Design, development, and analysis of hybrid metal-composite tube for industrial application

In the aerospace, automotive, printing, and sports industries, the development of hybrid Carbon Fiber Reinforced Polymer (CFRP)-metal components is becoming increasingly important. The coupling of metal with CFRP in axial symmetric components results in reduced production costs and increased mechanical properties such as bending, torsional stiffness, mass reduction, damping, and critical speed compared to the single material-built ones. In this thesis, thanks to a novel methodology involving a rubbery/viscoelastic interface layer, several hybrid aluminum-CFRP prototype tubes were produced. Besides, an innovative system for the cure of the CFRP part has been studied, analyzed, tested, and developed in the company that financed these research activities (Reglass SRL, Minerbio BO, Italy). The residual thermal stresses and strains have been investigated with numerical models based on the Finite Element Method (FEM) and compared with experimental tests. Thanks to numerical models, it was also possible to reduce residual thermal stresses by optimizing the lamination sequence of CFRP and determining the influence of the system parameters. A novel software and methodology for evaluating mechanical and damping properties of specimens and tubes made in CFRP were also developed. Moreover, to increase the component's damping properties, rubber nanofibers have been produced and interposed throughout the lamination of specimens. The promising results indicated that the nanofibrous mat could improve the material damping factor over 77% and be adopted in CFRP components with a negligible increment of weight or losing mechanical properties.

Advanced electrospun nanofibrous mats for hindering delamination, improving damping and for sensing of composite laminates

Carbon Fiber Reinforced Polymers (CFRPs) display high specific mechanical properties, allowing the creation of lightweight components and products by metals replacement. To reach outstanding mechanical performances, the use of stiff thermoset matrices, like epoxy, is preferred. Laminated composites are commonly used for their ease of manipulation during object manufacturing. However, the natural anisotropic structure of laminates makes them vulnerable toward delamination. Moreover, epoxy-based CFRPs are very stiff materials, thus showing low damping capacity, which results in unwanted vibrations and structure-borne noise that may contribute to delamination triggering. Hence, searching for systems able to limit these drawbacks is of primary importance for safety reasons, as well as for economic ones. In this experimental thesis, the production and integration of innovative rubbery nanofibrous mats into CFRP laminates are presented. A smart approach, based on single-needle electrospinning of rubber-containing blends, is proposed for producing dimensionally stable rubbery nanofibers without the need for rubber crosslinking. Nano-modified laminates aim at obtaining structural composites with improved delamination resistance and enhanced damping capacity, without significantly lowering other relevant mechanical properties. The possibility of producing nanofibers nano-reinforced with graphene to be applied for reinforcing composite laminates is also investigated. Moreover, the use of piezoelectric nanofibrous mats in hybrid composite laminates for achieving self-sensing capability is presented too as a different approach to prevent the catastrophic consequences of possible structural laminate failure. Finally, an accurate, systematic, and critical study concerning tensile testing of nonwovens, using electrospun Nylon 66 random nanofibrous mats as a case study, is proposed. Nanofibers diameter and specimen geometry were investigated to thoroughly describe the nanomat tensile behaviour, also considering the polymer thermal properties, and the number of nanofibers crossings as a function of the nanofibers diameter. Stress-strain data were also analysed using a phenomenological data fitting model to interpret the tensile behaviour better.

Production and characterization of novel thermoplastic (nano)composite materials for additive manufacturing applications

The increasing environmental global regulations have directed scientific research towards more sustainable materials, even in the field of composite materials for additive manufacturing. In this context, the presented research is devoted to the development of thermoplastic composites for FDM application with a low environmental impact, focusing on the possibility to use wastes from different industrial processes as filler for the production of composite filaments for FDM 3D printing. In particular carbon fibers recycled by pyro-gasification process of CFRP scraps were used as reinforcing agent for PLA, a biobased polymeric matrix. Since the high value of CFs, the ability to re-use recycled CFs, replacing virgin ones, seems to be a promising option in terms of sustainability and circular economy. Moreover, wastes from different agricultural industries, i.e. wheat and rice production processes, were valorised and used as biofillers for the production of PLA-biocomposites. The integration of these agricultural wastes into PLA bioplastic allowed to obtain biocomposites with improved eco-sustainability, biodegradability, lightweight, and lower cost. Finally, the study of novel composites for FDM was extended towards elastomeric nanocomposite materials, in particular TPU reinforced with graphene. The research procedure of all projects involves the optimization of production methods of composite filaments with a particular attention on the possible degradation of polymeric matrices. Then, main thermal properties of 3D printed object are evaluated by TGA, DSC characterization. Additionally, specific heat capacity (CP) and Coefficient of Linear Thermal Expansion (CLTE) measurements are useful to estimate the attitude of composites for the prevention of typical FDM issues, i.e. shrinkage and warping. Finally, the mechanical properties of 3D printed composites and their anisotropy are investigated by tensile test using distinct kinds of specimens with different printing angles with respect to the testing direction.

