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Article

From Marble Waste to Eco-Friendly Filament for 3D Printing to Help Renaturalization of Quarries

by
Daniela Fico
1,*,
Daniela Rizzo
2,
Valentina De Carolis
3,
Francesca Lerario
4,
Annalisa Di Roma
4 and
Carola Esposito Corcione
3
1
Italian National Council of Research-Institute of Heritage Sciences (CNR-ISPC), Campus Ecotekne, 73100 Lecce, Italy
2
Department of Cultural Heritage, University of Salento, via D. Birago 64, 73100 Lecce, Italy
3
Department of Engineering for Innovation, University of Salento, P, Campus Ecotekne, s.p. 6 Lecce-Monteroni, 73100 Lecce, Italy
4
Department of Civil Engineering and Architectural Sciences (DICAR), Polytechnic of Bari, Via Amendola 126/B, 70126 Bari, Italy
*
Author to whom correspondence should be addressed.
Sustainability 2025, 17(5), 1977; https://doi.org/10.3390/su17051977
Submission received: 19 January 2025 / Revised: 12 February 2025 / Accepted: 21 February 2025 / Published: 25 February 2025
(This article belongs to the Special Issue Research Progress and Evaluation Challenges of By-Product and Waste Valorization)
Browse Figures
Figure 1
<p>Sample measurements designed for FFF printing of prototypes for aesthetic tests.</p> "> Figure 2
<p>Diagram of the research phases from left to right: from the selection of raw materials (PLA and MW) to the production of green composite filaments and 3D printing of aesthetic and functional prototypes to the renaturalization of the quarry.</p> "> Figure 3
<p>XRD diffractogram of PLA (<b>A</b>) and MW (<b>B</b>); ATR-FTIR spectra of PLA (<b>C</b>) and MW (<b>D</b>) with indication of main peaks identified.</p> "> Figure 4
<p>New developed filaments for FFF and DSC thermograms of 100PLA_f, 90PLA/10MW_f, 80PLA/20MW_f, and 70PLA/30MW_f, and of the PLA pellet.</p> "> Figure 5
<p>CAD model of the aesthetic prototype designed with Rhinoceros software (<b>A</b>) and modified with Cura software (<b>B</b>); printing of the aesthetic prototype using the Creality CP-01 printer (<b>C</b>) and final printed aesthetic tests (<b>D</b>).</p> "> Figure 6
<p>Top: adaptability of the device to the side of the quarry, scale 1:50, angle 90°–30°–45° and example of arrangement in quarry with simulated route, scale 1:100; bottom: study on the adaptability of plants and prototype in the quarry.</p> ">
Versions Notes

Abstract

:
The excessive use of materials that are generally difficult to discard, such as stone materials, has caused growing ecological concern. Among these, marble is extracted from quarries, but when the raw material is exhausted, these places are deserted. For this reason, several measures have been adopted in recent years to requalify these areas. In addition, recent technological developments involve the creation of innovative green materials that privilege the circular economy and waste recycling. This research presents the development of innovative, sustainable filaments for the fused filament fabrication (FFF) printing technique from recycled marble waste (MW) and biocompostable and biodegradable polylactic acid (PLA) matrix. MW was added to the polymer in concentrations of 10 wt.%, 20 wt.%, and 30 wt.%, and the blends were extruded to develop innovative green filaments. The chemical/structural properties of the raw materials and the thermal and mechanical features of the new composites were investigated. Composites containing 10 and 20 wt.% of MW showed good printability. In contrast, extrusion and printing difficulties were observed with 30 wt.% of MW. Finally, this paper proposes a project to renaturalize and requalify a disused marble quarry located in Trani (Apulia, Italy) with 3D printing devices using the newly produced eco-filaments, which have better features. The main purpose of this article is to propose a concrete, economic, and sustainable application of 3D printing involving processes such as waste and by-product recycling and renaturalization of disused quarries, with both economic and environmental benefits.

