Application of FTIR microscopy to cultural heritage materials

Research in art conservation has been developed from the early 1950s, giving a significant contribution to the conservation-restoration of cultural heritage artefacts. In fact, only through a profound knowledge about the nature and conditions of constituent materials, suitable decisions on the conservation and restoration measures can thus be adopted and preservation practices enhanced. The study of ancient artworks is particularly challenging as they can be considered as heterogeneous and multilayered systems where numerous interactions between the different components as well as degradation and ageing phenomena take place. However, difficulties to physically separate the different layers due to their thickness (1-200 µm) can result in the inaccurate attribution of the identified compounds to a specific layer. Therefore, details can only be analysed when the sample preparation method leaves the layer structure intact, as for example the preparation of embedding cross sections in synthetic resins. Hence, spatially resolved analytical techniques are required not only to exactly characterize the nature of the compounds but also to obtain precise chemical and physical information about ongoing changes. This thesis focuses on the application of FTIR microspectroscopic techniques for cultural heritage materials. The first section is aimed at introducing the use of FTIR microscopy in conservation science with a particular attention to the sampling criteria and sample preparation methods. The second section is aimed at evaluating and validating the use of different FTIR microscopic analytical methods applied to the study of different art conservation issues which may be encountered dealing with cultural heritage artefacts: the characterisation of the artistic execution technique (chapter II-1), the studies on degradation phenomena (chapter II-2) and finally the evaluation of protective treatments (chapter II-3). The third and last section is divided into three chapters which underline recent developments in FTIR spectroscopy for the characterisation of paint cross sections and in particular thin organic layers: a newly developed preparation method with embedding systems in infrared transparent salts (chapter III-1), the new opportunities offered by macro-ATR imaging spectroscopy (chapter III-2) and the possibilities achieved with the different FTIR microspectroscopic techniques nowadays available (chapter III-3). In chapter II-1, FTIR microspectroscopy as molecular analysis, is presented in an integrated approach with other analytical techniques. The proposed sequence is optimized in function of the limited quantity of sample available and this methodology permits to identify the painting materials and characterise the adopted execution technique and state of conservation. Chapter II-2 describes the characterisation of the degradation products with FTIR microscopy since the investigation on the ageing processes encountered in old artefacts represents one of the most important issues in conservation research. Metal carboxylates resulting from the interaction between pigments and binding media are characterized using synthesised metal palmitates and their production is detected on copper-, zinc-, manganese- and lead- (associated with lead carbonate) based pigments dispersed either in oil or egg tempera. Moreover, significant effects seem to be obtained with iron and cobalt (acceleration of the triglycerides hydrolysis). For the first time on sienna and umber paints, manganese carboxylates are also observed. Finally in chapter II-3, FTIR microscopy is combined with further elemental analyses to characterise and estimate the performances and stability of newly developed treatments, which should better fit conservation-restoration problems. In the second part, in chapter III-1, an innovative embedding system in potassium bromide is reported focusing on the characterisation and localisation of organic substances in cross sections. Not only the identification but also the distribution of proteinaceous, lipidic or resinaceous materials, are evidenced directly on different paint cross sections, especially in thin layers of the order of 10 µm. Chapter III-2 describes the use of a conventional diamond ATR accessory coupled with a focal plane array to obtain chemical images of multi-layered paint cross sections. A rapid and simple identification of the different compounds is achieved without the use of any infrared microscope objectives. Finally, the latest FTIR techniques available are highlighted in chapter III-3 in a comparative study for the characterisation of paint cross sections. Results in terms of spatial resolution, data quality and chemical information obtained are presented and in particular, a new FTIR microscope equipped with a linear array detector, which permits reducing the spatial resolution limit to approximately 5 µm, provides very promising results and may represent a good alternative to either mapping or imaging systems.

