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Recently, Fused Filament Fabrication (FFF), one of the most encouraging additive manufacturing (AM) techniques, has fascinated great attention. Although FFF is growing into a manufacturing device with considerable technological and material innovations, there still is a challenge to convert FFF-printed prototypes into functional objects for industrial applications. Polymer components manufactured by FFF process possess, in fact, low and anisotropic mechanical properties, compared to the same parts, obtained by using traditional building methods. The poor mechanical properties of the FFF-printed objects could be attributed to the weak interlayer bond interface that develops during the layer deposition process and to the commercial thermoplastic materials used. In order to increase the final properties of the 3D printed models, several polymer-based composites and nanocomposites have been proposed for FFF process. However, even if the mechanical properties greatly increase, these materials are not all biodegradable. Consequently, their waste disposal represents an important issue that needs an urgent solution. Several scientific researchers have therefore moved towards the development of natural or recyclable materials for FFF techniques. This review details current progress on innovative green materials for FFF, referring to all kinds of possible industrial applications, and in particular to the field of Cultural Heritage.

Microplastic (MP) pollution represents one of the biggest environmental problems that is further exacerbated by the continuous degradation in the marine environment of MPs to nanoplastics (NPs). The most diffuse plastics in oceans are commodity polymers, mainly thermoplastics widely used for packaging, such as polyethylene terephthalate (PET). However, the huge interest in the chemical vector role of micro/nanoplastics, their fate and negative effects on the environment and human health is still under discussion and the research is still sparse due also to the difficulties of sampling MPs and NPs from the environment or producing NPs in laboratory. Moreover, the research on MPs and NPs pollution relies on the availability of engineered nanoparticles similar to those present in the marine environment for toxicological, transport and adsorption studies in biological tissues as well as for wastewater remediation studies. This work aims to develop an easy, fast and scalable procedure for the production of representative model nanoplastics from PET pellets. The proposed method, based on a simple and economic milling process, has been optimized considering the peculiarities of the polymer. The results demonstrated the reliability of the method for preparing particle suspensions for aquatic microplastic research, with evident advantages compared to the present literature procedures, such as low cost, the absence of liquid nitrogen, the short production time, the high yield of the process, stability, reproducibility and polydisperse size distribution of the produced water dispersed nanometric PET.

In this study, novel biocomposite filaments incorporating cocoa bean shell waste (CBSW) and poly(lactic acid) (PLA) were formulated for application in Fused Filament Fabrication (FFF) technology. CBSW, obtained from discarded chocolate processing remnants, was blended with PLA at concentrations of 5 and 10 wt.% to address the challenge of waste material disposal while offering eco-friendly composite biofilaments for FFF, thereby promoting resource conservation and supporting circular economy initiatives. A comprehensive analysis encompassing structural, morphological, thermal, and mechanical assessments of both raw materials and resultant products (filaments and 3D printed bars) was conducted. The findings reveal the presence of filler aggregates only in high concentrations of CBSW. However, no significant morphological or thermal changes were observed at either CBSW concentration (5 wt.% and 10 wt.%) and satisfactory printability was achieved. In addition, tensile tests on the 3D printed objects showed improved stiffness and load resistance in these samples at the highest CBSW concentrations. In addition, to demonstrate their practical application, several 3D prototypes (chocolate-shaped objects) were printed for presentation in the company’s shop window as a chocolate alternative; while retaining the sensory properties of the original cocoa, the mechanical properties were improved compared to the base raw material. Future research will focus on evaluating indicators relevant to the preservation of the biocomposite’s sensory properties and longevity.

Marine pollution is one of the biggest environmental problems, mainly due to single-use or disposable plastic waste fragmenting into microplastics (MPs) and nanoplastics (NPs) and entering oceans from the coasts together with human-made MPs. A rapidly growing worry concerning environmental and human safety has stimulated research interest in the potential risks induced by the chemicals associated with MPs/NPs. In this framework, the present review analyzes the recent advances in adsorption and desorption studies of different contaminants species, both organic and metallic, on MPs made of Poly(Ethylene terephthalate). The choice of PET is motivated by its great diffusion among plastic items and, unfortunately, also in marine plastic pollution. Due to the ubiquitous presence of PET MPS/NPs, the interest in its role as a vector of contaminants has abruptly increased in the last three years, as demonstrated by the very high number of recent papers on sorption studies in different environments. The present review relies on a chemical engineering approach aimed at providing a deeper overview of both the sorption mechanisms of organic and metal contaminants to PET MPs/NPs and the most used adsorption kinetic models to predict the mass transfer process from the liquid phase to the solid adsorbent.

Bio-based polymers, obtained from natural biomass, are nowadays considered good candidates for the replacement of traditional fossil-derived plastics. The need for substituting traditional synthetic plastics is mainly driven by many concerns about their detrimental effects on the environment and human health. The most innovative way to produce bioplastics involves the use of raw materials derived from wastes. Raw materials are of vital importance for human and animal health and due to their economic and environmental benefits. Among these, wood waste is gaining popularity as an innovative raw material for biopolymer manufacturing. On the other hand, the use of wastes as a source to produce biopolymers and biocomposites is still under development and the processing methods are currently being studied in order to reach a high reproducibility and thus increase the yield of production. This study therefore aimed to cover the current developments in the classification, manufacturing, performances and fields of application of bio-based polymers, especially focusing on wood waste sources. The work was carried out using both a descriptive and an analytical methodology: first, a description of the state of art as it exists at present was reported, then the available information was analyzed to make a critical evaluation of the results. A second way to employ wood scraps involves their use as bio-reinforcements for composites; therefore, the increase in the mechanical response obtained by the addition of wood waste in different bio-based matrices was explored in this work. Results showed an increase in Young’s modulus up to 9 GPa for wood-reinforced PLA and up to 6 GPa for wood-reinforced PHA.