1. Introduction

The overuse of materials which are difficult to dispose of, like stone, has raised environmental concerns, especially during extraction and processing [1]. Among these, marble, a limestone rock that has always been used in construction and architecture, generates a significant amount of non-biodegradable waste [2]. While quarrying contributes to economic development, it causes serious environmental impacts, including landscape changes, soil depletion, loss of vegetation, and pollution. Quarrying also produces large amounts of waste, including stone and sludge. Since 2008, Legambiente has been monitoring the environmental impact of quarries in Italy [3]. Abandoned quarries, if not redeveloped, become illegal dumps, leaving lasting scars on the landscape. However, rehabilitating these areas can benefit communities by improving quality of life and fostering biodiversity. Successful examples include the Eden Project in Cornwall, the La Palomba Sculpture Park in Matera, and the Parco delle Cave in Milan, which is now a UNESCO-recognized green space [3].
Moreover, growing environmental concerns call for a shift in production strategies, focusing on the use of by-products and waste materials to create new products in line with circular economy principles [4,5]. In the field of additive manufacturing (AM), innovations in fused filament fabrication (FFF) 3D printing technology are focusing on the development of eco-friendly filaments such as PLA enriched with waste material powders, including marble. These composites help reduce environmental impact while offering unique aesthetic and mechanical properties [6,7]. This approach aligns with the increasing demand for sustainable materials with high technical performance. For example, designers like Lorenzo Palmieri, Moreno Ratti, and Paolo Ulian have proposed solutions to optimize design, reducing waste or reusing stone waste to create new objects [8].
This paper intends to design and construct a 3D prototype from recycled marble to be placed within the abandoned quarries to contribute to their renaturalization. The creation of the 3D model is achieved through an AM technology called fused filament fabrication (FFF), which uses a biocomposite filament developed from polylactic acid (PLA) and industrial marble by-products. A complete morphological/structural, chemical, and thermal characterization was carried out on the raw materials, while the mechanical properties and printability were investigated on 3D-printed prototypes. The topic fits within the framework of environmental sustainability, geared toward an industrial ecology, with the objective of strengthening the regional circular economy through the reutilization of marble waste by transforming it into new materials and defining its main application. The idea to use marble waste is also due to the high calcium carbonate content in the composition of marble. This latter compound is, in fact, widely used in agriculture to improve plant growth by correcting soil acidity and providing calcium essential for plant development. The use of calcium carbonate helps to improve soil structure and optimize nutrient uptake by plants [9]. Furthermore, the selection of PLA as a polymer for the production of the biocomposite filaments for FFF is not only due to the large use of this material in 3D printing but also for its biodegradability. Several studies have investigated the timing and behavior of PLA degradation in soil. Studies show that the subsoil degradation process of polylactic acid is very slow. For example, Ohkita and Lee, 2006 showed no degradation of buried PLA films for six weeks [10]. Uryama et al., 2002 [11] showed that the molecular weight of PLA films (having an optical purity of 100% L and 70% L lactate units) decreased by 20% and 75%, respectively, after 20 months of interment. To the best of our knowledge, this is the first time that a biocomposite filament based on PLA and marble waste has been proposed to produce a 3D-printed model to be used for the rehabilitation and redevelopment of a query. Similar papers are already present in the literature, but they only analyzed the impact of the presence of marble waste on the thermal and mechanical features of the PLA and on the printability of the composite filament. It has already been demonstrated that the use of marble scraps is an advantageous solution to reduce the use of synthetic fillers and to recycle wastes from mining and processing industries. Such powders, when properly integrated, can increase the stiffness of the material, reduce its tendency to warp, and improve the quality of the molded product [4,12]. Almansoori and Pervaiz, 2023 have shown that the mechanical properties of PLA and marble prints can be optimized by adjusting printing settings such as layer height and extrusion rate [13]. However, it is interesting to note that this type of filament not only can offer an environmentally sustainable alternative but also contributes to enhanced aesthetics, with surfaces that evoke the naturalness of marble, expanding the capabilities of 3D-printed models in the interior design sector and in the creation of everyday objects [13]. As suggested by Liu et al., 2023 [14], PLA- and marble-derived materials lend themselves to various applications that include the restoration and preservation of cultural heritage. Indeed, the use of filaments that combine sustainability and aesthetic design provides the opportunity to create models and reproductions of historical artifacts, enriching the field of preservation with innovative tools that maintain a minimal ecological impact. The aesthetic features of these materials make them ideal for applications ranging from furniture to decorative objects, increasing the perceived value of waste materials and promoting a new material aesthetic that enhances the intrinsic qualities of the waste itself [15,16]. Such innovations also find practical application in building and architectural contexts, where structural stability and resistance to weathering are critical. Also, Taranto et al., 2023 [17] have highlighted the importance of using local and waste materials to adapt products to specific geographic needs, supporting a modular and flexible approach that respects the natural resources and ecological specificities of the host context. Other studies, such as “Bioreceptive Ceramic Surfaces: Material Experimentations for Responsible Research and Design Innovation in Circular Economy Transition and Ecological Augmentation” [15], through material experiments, aim to examine how they can integrate ecology and responsible design, proposing new models for recycling and material recovery in architecture and sustainable construction, working on ceramic surfaces suitable for supporting the growth of living organisms (such as mosses and lichens) to improve the quality of the urban environment.
The design practices presented for the first time in this work represent an evolution of the concept of sustainability and circularity in materials design. The design of innovative green PLA filaments based on marble dust and other mineral wastes offers an innovative response to today’s environmental challenges, harnessing the potential of material reuse to reduce dependence on virgin resources and to develop objects to be used for aesthetic or functional purposes in an easy, sustainable, and cost-effective method (such as fused filament fabrication printing), as explored in the next sections.