Sintesi e caratterizzazione di nanopolveri composite allumina-zirconia

Il presente lavoro di tesi riguarda la sintesi di nanopolveri allumina-zirconia, seguendo tre differenti metodologie (sintesi per coprecipitazione, sintesi con il metodo dei citrati, sintesi idrotermale assistita da microonde) e il trattamento termico (calcinazione) delle polveri ottenute, mediante tecniche di riscaldamento convenzionali ed alternative (microonde). Lo scopo del lavoro è consistito nell’individuare, tra le tecniche esaminate, quella più idonea e conveniente, per la preparazione di nanopolveri cristalline 95 mol% Al2O3 – 5 mol% ZrO2 e nell’esaminare gli effetti che la calcinazione condotta con le microonde, ha sulle caratteristiche finali delle polveri, rispetto ai trattamenti termici convenzionali. I risultati ottenuti al termine del lavoro hanno evidenziato che, tra le tecniche di sintesi esaminate, la sintesi idrotermale assistita da microonde, risulta il metodo più indicato e che, il trattamento termico eseguito con le microonde, risulta di gran lunga vantaggioso rispetto a quello convenzionale. La sintesi idrotermale assistita da microonde consente di ottenere polveri nano cristalline poco agglomerate, che possono essere facilmente disaggregate e con caratteristiche microstrutturali del tutto peculiari. L’utilizzo di tale tecnica permette, già dopo la sintesi a 200°C/2ore, di avere ossido di zirconio, mentre per ottenere gli ossidi di alluminio, è sufficiente un ulteriore trattamento termico a basse temperature e di breve durata (400°C/ 5 min). Si è osservato, inoltre, che il trattamento termico condotto con le microonde comporta la formazione delle fasi cristalline desiderate (ossidi di alluminio e zirconio), impiegando (come per la sintesi) tempi e temperature significativamente ridotti. L’esposizione delle polveri per tempi ridotti e a temperature più basse consente di evitare la formazione di aggregati duri nelle nanopolveri finali e di contrastare il manifestarsi di fenomeni di accrescimento di grani, preservando così la “nanostruttura” delle polveri e le sue caratteristiche proprietà.

Polymeric membranes for CO2 separation: effect of aging, humidity and facilitated transport

Polymeric membranes represent a promising technology for gas separation processes, thanks to low costs, reduced energy consumption and limited waste production. The present thesis aims at studying the transport properties of two membrane materials, suitable for CO2 purification applications. In the first part, a polyimide, Matrimid 5218, has been throughout investigated, with particular reference to the effect of thermal treatment, aging and the presence of water vapor in the gas transport process. Permeability measurements showed that thermal history affects relevantly the diffusion of gas molecules across the membrane, influencing also the stability of the separation performances. Subsequently, the effect of water on Matrimid transport properties has been characterized for a wide set of incondensable penetrants. A monotonous reduction of permeability took place at increasing the water concentration within the polymer matrix, affecting the investigated gaseous species to the same extent, despite the different thermodynamic and kinetic features. In this view, a novel empirical model, based on the Free Volume Theory, has been proposed to qualitatively describe the phenomenon. Moreover, according to the accurate representation of the experimental data, the suggested approach has been combined with a more rigorous thermodynamic tool (NELF Model), allowing an exhaustive description of water influence on the single parameters contributing to the gas permeation across the membrane. In the second part, the study has focused on the synthesis and characterization of facilitated transport membranes, able to achieving outstanding separation performances thanks to the chemical enhancement of CO2 permeability. In particular, the transport properties have been investigated for high pressure CO2 separation applications and specific solutions have been proposed to solve stability issues, frequently arising under such severe conditions. Finally, the effect of different process parameters have been investigated, aiming at the identification of the optimal conditions capable to maximize the separation performance.

