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.

Nanostructured smart materials as functional components of medical devices

The field of medical devices has experienced, more than others, technological advances, developments and innovations, thanks to the rapidly expanding scientific knowledge and collaboration between different disciplines such as biology, engineering and materials science. The design of functional components can be achieved by exploiting composite materials based on nanostructured smart materials, that due to the inherent characteristics of single constituents develop unique properties that make them suitable for different applications preserving excellent mechanical proprieties. For instance, recent developments have focused on the fabrication of piezoelectric devices with multiple biomedical functions, as actuation and sensing functions in one component for monitoring pressure signals. The present Ph.D. Thesis aims at investigating nanostructured smart materials embedded into a polymeric matrix to obtain a composite material that can be used as a functional component for medical devices. (i) Nanostructured piezoelectric material with self-sensing capability was successfully manufactured by using ceramic (i.e. lead zirconate titanate (PZT)) and (ii) polymeric (i.e. poly(vinylidene fluoride-trifluoro ethylene (PVDF-TRFE)) piezoelectric materials. PZT nanofibers were obtained by sol-gel electrospinning starting from synthetized PZT precursor solution. Synthesis, sol-gel electrospinning process, and thermal treatment were accurately controlled to obtain PZT nanofibers dimensionally stable with densely packed grains in the perovskite phase. To guarantee the impact resistance of the laminate, the morphology and size of the hosting filler were accurately designed by increasing the surface area to volume ratio. Moreover, to solve the issue relative to the mechanical discrepancy between rigid electronic materials/soft human tissues/different material of the device (iii) a nanostructured flexible composite material based on a network of Poly-L-lactic acid (PLLA) made of curled nanofibers that present a tuneable mechanical response as a function of the applied stress was successful fabricated.

Synthesis of KOH-based geopolymers for innovative applications

This study presents an evaluation on compressive strength of metakaolin-based geopolymers synthetized by using different activators, KOH and NaOH. The influence of NaOH/KOH concentration ratio together with curing temperature and time were investigated to find the best results from the compressive strength tests of metakaolin-based geopolymers, synthesized with a commercial metakaolin. Aggregates of small grain size referred as fillers, were added to reduce brittleness, and minimize the pore size and shrinkage of the final mixture creating a stronger network. In this work, silt recovered from industrial processes of wash water used for aggregates production was used as a filler in the production of KOH-based geopolymers, examining the possible influence on the mechanical strength of the final product. The curing temperatures chosen for the synthesis were 85°C, 60°C and 40°C. The samples were tested after 7 days and 28 days, according to the UNI EN 1015-11:2019 applied on Ca-based cements, analyzing the differences in mechanical strength comparing samples with similar and different compositions. The study presented in total 72 synthetized geopolymer specimens that were analyzed with unconfined compression test (UCT). The characterization of the starting materials metakaolin and silt was carried out using X- ray diffraction analysis (XRD). Whereas, the formed geopolymers were analyzed using X- ray diffraction (XRD), and scanning electron microscopy (SEM) with energy dispersive X- ray spectroscopy (EDS).

Sviluppo di biocompositi rinforzati con fibre naturali

Negli ultimi anni sta diventando sempre più insistente la necessità di sviluppare nuovi materiali in grado di sostituire le comuni plastiche derivanti dal petrolio con bioplastiche ottenute da biopolimeri che spesso vengono rinforzate mediante riutilizzo di scarti agricoli, come fibre di bambù, in grado di conferire proprietà meccaniche migliori, dando vita ai biocompositi. In particolare, una delle risorse rinnovabili più promettenti al giorno d'oggi è la cellulosa, come quella contenuta nella fibra di bambù, che, usata come filler rinforzante, permette di ottenere biocompositi con caratteristiche meccaniche e termiche migliori rispetto alle matrici polimeriche pure tipo PHB e PLA. Questa nuova generazione di biocompositi può essere vista come evoluzione dei vecchi compositi e punta l’attenzione alla sostenibilità ed ecoefficienza ponendosi sul mercato come prodotti sostenibili, ecologici e competitivi, utilizzabili in svariati ambiti, dal packaging alimentare ai complementi d’arredo, dall’automotive all’edilizia, dall’industria tessile alle applicazioni biomedicali. Lo scopo di questo lavoro di Tesi è stato quello di realizzare e caratterizzare dal punto di vista termico e meccanico biocompositi a base di PLA con tre percentuali crescenti di filler naturale ed a base di PHB con le stesse percentuali di filler. I sei biocompositi sono stati realizzati tramite plastografo Brabender. In seguito, sono state effettuate le seguenti prove: 1) Calorimetria a scansione differenziale (DSC); 2) Stampaggio ad iniezione per la realizzazione dei campioni secondo la normativa; 3) Prove di trazione, al fine di capire se il filler avesse modificato il modulo di Young e l’allungamento a rottura della matrice pura; 4) Prove di impatto, effettuate per studiare la tenacità del materiale al variare delle diverse percentuali di filler; 5) Microscopio a scansione elettronica (SEM), con lo scopo di osservare l’adesione matrice-filler.