2. Materials and Methods

2.1. Materials

Poly(lactic acid) Ingeo 4043D (NatureWorks LLC, Blair, NE, USA) in pellet form (PLA) was used for the experiment, having the following technical properties: density of 1.24 g cm−3, melt flow index (MFI) of 6 g/10 min (at a temperature of 210 °C) and a particle diameter of approximately 5 mm. The marble powder waste (MW) used in the research was supplied by the company Gurrado Marmi SRL (Gravina in Puglia, Bari, Italy). The waste comes from the processing of marble obtained from water cutting. By allowing the sludge produced to dry, the company obtained a brown, odorless powder of heterogeneous grain size, which was kindly given to the University of Salento for experimentation. Before utilization, both the PLA pellets and the MW powder were conditioned for 24 h in an oven (Bicasa, Bernareggio, Monza Brianca, Italy) at 60 °C. Then, the particles were reduced using the Retsch ZM 100 Ultracentrifugal mill (Retsch GmbH, Haan, Germany) to a diameter of 0.75 mm for PLA and 0.25 mm for MW. The resulting powders were kept in an oven at 60 °C until their use.

2.2. Production of Innovative Sustainable Filaments for FFF

Initially, PLA and MW powders were mixed manually at room temperature and placed in the 3Devo Composer 450 Filament Maker single-screw extruder (Utrecht, The Netherlands) to produce the innovative sustainable filaments for FFF. All filaments produced had a diameter of approx. 1.75 mm ± 0.1 mm. Specifically, PLA was used in its pure form for extrusion of a pure filament (100PLA_f) and as a polymer matrix of MW powder for the development of composite biofilaments, by incorporating the following percentages of MW as filler: 10 wt.% (filament labeled as 90PLA/10MW_f), 20 wt.% (filament labeled as 80PLA/20MW_f), and 30 wt.% (filament labeled as 70PLA/30MW_f). The extrusion parameters used to develop the innovative sustainable filaments (90PLA/10MW_f, 80PLA/20MW_f) are the following: screw speed 3.5 rpm, feed zone temperature 170 °C, compression zone temperature 185 °C, metering zone temperature 190 °C, and die temperature 200 °C for 100PLA_f. The extrusion parameters used to develop the 70PLA/30MW_f are the following: screw speed 3.5 rpm, feed zone temperature 215 °C, compression zone temperature 210 °C, metering zone temperature 195 °C, die temperature 190 °C, and fan cooling speed 30%.

2.3. Three-Dimensional Printing of Specimens for Bending Tests and Aesthetic Tests

Specimens for bending tests were printed using each marble-based product filament (90PLA/10MW_f, 80PLA/20MW_f, and 70PLA/10MW_f). The Creality CP-01 printer (Creality, London, UK) was employed for FFF printing with the specified settings: nozzle 1 mm, extrusion and plate temperature 200 °C and 50 °C, print speed 50 mm/s, infill 100%, raster angle 45°, fan speed 100%. Rhinoceros software version 7 (Robert McNeel & Associates, Seattle, WA, USA) was used for the creation of the CAD model, and Cura software version 5.1.1 (Ultimaker B.V., Utrecht, The Netherlands) for the conversion to G-code file. The 3D bar specimens (100PLA_3D, 90PLA/10MW_3D, 80PLA/20MW_3D, and 70PLA/30MW_3D) for the bending tests were printed in accordance with the EN ISO 178 standard [18] with dimensions of 80 × 10 × 4 mm.
In addition to mechanical tests, prototypes for aesthetic tests were designed and 3D printed from composite developed filaments. Specifically, the 3D model was designed with a complex geometry (5 × 30 × 30 mm) suitable for FFF printing, and the dimensional specifications are shown in Figure 1. The model features a square base 1 mm thick and is divided into two sections: one section includes zigzag lines 1.5 mm wide, chosen to incorporate sharp edges. This line width was determined through various tests to establish the minimum printable size for this type of filament using a 1 mm nozzle (selected based on the inclusion of marble fillers in the polymer matrix to promote extrusion), with the goal of achieving a readable and well-defined line to assess print quality on thin lines and precise details, such as edges. The second section of the model divides the volume into parallelepipeds of equal size. The different heights of the zigzag lines and parallelepipeds were studied to evaluate the quality of the printed layers and the transparency of the material as the number of print layers and the filament fill percentage vary. The model is planned from 3 to 16 layers of 0.32 mm. The Creality CP-01 printer (Creality, London, UK) was employed for FFF printing using the specified settings: nozzle 1 mm, extrusion and plate temperature 200 °C and 50 °C, print speed 50 mm/s, raster angle 45°, infill 30%. Rhinoceros software version 7 (Robert McNeel & Associates, USA) was used to create the CAD model, and Cura software version 5.1.1. (Ultimaker B.V., Utrecht, The Netherlands) for the transformation to G-code, using the “Draft quality” function in slicing.