MCAO for Extremely Large Telescopes: the cases of LBT and E-ELT

Several MCAO systems are under study to improve the angular resolution of the current and of the future generation large ground-based telescopes (diameters in the 8-40 m range). The subject of this PhD Thesis is embedded in this context. Two MCAO systems, in dierent realization phases, are addressed in this Thesis: NIRVANA, the 'double' MCAO system designed for one of the interferometric instruments of LBT, is in the integration and testing phase; MAORY, the future E-ELT MCAO module, is under preliminary study. These two systems takle the sky coverage problem in two dierent ways. The layer oriented approach of NIRVANA, coupled with multi-pyramids wavefront sensors, takes advantage of the optical co-addition of the signal coming from up to 12 NGS in a annular 2' to 6' technical FoV and up to 8 in the central 2' FoV. Summing the light coming from many natural sources permits to increase the limiting magnitude of the single NGS and to improve considerably the sky coverage. One of the two Wavefront Sensors for the mid- high altitude atmosphere analysis has been integrated and tested as a stand- alone unit in the laboratory at INAF-Osservatorio Astronomico di Bologna and afterwards delivered to the MPIA laboratories in Heidelberg, where was integrated and aligned to the post-focal optical relay of one LINC-NIRVANA arm. A number of tests were performed in order to characterize and optimize the system functionalities and performance. A report about this work is presented in Chapter 2. In the MAORY case, to ensure correction uniformity and sky coverage, the LGS-based approach is the current baseline. However, since the Sodium layer is approximately 10 km thick, the articial reference source looks elongated, especially when observed from the edge of a large aperture. On a 30-40 m class telescope, for instance, the maximum elongation varies between few arcsec and 10 arcsec, depending on the actual telescope diameter, on the Sodium layer properties and on the laser launcher position. The centroiding error in a Shack-Hartmann WFS increases proportionally to the elongation (in a photon noise dominated regime), strongly limiting the performance. To compensate for this effect a straightforward solution is to increase the laser power, i.e. to increase the number of detected photons per subaperture. The scope of Chapter 3 is twofold: an analysis of the performance of three dierent algorithms (Weighted Center of Gravity, Correlation and Quad-cell) for the instantaneous LGS image position measurement in presence of elongated spots and the determination of the required number of photons to achieve a certain average wavefront error over the telescope aperture. An alternative optical solution to the spot elongation problem is proposed in Section 3.4. Starting from the considerations presented in Chapter 3, a first order analysis of the LGS WFS for MAORY (number of subapertures, number of detected photons per subaperture, RON, focal plane sampling, subaperture FoV) is the subject of Chapter 4. An LGS WFS laboratory prototype was designed to reproduce the relevant aspects of an LGS SH WFS for the E-ELT and to evaluate the performance of different centroid algorithms in presence of elongated spots as investigated numerically and analytically in Chapter 3. This prototype permits to simulate realistic Sodium proles. A full testing plan for the prototype is set in Chapter 4.

Image analysis in the morphological and morphometric study of teeth

The subject of this doctoral dissertation concerns the definition of a new methodology for the morphological and morphometric study of fossilized human teeth, and therefore strives to provide a contribution to the reconstruction of human evolutionary history that proposes to extend to the different species of hominid fossils. Standardized investigative methodologies are lacking both regarding the orientation of teeth subject to study and in the analysis that can be carried out on these teeth once they are oriented. The opportunity to standardize a primary analysis methodology is furnished by the study of certain early Neanderthal and preneanderthal molars recovered in two caves in southern Italy [Grotta Taddeo (Taddeo Cave) and Grotta del Poggio (Poggio Cave), near Marina di Camerata, Campania]. To these we can add other molars of Neanderthal and modern man of the upper Paleolithic era, specifically scanned in the paleoanthropology laboratory of the University of Arkansas (Fayetteville, Arkansas, USA), in order to increase the paleoanthropological sample data and thereby make the final results of the analyses more significant. The new analysis methodology is rendered as follows: 1. Standardization of an orientation system for primary molars (superior and inferior), starting from a scan of a sample of 30 molars belonging to modern man (15 M1 inferior and 15 M1 superior), the definition of landmarks, the comparison of various systems and the choice of a system of orientation for each of the two dental typologies. 2. The definition of an analysis procedure that considers only the first 4 millimeters of the dental crown starting from the collar: 5 sections parallel to the plane according to which the tooth has been oriented are carried out, spaced 1 millimeter between them. The intention is to determine a method that allows for the differentiation of fossilized species even in the presence of worn teeth. 3. Results and Conclusions. The new approach to the study of teeth provides a considerable quantity of information that can better be evaluated by increasing the fossil sample data. It has been demonstrated to be a valid tool in evolutionary classification that has allowed (us) to differentiate the Neanderthal sample from that of modern man. In a particular sense the molars of Grotta Taddeo, which up until this point it has not been possible to determine with exactness their species of origin, through the present research they are classified as Neanderthal.

