Electrochemistry of carbon based engineered structures

The main aims of my PhD research work have been the investigation of the redox, photophysical and electronic properties of carbon nanotubes (CNT) and their possible uses as functional substrates for the (electro)catalytic production of oxygen and as molecular connectors for Quantum-dot Molecular Automata. While for CNT many and diverse applications in electronics, in sensors and biosensors field, as a structural reinforcing in composite materials have long been proposed, the study of their properties as individual species has been for long a challenging task. CNT are in fact virtually insoluble in any solvent and, for years, most of the studies has been carried out on bulk samples (bundles). In Chapter 2 an appropriate description of carbon nanotubes is reported, about their production methods and the functionalization strategies for their solubilization. In Chapter 3 an extensive voltammetric and vis-NIR spectroelectrochemical investigation of true solutions of unfunctionalized individual single wall CNT (SWNT) is reported that permitted to determine for the first time the standard electrochemical potentials of reduction and oxidation as a function of the tube diameter of a large number of semiconducting SWNTs. We also established the Fermi energy and the exciton binding energy for individual tubes in solution and, from the linear correlation found between the potentials and the optical transition energies, one to calculate the redox potentials of SWNTs that are insufficiently abundant or absent in the samples. In Chapter 4 we report on very efficient and stable nano-structured, oxygen-evolving anodes (OEA) that were obtained by the assembly of an oxygen evolving polyoxometalate cluster, (a totally inorganic ruthenium catalyst) with a conducting bed of multiwalled carbon nanotubes (MWCNT). Here, MWCNT were effectively used as carrier of the polyoxometallate for the electrocatalytic production of oxygen and turned out to greatly increase both the efficiency and stability of the device avoiding the release of the catalysts. Our bioinspired electrode addresses the major challenge of artificial photosynthesis, i.e. efficient water oxidation, taking us closer to when we might power the planet with carbon-free fuels. In Chapter 5 a study on surface-active chiral bis-ferrocenes conveniently designed in order to act as prototypical units for molecular computing devices is reported. Preliminary electrochemical studies in liquid environment demonstrated the capability of such molecules to enter three indistinguishable oxidation states. Side chains introduction allowed to organize them in the form of self-assembled monolayers (SAM) onto a surface and to study the molecular and redox properties on solid substrates. Electrochemical studies on SAMs of these molecules confirmed their attitude to undergo fast (Nernstian) electron transfer processes generating, in the positive potential region, either the full oxidized Fc+-Fc+ or the partly oxidized Fc+-Fc species. Finally, in Chapter 6 we report on a preliminary electrochemical study of graphene solutions prepared according to an original procedure recently described in the literature. Graphene is the newly-born of carbon nanomaterials and is certainly bound to be among the most promising materials for the next nanoelectronic generation.

Crashworthiness and composite materials: development of an experimental test method for the energy absorption determination and implementation of the relative numerical model

In this PhD thesis the crashworthiness topic is studied with the perspective of the development of a small-scale experimental test able to characterize a material in terms of energy absorption. The material properties obtained are then used to validate a nu- merical model of the experimental test itself. Consequently, the numerical model, calibrated on the specific ma- terial, can be extended to more complex structures and used to simulate their energy absorption behavior. The experimental activity started at University of Washington in Seattle, WA (USA) and continued at Second Faculty of Engi- neering, University of Bologna, Forl`ı (Italy), where the numerical model for the simulation of the experimental test was implemented and optimized.

Fracture Mechanics Investigation of Structures with Defects

Fracture mechanics plays an important role in the material science, structure design and industrial production due to the failure of materials and structures are paid high attention in human activities. This dissertation, concentrates on some of the fractural aspects of shaft and composite which have being increasingly used in modern structures, consists four chapters within two parts. Chapters 1 to 4 are included in part 1. In the first chapter, the basic knowledge about the stress and displacement fields in the vicinity of a crack tip is introduced. A review involves the general methods of calculating stress intensity factors are presented. In Chapter 2, two simple engineering methods for a fast and close approximation of stress intensity factors of cracked or notched beams under tension, bending moment, shear force, as well as torque are presented. New formulae for calculating the stress intensity factors are proposed. One of the methods named Section Method is improved and applied to the three dimensional analysis of cracked circular section for calculating stress intensity factors. The comparisons between the present results and the solutions calculated by ABAQUS for single mode and mixed mode are studied. In chapter 3, fracture criteria for a crack subjected to mixed mode loading of two-dimension and three-dimension are reviewed. The crack extension angle for single mode and mixed mode, and the critical loading domain obtained by SEDF and MTS are compared. The effects of the crack depth and the applied force ratio on the crack propagation angle and the critical loading are investigated. Three different methods calculating the crack initiation angle for three-dimension analysis of various crack depth and crack position are compared. It should be noted that the stress intensity factors used in the criteria are calculated in section 2.1.