2.4. Study of the Properties of the Raw Materials and the Developed Biocomposite

The chemical characterization of the raw materials (PLA and MW) was carried out using Fourier transform infrared spectroscopy (FTIR). A FT/IR 6300 spectrometer (Jasco, Easton, MD, USA) was used for FTIR analysis (4 cm−1 resolution, 64 scans, region of 4000 to 700 cm−1). Samples were embedded in KBr pellets and five measurements were made for each specimen. The Ultima+ diffractometer (Rigaku, Tokyo, Japan) was used for the structural analysis of the innovative filaments and the following parameters: CuKα radiation (λ = 1.5418 Å) in the step scan mode recorded in the 2θ range from 2 to 60°, with a step size of 0.02° and a step duration of 0.5 s. Five measurements were made for each sample. Differential scanning calorimetry (DSC) (DSC1 StareSystem, Mettler Toledo, Columbus, OH, USA) was carried out on polylactic acid pellets and biocomposites to evaluate the effect of adding MW to the polymer matrix. DSC analyses were conducted under a nitrogen atmosphere with a heating rate of 10 °C min−1 in the temperature range from 25 °C to 200 °C. Glass transition temperature (Tg), crystallization temperature (Tc), and melting temperature (Tm) were measured from sample analyses. The Lloyd LR5K dynamometer (Lloyd Instruments Ltd., Bognor Regis, UK) was used to evaluate the flexural properties of biocomposites. The flexural tests were performed in accordance with EN ISO 178 standard [18], with a test speed of 2 mm/min and a specimen support distance of 64 mm. Five measurements were performed for each sample.

2.5. Proof of Concept

After investigating the chemical/structural features of the raw materials, the mechanical performance of the biocomposites, and the aesthetic properties of the 3D specimens, the proof of concept was set up. The different stages of the research are schematized in Figure 2. The aim was to try to use the innovative biocomposites produced by recycling waste materials in a real natural environment to study the renaturalization process through a complete sustainable process. The final goal of the research was to value marble waste at the same time as maintaining a link to its place of origin. After exploring the context of marble extraction, its applications over time, environmental impact, and issues related to the disuse of extractive quarries, the authors designed a biodegradable and sustainable device suitable for facilitating the rooting of plants on stone in deserted quarries, contributing to renaturalization.
The final prototype for quarry installation was created with the following dimensions: 1000 × 454 × 593 mm. Rhinoceros software version 7 (Robert McNeel & Associates, USA) was used to create the CAD model, while the texture was created with Rhinoceros’ additive tool called Grasshopper. Cura software version 5.1.1. (Ultimaker B.V., Utrecht, The Netherlands) was employed to generate the G-code file. The Creality CP-01 printer (Creality, London, UK) was used to fabricate 3D prints with the following specifications: nozzle 1 mm, extrusion and platen temperature 190 °C and 50 °C, print speed 60 mm/s, raster angle 45 °, infill 20%. Finally, a disused quarry located in Trani (Apulia, Italy) was selected as a possible site for the installation of the new 3D-printed sustainable object suitable for stimulating plant growth.