Fracture Toughening and Self-Healing of Composite Laminates by Nanofibrous Mats Interleaving

Composite laminates present important advantages compared to conventional monolithic materials, mainly because for equal stiffness and strength they have a weight up to four times lower. However, due to their ply-by-ply nature, they are susceptible to delamination, whose propagation can bring the structure to a rapid catastrophic failure. In this thesis, in order to increase the service life of composite materials, two different approaches were explored: increase the intrinsic resistance of the material or confer to them the capability of self-repair. The delamination has been hindered through interleaving the composite laminates with polymeric nanofibers, which completed the hierarchical reinforcement scale of the composite. The manufacturing process for the integration of the nanofibrous mat in the laminate was optimized, resulting in an enhancement of mode I fracture toughness up to 250%. The effect of the geometrical dimensions of the nano-reinforcement on the architecture of the micro one (UD and woven laminates) was studied on mode I and II. Moreover, different polymeric materials were employed as nanofibrous reinforcement (Nylon 66 and polyvinylidene fluoride). The nano toughening mechanism was studied by micrograph analysis of the crack path and SEM analysis of the fracture surface. The fatigue behavior to the onset of the delamination and the crack growth rate for woven laminates interleaved with Nylon 66 nanofibers was investigated. Furthermore, the impact behavior of GLARE aluminum-glass epoxy laminates, toughened with Nylon 66 nanofibers was investigated. Finally, the possibility of confer to the composite material the capability of self-repair was explored. An extrinsic self-healing-system, based on core-shell nanofibers filled with a two-component epoxy system, was developed by co-electrospinning technique. The healing potential of the nano vascular system has been proved by microscope electron observation of the healing agent release as result of the vessels rupture and the crosslinking reaction was verified by thermal analysis.

Fatigue and Damage Tolerance in Primary Composite Aeronautical Structures

The challenging requirements set on new full composite aeronautical structures are mostly related to the demonstration of damage tolerance capability of their primary structures, required by the airworthiness bodies. And while composite-made structures inherently demonstrate exceptional fatigue properties, when put in real life working conditions, a number of external factors can lead to impact damages thus reducing drastically their fatigue resistance due to fiber delamination, disbonding or breaking. This PhD aims towards contributing to the better understanding of the behavior of the primary composite aeronautical structure after near-edge impacts which are inevitable during the service life of an aircraft. The behavior of CFRP structures after impacts in only one small piece of the big picture which is the certification of CFRP built aircraft, where several other parameters need to be evaluated in order to fulfill the airworthiness requirements. These parameters are also discussed in this PhD thesis in order to give a better understanding of the complex task of CFRP structure certification, in which behavior of the impacted structure plays an important role. An experimental and numerical campaign was carried out in order to determine the level of delamination damage in CFRP specimens after near-edge impacts. By calibrating the numerical model with experimental data, it was possible, for different configurations and energy levels, to predict the extension of a delamination in a CFRP structure and to estimate its residual static strength using a very simple but robust technique. The original contribution of this work to the analysis of CFRP structures is the creation of a model which could be applicable to wide range of thicknesses and stacking sequences of CFRP structures, thus potentially being suitable for industrial application, as well.

Innovative electrospun nanofibers for improving delamination resistance and damping of CFRP laminates

Carbon Fiber Reinforced Polymers (CFRPs) are well renowned for their excellent mechanical properties, superior strength-to-weight characteristics, low thermal expansion coefficient, and fatigue resistance over any conventional polymer or metal. Due to the high stiffness of carbon fibers and thermosetting matrix, CFRP laminates may display some drawbacks, limiting their use in specific applications. Indeed, the overall laminate stiffness may lead to structural problems arising from their laminar structure, which makes them susceptible to structural failure by delamination. Moreover, such stiffness given by the constituents makes them poor at damping vibration, making the component more sensitive to noise and leading, at times, to delamination triggering. Nanofibrous mat interleaving is a smart way to increase the interlaminar fracture toughness: the use of thermoplastic polymers, such as poly(ε- caprolactone) (PCL) and polyamides (Nylons), as nonwovens are common and well established. Here, in this PhD thesis, a new method for the production of rubber-rich nanofibrous mats is presented. The use of rubbery nanofibers blended with PCL, widely reported in the literature, was used as matrix tougheners, processing DCB test results by evaluating Acoustic Emissions (AE). Moreover, water-soluble electrospun polyethylene oxide (PEO) nanofibers were proposed as an innovative method for reinforcing layers and hindering delamination in epoxy-based CFRP laminates. A nano-modified CFRP was then aged in water for 1 month and its delamination behaviour compared with the ones of the commercial laminate. A comprehensive study on the use of nanofibers with high rubber content, blended with a crystalline counterpart, as enhancers of the interlaminar properties were then investigated. Finally, PEO, PCL, and Nylon 66 nanofibers, plain or reinforced with Graphene (G), were integrated into epoxy-matrix CFRP to evaluate the effect of polymers and polymers + G on the laminate mechanical properties.