In the last years, the excessive use of plastic and other synthetic materials, that are generally difficult to dispose of, has caused growing ecological worries. These are contributing to redirecting the world’s attention to sustainable materials and a circular economy (CE) approach using recycling routes. In this work, bio-filaments for the Fused Filament Fabrication (FFF) 3D printing technique were produced from recycled polylactic acid (PLA) and artisanal ceramic waste by an extrusion process and fully characterized from a physical, thermal, and mechanical point of view. The data showed different morphological, thermal, rheological, and mechanical properties of the two produced filaments. Furthermore, the 3D objects produced from the 100% recycled PLA filament showed lower mechanical performance. However, the results have demonstrated that all the produced filaments can be used in a low-cost FFF commercial printer that has been modified with simple hand-made operations in order to produce 3D-printed models. The main objective of this work is to propose an example of easy and low-cost application of 3D printing that involves operations such as the reprocessing and the recyclability of materials, that are also not perfectly mechanically performing but can still provide environmental and economic benefits.

This paper reports a comparison between the advantages and disadvantages of fused filament fabrication (FFF) and computer numerical control (CNC) milling, when applied to a specific case of conservation of cultural heritage: the reproduction of four missing columns of a 17th-century tabernacle. To make the replica prototypes, European pine wood (the original material) was used for CNC milling, while polyethylene terephthalate glycol (PETG) was used for FFF printing. Neat materials were chemically and structurally characterized (FTIR, XRD, DSC, contact angle measurement, colorimetry, and bending tests) before and after artificial aging, in order to study their durability. The comparison showed that although both materials are subject to a decrease in crystallinity (an increase in amorphous bands in XRD diffractograms) and mechanical performance with aging, these characteristics are less evident in PETG (E = 1.13 ± 0.01 GPa and σ = 60.20 ± 2.11 MPa after aging), which retains water repellent (ca = 95.96 ± 5.56°) and colorimetric (∆E = 2.6) properties. Furthermore, the increase in flexural strain (%) in pine wood, from 3.71 ± 0.03% to 4.11 ± 0.02%, makes it not suitable for purpose. Both techniques were then used to produce the same column, showing that for this specific application CNC milling is quicker than FFF, but, at the same time, it is also much more expensive and produces a huge amount of waste material compared to FFF printing. Based on these results, it was assessed that FFF is more suitable for the replication of the specific column. For this reason, only the 3D-printed PETG column was used for the subsequent conservative restoration.

This work is aimed at proposing demonstrative actions devoted to show reprocessing and recyclability of PET originating from bottles collected from the seaside, in order to increase the consumer awareness on the importance of recycling plastics. To this purpose, collected bottles were washed, cut, grinded, extruded in the form of a thin wire adopting different cooling rates, which leads to a modulation of the crystallinity content. Once having optimized the processing parameters, the extruded wire was used to produce 3D printed samples through the fused deposition modelling (FDM). The changes in the crystalline structure due to the different processing conditions were assessed by DSC and XRD analyses, while rheological tests were performed in order to evaluate any modification in the viscosity of PET after repeated processing cycles. The reduction in thermal stability was confirmed by TGA analysis, which showed a progressive decrease in the degradation temperature as processing cycles increased. Finally, tensile tests highlighted the difference in the mechanical response due to the predominance of the crystalline or amorphous phase in the tested sample. In particular, a good mechanical behavior was found for the 3D-printed samples.

The protection of the stone surfaces of the buildings of the city of Lecce (Apulia, Italy) represents an ancient practice, which has always allowed the conservation of the historical-artistic heritage of the city, which nowadays is an international touristic and cultural destination. The identification of ancient recipes, materials and methodologies for the protection of historical buildings plays an important role in establishing correct protocols in order to ensure the durability of stone surfaces over time. This work presents a historically accurate reconstruction of the materials and conservation technologies used on the facades of the artistic buildings in Lecce. Several historical buildings, both civil and religious, have been selected in order to investigate the treatments applied on their facades and to know the traditions spread in the past in the field of building conservation in the Salento territory. Thanks to non-invasive or micro-destructive techniques (optical microscopy, ATR-FTIR spectroscopy, pyrolysis–gas chromatography–mass spectrometry), the characteristic molecular markers of the materials and the products of degradation have been identified, deepening the knowledge of the mechanisms of deterioration and interaction between the stone material, the surface finish and the surrounding environment. The paper is a valuable tool for the knowledge of ancient traditions and the planning of proper restoration works.

3D modelling and 3D printing techniques have become increasingly popular in different fields, including cultural heritage. In this field, there are still many challenges to overcome, such as the difficulty of faithfully reproducing complex geometries or finding materials suitable for restoration, due to the limited scientific studies. This work proposes an example of the application of advanced technologies for the reproduction of four missing columns of a 17th century polychrome wooden ciborium. The difficulties of an automatic scan due to its reflective surface (water gilding and estofado decorations) were overcome by creating a 2D manual survey and a subsequent manual 3D redrawing. The CAD model was used to print the missing elements with fused filament fabrication (FFF) in polyethylene terephthalate glycol (PETG), using the following printing parameters: nozzle 0.4 mm, infill 20%, extrusion temperature of PLA 200 °C and of PETG 220 °C, plate temperature 50 °C, printing speed 60 mm/s, layer height 0.2 mm. The conservation and restoration of the ciborium is nearing completion. This study highlights the importance of collaboration between different professionals for the correct design of a restoration, as well as the need to promote scientific research into the development of new high-performance 3D printing materials suitable for conservation.