3. Results and Discussion

3.1. Characterization of Raw Materials, New Composite, and Prototypes

The chemical/structural properties of PLA and MW powders used to produce innovative sustainable filaments for 3D printing were investigated (Figure 3). Diffraction peaks at 2θ = 16.70° and 2θ = 19.10° associated with crystalline planes (110) and (203) are present in the XRD diffractogram of polylactic acid (Figure 3A) [12]. In that of the MW powder (Figure 3B), diffraction peaks mainly due to calcite (CaCO3) are present. The main diffraction peaks are located at 2θ = 23.40°, 29.70°, 36.20°, 39.70°, and 43.55°, and are attributable to the crystalline planes (012), (104), (110), (113), and (202), respectively [19,20]. This indicates that the marble powder used in the experiment consists predominantly of calcite [20,21]. A diffraction peak located at 31.50° attributable to the crystalline plane (104) also indicates the presence of a minor amount of dolomite (CaMg(CO3)2) in the marble powder (Figure 3B) [21].
ATR-FTIR spectroscopy was used to chemically investigate the raw materials (PLA and MW). In the infrared spectrum of the PLA (Figure 3C), there are peaks at 2995 cm−1 and 2946 cm−1 associated with the asymmetrical and symmetrical stretching vibrations of the -CH3 and -CH3 groups, respectively [4,22]. In addition, a band at 1746 cm−1 of the stretching of the C=O group and peaks at 1452 cm−1 and 1365 cm−1 relating to the asymmetric and symmetric bending vibrations of the -CH3 groups appear in the infrared spectrum [4,22]. Finally, an infrared signal at 1084 cm−1 corresponds to the C-O bond of PLA [4,22].
The infrared spectrum of the marble powders (Figure 3D) shows mainly bands associated with the presence of calcium carbonate (more commonly known as calcite (CaCO3)) and dolomite (CaMg(CO3)2), at 1415 cm−1, 989 cm−1, 874 cm−1, and 711 cm−1 due to the vibrational bands of the -CO32− groups, and an infrared peak at 1070 cm−1 relating to the Si-O-Si bond of silica dioxide (silica SiO2), often present as impurities or inclusions of marble in small quantities [19,23].
The 100PLA_f filament shows a slightly lower Tg than the pellet (Figure 4, Table 1), as also reported in the literature [5]. This is usually attributable to the degradation process that the polymers undergo during extrusion, since they are subjected to shear stress and changes in environmental conditions, such as temperature and humidity [24,25]. DSC analyses indicate that the presence of marble powder affected the polymer on a molecular scale (Figure 4) [26]. In fact, composite filaments show a slightly higher glass transition temperature (Tg) than 100PLA_f (Figure 4, Table 1). This phenomenon is often observed in composites and depends mainly on the added filler and its properties, such as particle shape and size, amount of agglomeration [5,26]. For example, Ledvai et al. showed a consistent increase in Tg in matrix composites made of polylactic acid and having 20 wt.% MW, emphasizing a limited mobility of the polymer molecules caused by the filler [20]. The main changes resulting from the interaction between polymer and MW particles are found in the changes in the crystallization (Tc) and melting (Tm) temperatures. The Tc in the 90PLA/10MW_f, 80PLA/20MW_f, and 70PLA/30MW_f filaments, compared to 100PLA_f (Tc of 124.4 °C), drops to 117.2 °C, 115.9 °C, and 113.7 °C, respectively. The temperature range of cold crystallization always seems to depend on the increased molecular mobility of the PLA chains [20]. Similarly, the enthalpy of crystallization (Hc) increases significantly in samples 90PLA/10MW_f and 70PLA/30MW_f. In contrast, the Hc value of 29.4 Jg−1 of the 80PLA/20MW_f sample appears to be less variable than the crystallization enthalpy of 100PLA_f (Table 1). Regarding the melting process, a double melting peak (Tm and Tm1) emerges in the DSC curves of the composite filaments, which is not present in 100PLA_f (Table 1, Figure 4). Usually, the presence of the double melt peak indicates a different behavior during the phase transition between the polymer and the filler, due to a different nature; this phenomenon has already been observed by the authors mainly in polymer composites developed from organic (olive wood and cocoa beans) [20,27] and sometimes inorganic (ceramics) waste [5].
The 3D specimens for bending testing (80 × 10 × 4 mm) were printed by FFF, in accordance with EN ISO 178 standard [18]. Table 2 summarizes the results of the mechanical tests. Overall, the results obtained from the analysis of neat PLA correspond to the values reported in the literature. Often, the addition of aggregates to polymer for composite development causes an increase in viscosity, which is also dependent on several factors (e.g., the size or shape of the filler particles and their content) [26]. In this study, some differences in the Young’s modulus (E) of the composite samples compared with pure PLA are observed (Table 2). Specifically, the values of samples 90PLA/10MW_3D and 70PLA/30MW_3D appear to be reduced compared to that of PLA, approximately 0.59 GPa and 0.10 GPa, respectively. Only sample 80PLA/20MW_3D shows a slightly higher E value, which may indicate an increment in the viscosity of the melt polymer due to the filling addition [26]. Subsequently, after reaching the maximum value following the addition of 20 wt.% of MW, the elastic modulus decreases. This phenomenon may depend on the combination of MW particles and consequently a lower surface area available for interphase contact between the polymer matrix and the marble [5,26]. This trend of the flexural modulus to change according to the weight percentage of filler content, independent of particle size, has already been shown by Nayak and Satapathy in 2021 [28], when they recorded a maximum increase to 8 wt.% filler, which then decreased to higher percentages. Before their study, the phenomenon was known for composites based on ceramic fillers [29]. The values of flexural strain εR (%) and stress σR (MPa) always show a decrease in the samples resulting from the addition of MW (Table 2). Moreover, these decreases are more evident in sample 70PLA/30MW_3D. The decrease appears to have a linear trend and to be proportional to the increase in MW concentration in the PLA matrix; moreover, the fragility of the composites increases compared to the neat polymer.
Aesthetic tests were performed on prototypes produced from the newly sustainable filaments (Figure 5). The preliminary results show a linear growth in shade and opacity with increasing percentage content of MW in the PLA matrix. Similarly, the inclusion of filler also affects the roughness and printability of the prototypes. For example, the initial print layer in contact with the heated bed appears compact and homogeneous in the prototype printed with the 90PLA/10MW_f filament, where the print layers adhere perfectly to each other. The same characteristics are shown by the prototype created with the 80PLA/20MW_f filament, while the prototype with a major MW content derived from the FFF print with the 70PLA/30MW_f filament shows imperfections and discontinuities, such as surface voids. The edge detail precision along the zigzag patterns is more evident in the prototype obtained from 80PLA/20MW_f filament, while it decreases in the other two models.
Overall, the prototypes printed for aesthetic tests exhibit typical defects related to filament underextrusion, such as imperfect and discontinuous lines that cause voids on the surface, and overextrusion, such as imperfections on the outer wall layers. Both types of defects can be attributed to the inhomogeneity of the filament diameter, a problem that can be overcome by optimizing the extrusion process.

