QENS techniques aiming to characterize morphological and dynamical features in the melt state. These experimental evidences provide support to the proposed heterogeneous scenario for polymer electrolytes. In particular, the existence of PEO–cation complexes is proposed to play a major role in intramolecular cooperation and intermolecular transient crosslinks, which affects the mixture properties.

Scattering studies of large scale structures at the ultra small angle neutron scattering instrument S18

In recent years ultra small angle neutron scattering (USANS) has developed into a powerful standard method for large scale structure investigations. The upgraded instrument S18 at the ILLs 58MW high flux reactor is operated routinely with increasing beam time demand. The performance of the instrument and its abilities will be discussed in this paper. A peak to background ratio better than 105 is reached using Agamalians tail reduction method. A q-range from 2.10−5 up to 5.10−2A−1 can be covered. This allows a clear overlap with standard pinhole SANS instruments. The new way collecting scattering data logarithmically equidistant in q-space saves measuring time. This allows measuring times of about 1.5h for strong scattering specimens with reasonable statistics. We will present an overview of recent experiments which have been performed in co-operation with different groups from the international user community. This work comprises of structure investigations of petroliferous sedimentary rocks showing fractal scattering behaviour and time resolved USANS studies of the dynamics of hydration of cement paste. Concerning soft matter structures, Pirelli rubber nanocomposites have been investigated. In addition, time resolved measurement on a D2O solution of a PPO–PEO–PPO block copolymer (Reverse Pluronic 25R5) and the dynamics of phase separation of methyl-hydroxy-propyl cellulose (MHPC) have been studied using a sample temperature control system.

Kinetics of block-copolymer aggregation in super critical CO2

Small angle X-ray and neutron scattering (SAXS and SANS) are used to obtain structural information on the aggregation behavior of block-copolymers dissolved in supercritical CO2. The SANS technique is used to provide a detailed structural model for the micellar aggregates, which form below the critical micellization density (CMD), that we defined in our previous work. The SAXS technique (with a synchrotron source) is used to provide the first experimental information concerning the kinetic features of both formation and decomposition of such aggregates as soon as pressure jumps are applied to the solutions across the CMD. 2002 Elsevier Science B.V. All rights reserved.

Neutron tomography of ancient lead artefacts

The investigations presented here show the results of an epigraphic analysis on ancient Roman lead ingots rescued from shipwrecks along the coast of Sicily (Italy) by means of Neutron Tomography (NT). The artefacts, including a lead horn, can be dated back to a period between the 3rd and 1st century BC. The three dimensional NT reconstructions helped the decipherment of hidden signs and partially visible details on the severely damaged objects. The findings obtained using the non-destructive procedure allowed us also to reach plausible conclusions in the context of the known commercial routes.

Pressure-induced formation of diblock copolymer “micelles” in supercritical fluids. A combined study by small angle scattering experiments and mean-field theory. II. Kinetics of the unimer–aggregate transition

We developed a simple time-dependent mean-field theory to describe the phase separation kinetics of either homopolymers or AB-diblock copolymers in supercritical (SC) fluids. The model, previously used to describe the phase behavior of AB-block copolymers under the assumption of strong solvent selectivity for just one copolymer chain, has been extended to study the kinetics of the phase separation process. Time resolved small angle x-ray scattering (TR-SAXS) measurements have been performed on different AB-diblock copolymers containing a perfluorinated chain and dissolved in SC-CO2. The data obtained over a wide range of pressure and temperature confirm our theoretical predictions. Particularly interesting is the presence of two relaxation frequencies for the homogeneous solution --> spherical aggregate transition, where the two relaxation processes depend on the depth of the pressure jump and on temperature. The whole phenomenon could be explained as an initial SC solvent/polymer phase separation followed by a slow reorientation process to form spherical aggregates driven by the copolymer solvophilic moiety.

Pressure-induced formation of diblock copolymer “micelles” in supercritical fluids. A combined study by small angle scattering experiments and mean-field theory. I. The critical micellization density concept

We developed a simple mean-field theory to describe polymer and AB diblock copolymer phase separation in supercritical (SC) fluids. The highly compressible SC fluid has been described by using a phenomenological hole theory, properly extended to consider the solvent/polymer/vacancy pseudoternary mixture. The model has been applied to describe the phase behavior of AB-diblock copolymers under the assumption of a strong solvent selectivity for just one copolymer chain. In our model the solvent selectivity is a strong function of the external pressure because in compressible fluids vacancies reduce the number of favorable solvent-polymer contacts. The combined effect of the pressure on the average solvent quality and selectivity for a single polymer chain makes the phase behavior of a diblock copolymer in SC fluids quite complex. Small angle neutron and x-ray scattering (SANS and SAXS) measurements have been performed on SC-CO2 solutions of different AB-diblock copolymers containing a perfluorinated chain. The data obtained over a wide range of pressure and temperature confirm our theoretical predictions.

Dilute and semi dilute solutions of block copolymers in water, near-critical and super-critical CO2: a small angle scattering study of the monomer–aggregate transition

Small angle neutron (SANS) and X-ray (SAXS) Scattering measurements on aggregate formation of block copolymers in water and in near-critical and supercritical CO2 are reported here. Time Resolved SAXS (TR-SAXS) has also been performed in the supercritical region. Experiments have been carried out for a series of different thermodynamic conditions, changing the solvent density by profiling the pressure at constant temperature. A sharp transition between monomers dissolved as random coils and micelles characterized by a solvo-philic shell and a solvo-phobic core occurs when the solvent density reaches the critical micellization value. This is easily shown in the case of scCO2.

Nanoscale organization in the fluorinated room temperature ionic liquid: Tetraethyl ammonium (trifluoromethanesulfonyl)(nonafluorobutylsulfonyl)imide

Fluorinated Room Temperature Ionic Liquids (FRTILs) are a branch of ionic liquids that is the object of growing interest for a wide range of potential applications, due to the synergic combination of specifically ionic features and those properties that stem from fluorous tails. So far limited experimental work exists on the micro- and mesoscopic structural organization in this class of compounds. Such a work is however necessary to fully understand morphological details at atomistic level that would have strong implications in terms of bulk properties. Here we use the synergy between X-ray and neutron scattering together with molecular dynamics simulations to access structural details of a technologically relevant FRTIL that is characterised by an anion bearing a long enough fluorinated tail to develop specific morphological features. In particular, we find the first experimental evidence that in FRTILs bearing an asymmetric bis(perfluoroalkyl)sulfonyl-imide anion, fluorous side chains tend to be spatially segregated into nm-scale spatial heterogeneities. This feature together with the well-established micro-segregation of side alkyl chains in conventional RTILs leads to the concept of triphilic ILs, whose technological applications are yet to be fully developed.