Path planning for image based visual servoing

This thesis deals with Visual Servoing and its strictly connected disciplines like projective geometry, image processing, robotics and non-linear control. More specifically the work addresses the problem to control a robotic manipulator through one of the largely used Visual Servoing techniques: the Image Based Visual Servoing (IBVS). In Image Based Visual Servoing the robot is driven by on-line performing a feedback control loop that is closed directly in the 2D space of the camera sensor. The work considers the case of a monocular system with the only camera mounted on the robot end effector (eye in hand configuration). Through IBVS the system can be positioned with respect to a 3D fixed target by minimizing the differences between its initial view and its goal view, corresponding respectively to the initial and the goal system configurations: the robot Cartesian Motion is thus generated only by means of visual informations. However, the execution of a positioning control task by IBVS is not straightforward because singularity problems may occur and local minima may be reached where the reached image is very close to the target one but the 3D positioning task is far from being fulfilled: this happens in particular for large camera displacements, when the the initial and the goal target views are noticeably different. To overcame singularity and local minima drawbacks, maintaining the good properties of IBVS robustness with respect to modeling and camera calibration errors, an opportune image path planning can be exploited. This work deals with the problem of generating opportune image plane trajectories for tracked points of the servoing control scheme (a trajectory is made of a path plus a time law). The generated image plane paths must be feasible i.e. they must be compliant with rigid body motion of the camera with respect to the object so as to avoid image jacobian singularities and local minima problems. In addition, the image planned trajectories must generate camera velocity screws which are smooth and within the allowed bounds of the robot. We will show that a scaled 3D motion planning algorithm can be devised in order to generate feasible image plane trajectories. Since the paths in the image are off-line generated it is also possible to tune the planning parameters so as to maintain the target inside the camera field of view even if, in some unfortunate cases, the feature target points would leave the camera images due to 3D robot motions. To test the validity of the proposed approach some both experiments and simulations results have been reported taking also into account the influence of noise in the path planning strategy. The experiments have been realized with a 6DOF anthropomorphic manipulator with a fire-wire camera installed on its end effector: the results demonstrate the good performances and the feasibility of the proposed approach.

Detailed study of the seismotectonic setting in the Lucanian Apennines and surrounding areas (Southern Italy)

In this research work I analyzed the instrumental seismicity of Southern Italy in the area including the Lucanian Apennines and Bradano foredeep, making use of the most recent seismological database available so far. I examined the seismicity occurred during the period between 2001 and 2006, considering 514 events with magnitudes M ≥ 2.0. In the first part of the work, P- and S-wave arrival times, recorded by the Italian National Seismic Network (RSNC) operated by the Istituto Nazionale di Geofisica e Vulcanologia (INGV), were re-picked along with those of the SAPTEX temporary array (2001–2004). For some events located in the Upper Val d'Agri, I also used data from the Eni-Agip oil company seismic network. I computed the VP/VS ratio obtaining a value of 1.83 and I carried out an analysis for the one-dimensional (1D) velocity model that approximates the seismic structure of the study area. After this preliminary analysis, making use of the records obtained in the SeSCAL experiment, I incremented the database by handpicking new arrival times. My final dataset consists of 15,666 P- and 9228 S-arrival times associated to 1047 earthquakes with magnitude ML ≥ 1.5. I computed 162 fault-plane solutions and composite focal mechanisms for closely located events. I investigated stress field orientation inverting focal mechanism belonging to the Lucanian Apennine and the Pollino Range, both areas characterized by more concentrated background seismicity. Moreover, I applied the double difference technique (DD) to improve the earthquake locations. Considering these results and different datasets available in the literature, I carried out a detailed analysis of single sub-areas and of a swarm (November 2008) recorded by SeSCAL array. The relocated seismicity appears more concentrated within the upper crust and it is mostly clustered along the Lucanian Apennine chain. In particular, two well-defined clusters were located in the Potentino and in the Abriola-Pietrapertosa sector (central Lucanian region). Their hypocentral depths are slightly deeper than those observed beneath the chain. I suggest that these two seismic features are representative of the transition from the inner portion of the chain with NE-SW extension to the external margin characterized by dextral strike-slip kinematics. In the easternmost part of the study area, below the Bradano foredeep and the Apulia foreland, the seismicity is generally deeper and more scattered and is associated to the Murge uplift and to the small structures present in the area. I also observed a small structure NE-SW oriented in the Abriola-Pietrapertosa area (activated with a swarm in November 2008) that could be considered to act as a barrier to the propagation of a potential rupture of an active NW-SE striking faults system. Focal mechanisms computed in this study are in large part normal and strike-slip solutions and their tensional axes (T-axes) have a generalized NE-SW orientation. Thanks to denser coverage of seismic stations and the detailed analysis, this study is a further contribution to the comprehension of the seismogenesis and state of stress of the Southern Apennines region, giving important contributions to seismotectonic zoning and seismic hazard assessment.