3.2. Proof of Concept: The Reuse of Marble By-Products for the Renaturalization of a Quarry in Trani (Apulia, Italy)

A case study based on the reuse of waste marble within its natural environment in support of a circular economy and sustainability is reported by the authors in this section (Figure 6).
The reutilization of not easily disposable materials (such as marble) and biocompostable materials (such as polylactic acid), but which still require several months to degrade and incur heavy costs, provides numerous environmental and economic benefits [30]. In fact, scientific research conducted in recent years highlights the economic benefits of incorporating industrial waste aggregates into polymer matrices for the production of new reusable composites [31,32]; the 3D printing technique named fused filament fabrication has recently established itself as an innovative methodology for a green transition. However, examples of innovative composites developed from waste materials printed with FFF and returned to their original environment are still rare in the literature [4,33,34]. From this, the authors conceived of the idea to find an application for the developed biocomposites that could not only valorize the waste material and extend its life cycle but also promote the renaturalization of an abandoned quarry. It is known that monomers from agricultural resources of corn, beet, sugar, and other plants are used to chemically produce a biodegradable and biocompostable polymer: polylactic acid (PLA) [35,36]. Some studies have shown that finely ground marble can slowly release minerals useful for plants, acting as a source of calcium and improving soil nutrition [37]. In addition to acting as a natural fertilizer, calcium carbonate can be used to protect trees from pests and help mitigate the effects of excessive heat and soil pH [38].
An abandoned marble quarry located in Trani (Puglia, Italy) was identified for this renaturalization study. The research continued with the identification of the most suitable vegetation for the purpose and with the design study of the placement of the new 3D-printed composite object inside the quarry, considering the following factors:
1.
Plant species capable of adapting to the specific microclimate of the quarry were selected, considering soil composition and light availability. The goal is to prioritize native or adaptable species to ensure low-maintenance and optimal ecological integration.
2.
Great attention was given to the visual harmony between the natural environment and the artificial element. The object was designed to enhance the site’s appearance without altering its historical and environmental character, drawing on organic shapes already present in the location.
3.
The installation process was designed to minimize the impact on the local ecosystem, using sustainable and non-polluting materials.
Usually, abandoned quarries are characterized by both regular and irregular geometries. Therefore, it was decided to give the new device an irregular shape, so as to allow it to integrate harmoniously with the surrounding environment, while maintaining its functionality as a repeatable module. The shape of the module created is that of an irregular trapezium which, thanks to its four sides, offers a high degree of modularity, allowing it to be placed next to the next device and thus facilitating the creation of different, more versatile configurations. The assembly of these modules can create paths that not only facilitate the orientation of people inside the quarries but can also be transformed into real green sculptures thanks to the correct stacking and combination of the individual elements, positioned in the center of the quarry or on its sides. Finally, the designed device was printed using the FFF technique and the innovative filament derived from by-product marble and containing 20 wt.% of filler, with the ultimate goal of integrating with the natural environment thanks to the physical/chemical features of the starting materials and the specific shape designed, while promoting plant growth until the end of its life cycle and transforming an unused environment into a possible accessible and recreational space for people.

