Materiali ceramici a struttura Aurivillius per la produzione di solar fuels

Solar fuels from CO2 is a topic of current large scientific and industrial interest. In particular, photo-electrochemical cells (PECs) represent today one of the most promising technology for storing sun energy as chemical bonds exploiting carbon dioxide as starting reagent. In this thesis, the possibility of using Aurivillius-type compounds for the production of solar fuels was deeply investigated. Aurivillius-type perovskites, with general formula Bi(n+1)Fe(n-3)Ti3O(3n+3), were synthesized and fully characterized to study the influence of the number of perovskite layers as well as of the synthesis parameters onto their final properties. In particular, 8 different systems were considered increasing the amount of iron and, as a consequence, the number of perovskite layers. These compounds were synthesized through a standard solid-state reaction method as well as via a sol-gel technique and characterized by XRD, SEM and BET analyses. The band gap value and the photocatalytic activity towards Rhodamine B decomposition were assessed as well. For each system, a screen-printing ink was formulated to be deposited as photo-electrodes onto transparent conducting supports. The photo-electrodes were morphologically characterized by XRD and SEM analysis, and their electrochemical properties (cyclic and linear voltammetry, EIS, Mott-Schottky analysis) were determined. Finally, the most promising materials were tested as photo-cathode inside PEC cell under different illumination conditions, to quantify their ability to convert CO2. The obtained results show the potentiality of Aurivillius-type compounds as innovative material for carbon dioxide photo-electrochemical reduction.

Evaluation of a 2D multileader training system for improving sustainability and precision orchard management applications in italian apple orchards

The presented study aimed to evaluate the productive and physiological behavior of a 2D multileader apple training systems in the Italian environment both investigating the possibility to increase yield and precision crop load management resolution. Another objective was to find valuable thinning thresholds guaranteeing high yields and matching fruit market requirements. The thesis consists in three studies carried out in a Pink Lady®- Rosy Glow apple orchard trained as a planar multileader training system (double guyot). Fruiting leaders (uprights) dimension, crop load, fruit quality, flower and physiological (leaf gas exchanges and fruit growth rate) data were collected and analysed. The obtained results found that uprights present dependence among each other and as well as a mutual support during fruit development. However, individual upright fruit load and upright’s fruit load distribution on the tree (~ plant crop load) seems to define both upright independence from the other, and single upright crop load effects on the final fruit quality production. Correlations between fruit load and harvest fruit size were found and thanks to that valuable thinning thresholds, based on different vegetative parameters, were obtained. Moreover, it comes out that an upright’s fruit load random distribution presents a widening of those thinning thresholds, keeping un-altered fruit quality. For this reason, uprights resulted a partially physiologically-dependent plant unit. Therefore, if considered and managed as independent, then no major problems on final fruit quality and production occurred. This partly confirmed the possibility to shift crop load management to single upright. The finding of the presented studies together with the benefits coming from multileader planar training systems suggest a high potentiality of the 2D multileader training systems to increase apple production sustainability and profitability for Italian apple orchard, while easing the advent of automation in fruit production.

Numerical and experimental analysis of 3D printed smart structures and systems

Three dimensional (3D) printers of continuous fiber reinforced composites, such as MarkTwo (MT) by Markforged, can be used to manufacture such structures. To date, research works devoted to the study and application of flexible elements and CMs realized with MT printer are only a few and very recent. A good numerical and/or analytical tool for the mechanical behavior analysis of the new composites is still missing. In addition, there is still a gap in obtaining the material properties used (e.g. elastic modulus) as it is usually unknown and sensitive to printing parameters used (e.g. infill density), making the numerical simulation inaccurate. Consequently, the aim of this thesis is to present several work developed. The first is a preliminary investigation on the tensile and flexural response of Straight Beam Flexures (SBF) realized with MT printer and featuring different interlayer fiber volume-fraction and orientation, as well as different laminate position within the sample. The second is to develop a numerical analysis within the Carrera' s Unified Formulation (CUF) framework, based on component-wise (CW) approach, including a novel preprocessing tool that has been developed to account all regions printed in an easy and time efficient way. Among its benefits, the CUF-CW approach enables building an accurate database for collecting first natural frequencies modes results, then predicting Young' s modulus based on an inverse problem formulation. To validate the tool, the numerical results are compared to the experimental natural frequencies evaluated using a digital image correlation method. Further, we take the CUF-CW model and use static condensation to analyze smart structures which can be decomposed into a large number of similar components. Third, the potentiality of MT in combination with topology optimization and compliant joints design (CJD) is investigated for the realization of automated machinery mechanisms subjected to inertial loads.

PCM-based in-memory computing: architectures, circuits and applications

Analog In-memory Computing (AIMC) has been proposed in the context of Beyond Von Neumann architectures as a valid strategy to reduce internal data transfers energy consumption and latency, and to improve compute efficiency. The aim of AIMC is to perform computations within the memory unit, typically leveraging the physical features of memory devices. Among resistive Non-volatile Memories (NVMs), Phase-change Memory (PCM) has become a promising technology due to its intrinsic capability to store multilevel data. Hence, PCM technology is currently investigated to enhance the possibilities and the applications of AIMC. This thesis aims at exploring the potential of new PCM-based architectures as in-memory computational accelerators. In a first step, a preliminar experimental characterization of PCM devices has been carried out in an AIMC perspective. PCM cells non-idealities, such as time-drift, noise, and non-linearity have been studied to develop a dedicated multilevel programming algorithm. Measurement-based simulations have been then employed to evaluate the feasibility of PCM-based operations in the fields of Deep Neural Networks (DNNs) and Structural Health Monitoring (SHM). Moreover, a first testchip has been designed and tested to evaluate the hardware implementation of Multiply-and-Accumulate (MAC) operations employing PCM cells. This prototype experimentally demonstrates the possibility to reach a 95% MAC accuracy with a circuit-level compensation of cells time drift and non-linearity. Finally, empirical circuit behavior models have been included in simulations to assess the use of this technology in specific DNN applications, and to enhance the potentiality of this innovative computation approach.

Biopolyester fibers for sustainable and biocompatible applications

The rising of concerns around the scarcity of non-renewable resources has raised curiosity around new frontiers in the polymer science field. Biopolymers is a general term describing different kind of polymers that are linked with the biological world because of either monomer derivation, end of life degradation or both. The current work is aimed at studying one example of both biopolymers types. Polyhydroxibutyrate (P3HB) is a biodegradable microbial-produced polymer which holds massive potentiality as a substitute of polyolefins such as polypropylene. Though, its highly crystalline nature and stereoregularity of structure make it difficult to work with. The project P3HB-Mono take advantage of polarized Raman spectroscopy to see how annealing of chains with different weights influence the crystallinity and molecular structure of the polymer, eventually reflecting on its mechanical properties. The technique employed is also optimal in order to see how mesophase, a particular conformation of chains different from crystalline and amorphous phase, develops in the polymer structure and changes depending on temperature and mechanical stress applied to the fiber. Polycaprolactone (PCL) on the other hand is a biodegradable fossil-fuel polymer which has biocompatibility and bio-resorbability features. As a consequence this material is very appealing for medical industry and can be used for different applications in this field. One interesting option is to produce narrow and long liquid filled fibers for drug delivery inside human body, using a traditional technique in an innovative way. The project BioLiCoF investigates the feasability of producing liquid filled fibers using melt-spinning techniques and will examine the role that melt-spinning parameters and liquids employed as a core solution have on the final fiber. The physical analysis of the fibers is also interpreted and idea on future developments of the trials are suggested.