Corrosion on prehistoric Cu–Sn-alloys: the influence of artificial environment and storage

The paper contributes to the identification of different corrosion products detected on the cross-section specimens sampled from Bronze Age swords and one helmet found between 60–160 years ago. The objects are kept in 1889 built oak showcases at the Natural History Museum Vienna, having suffered unknown restoration treatments. The identified corrosion products not only affect further eventual treatment in conservation science of copper base objects but also contribute to identify the often unknown find context, which is meant to facilitate archaeological interpretation of the Bronze Age weapons. The analyses of the samples were carried out using SEM-EDXS-EBSD and optical microscopy.     

On the nonlinear effects of the mean wind force on the galloping onset in shallow cables

Nonlinear Dynamics - The critical aeroelastic behavior of horizontal, suspended, and shallow cables is analyzed via a continuous model accounting for both external and internal damping....     

Glass–metal objects from archaeological excavation: corrosion study

This paper contributes to the investigations on history, technology, and degradation of middle age objects (metallic rings with mounted glass beads) recently excavated under the Main Square in Krakow (Poland). Moreover, they were discovered in soil layers differing by chemical composition and microclimate parameters. Historical material is indeed very limited in terms of quantity and sample size, and the following nondestructive analyses were applied: scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS), X-ray diffraction (XRD), and X-ray fluorescence spectroscopy (XRF). The glass and the metal were separately tested. Metallography on cross-sections (by both optical and scanning electron microscopy) was applied only on microfragments sampled from metallic rings. The achieved results pointed out how the local microclimate affected the degradation of the analyzed rings developing locally different corrosion processes. Each tested glass of “ring eye” shows a specific chemical composition. All glass pieces were covered by silica gel, and locally more advanced corrosion has been found.     

Tuning the photophysical properties of pyrene-based systems: a theoretical study

Recently new molecular systems based on the pyrene moiety were developed for photovoltaic applications. Here we present the results of a quantum chemical study focused on the effects induced by some different substituents on the electronic properties of pyrene, to obtain general hints for the molecular design of new pyrene-based systems. In particular, a series of electron-donating (hydroxy, amino, acetylamino) and electron-withdrawing (cyano, carbamoyl, formyl, ethynyl, ethenyl) groups were considered. Furthermore, in addition to the single pyrene molecule, two pyrene units linked by ethenylene, ethynylene, 2,5-thienylene, and ethynylene-p-phenylene containing chains of different lengths were taken into account. For all of the model structures presented, the ground state geometries have been optimized using the density functional approach, while the vertical transition energies were calculated using the time-dependent density functional theory. We will show that the tuning of the lowest electronic excitation energy (i.e., the HOMO-LUMO energy gap) as well as the localization of the spatial distributions of the frontier molecular orbitals (i.e., the nature of the electron-hole pair, generated by photon absorption) can be obtained through the analysis of the pyrene frontier molecular orbitals. This approach allows to evaluate the most suitable position of the substituents on the pyrene moiety giving rise to enhanced electronic effects also in function of their electronic nature. In this way, pyrene-structures with tailored electronic properties could be modeled. Our screening shows that promising candidates for photovoltaic applications could be molecular structures formed by two pyrene units joined/linked by a short conjugated bridge containing double or triple bonds (henceforth pyrene-linked dimers). As far as the single pyrene units are considered, the most significant reduction of the transition energy of the lowest optical electronic excitation is obtained with disubstituted pyrenes with push-pull character.     

Advances in stability,bifurcations and nonlinear vibrations in mechanical systems

Nonlinear Dynamics -     

Postcritical Behavior of Cables Undergoing Two Simultaneous Galloping Modes

Abstract. A nonlinear two degree-of-freedom model, describing a flexible elastic suspended cable undergoing galloping oscillations, is analyzed. By using a perturbative approach, the critical conditions occuring for different values of the aerodynamic coefficients are described. Two different type of critical conditions, corresponding to simple or double Hopf bifurcations are found. The nonlinear postcritical behavior of single taut strings in 1:1 primary internal resonance is studied through the multiple scale perturbation method. In the double Hopf bifurcation case the influence of the detuning between the critical eigenvalues on the postcritical behavior is illustrated. It is found that quasi-periodic motions, which are likely to occur in the linear field when the two critical frequencies are incommensurable, are really unstable in the nonlinear range. Therefore, the postcritical behavior of the string consists of stable periodic motions for any detuning values.Sommario. Viene analizzato un modello non lineare a due gradi di libertrappresentativo di un cavo elastico flessibile sospeso alle estremite soggetto ad oscillazioni galoppanti. Utilizzando un approccio perturbativo, vengono descritte le condizioni critiche per differenti valori dei coefficienti aerodinamici. Sono presenti due diversi tipi di condizioni critiche, corrispondenti a biforcazioni di Hopf semplici e doppie. Attraverso il metodo perturbativo delle scale multiple viene studiato il comportamento post-critico non lineare di singole stringhe tese in risonanza interna primaria 1:1. Nel caso di biforcazione doppia di Hopf viene illustrata l'influenza del detuning tra gli autovalori critici sul comportamento post-critico. Si trova che i moti quasi-periodici, presenti in campo lineare quando le due frequenze critiche sono incommensurabili, sono in realtinstabili in campo non lineare. Quindi, il comportamento post-critico della stringa risulta composto da moti periodici stabili per un qualsiasi valore del detuning.     

Influence of environment on the corrosion of glass–metal connections

‘Glass sensors’ of the eighteenth century Backer glass and the sixteenth century enamel from Limoges have been chosen for a series of experiments. Combinations of these materials with different base materials such as copper and bronze has been investigated. To create surface changes on the ‘glass sensor’, a corrosion process was induced in a controlled environment. A variety of corrosive agents such as hydrochloric acid, sulfuric acid, water and formaldehyde were used. The sample immersed in the corrosive solution was exposed alternately to light and high temperature for a total of 38 weeks. During this period, macroscopic and microscopic observations were made and series of tests such as SEM/EDS and Raman spectroscopy were performed on the surface of the samples. ICP-MS methods were used to determine the change in the chemical composition of the solutions where the samples had corroded. The primary aim of this study was to identify the impact of a number of external corrosive variables such as temperature, humidity and local environment to identify the most damaging environments for glass–metal objects. The obtained results showed the chemical and physical phenomena acting on the surface of the glass, metal or in the place of their joints. Information obtained on this study was used to explain the influence of the environment on the surface of glass–metal materials. Results can be used in the design of conservation work as well as for sustainable conservation.