4. Conclusions

In recent years, several actions have been taken to overcome the problems associated with the disposal of marble by-products, which require costly practices, and the abandonment of quarries after they are exhausted. In this work, new sustainable filaments for the 3D printing technique fused filament fabrication (FFF) were developed from reused waste marble (MW) and biocompostable and biodegradable polylactic acid (PLA) matrix. Marble powder was added to the PLA polymer matrix in weight concentrations of 10 wt.%, 20 wt.%, and 30 wt.%. PLA-MW blends were extruded to develop innovative green filaments, from which composite prototypes were printed for the evaluation of chemical/structural, thermal, mechanical, and aesthetic properties. The results of thermal analysis on the developed green composites show that MW particle content affects the mobility of PLA chains and their viscosity. While the glass transition temperature decreases slightly compared to pure PLA, still indicating good printability of the filaments, major differences are observed in the melting phase. The incomplete miscibility and affinity between organic matrix and inorganic filler is evidenced by the presence of a double melting peak in the DSC curve, which is more evident in the sustainable composite containing 30 wt.% MW. In addition, flexural tests show a minimal increase in the elastic modulus of the composite at 20 wt.% MW content. The other composites always exhibit a reduction in elastic modulus, while fragility increases in all developed composites compared to pure PLA.
All three filaments were determined to be printable and suitable for use in FFF 3D printing processes, achieving legible and well-defined lines. The print quality for thin lines and detailed features, such as edges, was comparable to commercial filaments. Furthermore, the tests revealed that some properties of the filler added to the polymer (such as the percentage content and particle size of MW) allow for control over the surface roughness of the filament. This provides an opportunity to diversify the textural and tactile features of 3D-printed objects, broadening their potential applications. Overall, the results show better aesthetic properties (roughness, printability, and precision) of the composites obtained by the addition of 10 and 20 wt.% MW, in contrast to the prototypes having 30 wt.% MW. These mechanical and aesthetic properties make the newly developed filaments suitable for the 3D printing use of nonstructural prototypes, such as architectural/decorative or everyday objects (e.g., sculptures, vases, picture frames, furniture items), mainly for indoor use. In addition, this research proves that due to the inherent biodegradability and biocompostability features of polylactic acid and the fertilizing, anti-parasitic, and soil pH-modulating properties of marble noted in the literature, 3D-printed prototypes from green-developed composites can also be used in the outdoor environment. Filament containing 20 wt.% of marble waste powder was selected for the design of a prototype printed using the FFF technique to be placed in a disused marble quarry located in Trani (Apulia, Italy), with the aim of renaturalizing and requalifying it. Currently, examples of innovative composites developed from waste materials printed with FFF and returned to their original environment are still rare in the literature. Finally, a preliminary feasibility study of the placement of a new composite prototype in a desertified quarry was carried out, including finding the most suitable vegetation for proliferation in the selected environment (based on factors such as light and soil composition) and the geometry of the 3D prototype created from the recycled materials that would best respect the ecosystem without altering its natural and historical value. The new design device was printed using the innovative green filament developed from marble recycling, demonstrating the effectiveness of the new sustainable approach used to extend the life cycle of the industrial by-product while redeveloping an abandoned quarry and reintegrating it into its original habitat.

Author Contributions

Conceptualization, C.E.C. and A.D.R.; methodology, F.L. and D.F.; software, V.D.C.; validation, C.E.C., D.F. and D.R.; formal analysis, D.F.; investigation, V.D.C., D.F. and F.L.; resources, C.E.C.; data curation, D.F.; writing—original draft preparation, D.F.; writing—review and editing, C.E.C., D.R. and D.F.; visualization, A.D.R. and D.R.; supervision, C.E.C.; project administration, C.E.C.; funding acquisition, C.E.C. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by Ministero dell’Istruzione dell’Università e della Ricerca, project PON “Ricerca e Innovazione” 2014–2020, Asse IV “Istruzione e ricerca per il recupero”, Azione IV.5 “Dottorati su tematiche green”, DM 1061/2021 and project SPIDER (Sensors and 3D Printing for an Innovative and Detailed Exploration of local Resources) under the “Bando a cascata per Organismi di Ricerca e Imprese (riservato al Mezzoggiorno) project CHANGE (Cultural Heritage Active Innovation for Next-Gen Sustainable Society)”, SPOKE 7, Università degli Studi di Firenze, CUP B53C22004010006, Codice progetto PE00000020.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding author or other authors.

Acknowledgments

The authors thank the company “Gurrado Marmi SRL” (Gravina in Puglia, Bari, Italy) for providing the recycled raw material.

Conflicts of Interest

The authors declare no conflicts of interest.

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Sustainability 17 01977 g001
Figure 1. Sample measurements designed for FFF printing of prototypes for aesthetic tests.
Figure 1. Sample measurements designed for FFF printing of prototypes for aesthetic tests.
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Figure 2. Diagram of the research phases from left to right: from the selection of raw materials (PLA and MW) to the production of green composite filaments and 3D printing of aesthetic and functional prototypes to the renaturalization of the quarry.
Figure 2. Diagram of the research phases from left to right: from the selection of raw materials (PLA and MW) to the production of green composite filaments and 3D printing of aesthetic and functional prototypes to the renaturalization of the quarry.
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Figure 3. XRD diffractogram of PLA (A) and MW (B); ATR-FTIR spectra of PLA (C) and MW (D) with indication of main peaks identified.
Figure 3. XRD diffractogram of PLA (A) and MW (B); ATR-FTIR spectra of PLA (C) and MW (D) with indication of main peaks identified.
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Figure 4. New developed filaments for FFF and DSC thermograms of 100PLA_f, 90PLA/10MW_f, 80PLA/20MW_f, and 70PLA/30MW_f, and of the PLA pellet.
Figure 4. New developed filaments for FFF and DSC thermograms of 100PLA_f, 90PLA/10MW_f, 80PLA/20MW_f, and 70PLA/30MW_f, and of the PLA pellet.
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Figure 5. CAD model of the aesthetic prototype designed with Rhinoceros software (A) and modified with Cura software (B); printing of the aesthetic prototype using the Creality CP-01 printer (C) and final printed aesthetic tests (D).
Figure 5. CAD model of the aesthetic prototype designed with Rhinoceros software (A) and modified with Cura software (B); printing of the aesthetic prototype using the Creality CP-01 printer (C) and final printed aesthetic tests (D).
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Figure 6. Top: adaptability of the device to the side of the quarry, scale 1:50, angle 90°–30°–45° and example of arrangement in quarry with simulated route, scale 1:100; bottom: study on the adaptability of plants and prototype in the quarry.
Figure 6. Top: adaptability of the device to the side of the quarry, scale 1:50, angle 90°–30°–45° and example of arrangement in quarry with simulated route, scale 1:100; bottom: study on the adaptability of plants and prototype in the quarry.
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Table 1. Thermal properties of filaments: glass transition temperature (Tg), temperature and enthalpy of crystallization (Tc and ∆Hc), and melting temperature and enthalpy (Tm and ∆Hm).
Table 1. Thermal properties of filaments: glass transition temperature (Tg), temperature and enthalpy of crystallization (Tc and ∆Hc), and melting temperature and enthalpy (Tm and ∆Hm).
Label Weight Composition (wt.%)Tg (°C)Tc (°C)∆Hc (J g−1)Tm (°C)Tm1 (°C)∆Hm (J g−1)
PLA_pellet100 PLA Ingeo 4043D pellet61.7//154.6/19.9
100PLA_f100 PLA Ingeo 4043D59.2124.411.2155.2/22.1
90PLA/10MW_f90 PLA Ingeo 4043D and 10 marble powder waste 60.0117.244.1151.7156.437.1
80PLA/20MW_f80 PLA Ingeo 4043D and 20 marble powder waste 61.3115.929.4152.8157.424.0
70PLA/30MW_f70 PLA Ingeo 4043D and 30 marble powder waste 59.7113.740.4149.3155.130.6
Table 2. Mechanical properties from bending tests of 3D sample printed using Creality CP-01 printer: Young’s modulus E (GPa), flexural stress σR (MPa), and flexural strain εR (%).
Table 2. Mechanical properties from bending tests of 3D sample printed using Creality CP-01 printer: Young’s modulus E (GPa), flexural stress σR (MPa), and flexural strain εR (%).
Label E (GPa)σR (MPa)εR (%)
100PLA_3D3.74 ± 0.15102.50 ± 14.264.16 ± 0.13
90PLA/10MW_3D3.15 ± 0.3571.92 ± 12.193.19 ± 0.14
80PLA/20MW_3D4.06 ± 0.2267.66 ± 10.792.49 ± 0.12
70PLA/30MW_3D3.64 ± 0.1248.28 ± 13.891.65 ± 0.11
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MDPI and ACS Style

Fico, D.; Rizzo, D.; De Carolis, V.; Lerario, F.; Di Roma, A.; Esposito Corcione, C. From Marble Waste to Eco-Friendly Filament for 3D Printing to Help Renaturalization of Quarries. Sustainability 2025, 17, 1977. https://doi.org/10.3390/su17051977

AMA Style

Fico D, Rizzo D, De Carolis V, Lerario F, Di Roma A, Esposito Corcione C. From Marble Waste to Eco-Friendly Filament for 3D Printing to Help Renaturalization of Quarries. Sustainability. 2025; 17(5):1977. https://doi.org/10.3390/su17051977

Chicago/Turabian Style

Fico, Daniela, Daniela Rizzo, Valentina De Carolis, Francesca Lerario, Annalisa Di Roma, and Carola Esposito Corcione. 2025. "From Marble Waste to Eco-Friendly Filament for 3D Printing to Help Renaturalization of Quarries" Sustainability 17, no. 5: 1977. https://doi.org/10.3390/su17051977

APA Style

Fico, D., Rizzo, D., De Carolis, V., Lerario, F., Di Roma, A., & Esposito Corcione, C. (2025). From Marble Waste to Eco-Friendly Filament for 3D Printing to Help Renaturalization of Quarries. Sustainability, 17(5), 1977. https://doi.org/10.3390/su17051977

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