Recycling as a Key Enabler for Sustainable Additive Manufacturing of Polymer Composites: A Critical Perspective on Fused Filament Fabrication.

Additive manufacturing (AM, aka 3D printing) is generally acknowledged as a "green" technology. However, its wider uptake in industry largely relies on the development of composite feedstock for imparting superior mechanical properties and bespoke functionality. Composite materials are especially needed in polymer AM, given the otherwise poor performance of most polymer parts in load-bearing applications. As a drawback, the shift from mono-material to composite feedstock may worsen the environmental footprint of polymer AM. This perspective aims to discuss this chasm between the advantage of embedding advanced functionality, and the disadvantage of causing harm to the environment. Fused filament fabrication (FFF, aka fused deposition modelling, FDM) is analysed here as a case study on account of its unparalleled popularity. FFF, which belongs to the material extrusion (MEX) family, is presently the most widespread polymer AM technique for industrial, educational, and recreational applications. On the one hand, the FFF of composite materials has already transitioned "from lab to fab" and finally to community, with far-reaching implications for its sustainability. On the other hand, feedstock materials for FFF are thermoplastic-based, and hence highly amenable to recycling. The literature shows that recycled thermoplastic materials such as poly(lactic acid) (PLA), acrylonitrile-butadiene-styrene (ABS), and polyethylene terephthalate (PET, or its glycol-modified form PETG) can be used for printing by FFF, and FFF printed objects can be recycled when they are at the end of life. Reinforcements/fillers can also be obtained from recycled materials, which may help valorise waste materials and by-products from a wide range of industries (for example, paper, food, furniture) and from agriculture. Increasing attention is being paid to the recovery of carbon fibres (for example, from aviation), and to the reuse of glass fibre-reinforced polymers (for example, from end-of-life wind turbines). Although technical challenges and economical constraints remain, the adoption of recycling strategies appears to be essential for limiting the environmental impact of composite feedstock in FFF by reducing the depletion of natural resources, cutting down the volume of waste materials, and mitigating the dependency on petrochemicals.

Conducting polymer-based nanostructured materials for brain-machine interfaces.

As scientists discovered that raw neurological signals could translate into bioelectric information, brain-machine interfaces (BMI) for experimental and clinical studies have experienced massive growth. Developing suitable materials for bioelectronic devices to be used for real-time recording and data digitalizing has three important necessitates which should be covered. Biocompatibility, electrical conductivity, and having mechanical properties similar to soft brain tissue to decrease mechanical mismatch should be adopted for all materials. In this review, inorganic nanoparticles and intrinsically conducting polymers are discussed to impart electrical conductivity to systems, where soft materials such as hydrogels can offer reliable mechanical properties and a biocompatible substrate. Interpenetrating hydrogel networks offer more mechanical stability and provide a path for incorporating polymers with desired properties into one strong network. Promising fabrication methods, like electrospinning and additive manufacturing, allow scientists to customize designs for each application and reach the maximum potential for the system. In the near future, it is desired to fabricate biohybrid conducting polymer-based interfaces loaded with cells, giving the opportunity for simultaneous stimulation and regeneration. Developing multi-modal BMIs, Using artificial intelligence and machine learning to design advanced materials are among the future goals for this field. This article is categorized under: Therapeutic Approaches and Drug Discovery > Nanomedicine for Neurological Disease.

How Can We Provide Additively Manufactured Parts with a Fingerprint? A Review of Tagging Strategies in Additive Manufacturing.

Additive manufacturing (AM) is rapidly evolving from "rapid prototyping" to "industrial production". AM enables the fabrication of bespoke components with complicated geometries in the high-performance areas of aerospace, defence and biomedicine. Providing AM parts with a tagging feature that allows them to be identified like a fingerprint can be crucial for logistics, certification and anti-counterfeiting purposes. Whereas the implementation of an overarching strategy for the complete traceability of AM components downstream from designer to end user is, by nature, a cross-disciplinary task that involves legal, digital and technological issues, materials engineers are on the front line of research to understand what kind of tag is preferred for each kind of object and how existing materials and 3D printing hardware should be synergistically modified to create such tag. This review provides a critical analysis of the main requirements and properties of tagging features for authentication and identification of AM parts, of the strategies that have been put in place so far, and of the future challenges that are emerging to make these systems efficient and suitable for digitalisation. It is envisaged that this literature survey will help scientists and developers answer the challenging question: "How can we embed a tagging feature in an AM part?".

Is there a future for additive manufactured titanium bioglass composites in biomedical application? A perspective.

Additive manufacturing (AM) of orthopedic implants is growing in popularity as it offers almost complete design flexibility and freedom, meaning complex geometries mimicking specific body parts can be easily produced. Novel composite materials with optimized functionalities present opportunities for 3D printing osteoconductive implants with desirable mechanical properties. Standard metals for bone implants, such as titanium and its alloys, are durable and nontoxic but lack bioactivity. Bioactive glasses promote strong bone formation but are susceptible to brittle failure. Metal-bioactive glass composites, however, may combine the mechanical reliability of metals with the bone-bonding ability of bioactive glasses, potentially reducing the incidence of implant failure. Processing such composites by AM paves the way for producing unprecedented bespoke parts with highly porous lattices, whose stiffness can be tailored to meet the mechanical properties of natural bone tissue. This Perspective focuses on titanium-bioactive glass composites, critically discussing their processability by AM and highlighting their potential as a next-generation implantable biomaterial.

Technological Feasibility of Lattice Materials by Laser-Based Powder Bed Fusion of A357.0.

Lattice materials represent one of the utmost applications of additive manufacturing. The promising synergy between additive processes and topology optimization finds full development in achieving components that comprise bulky and hollow areas, as well as intermediate zones. Yet, the potential to design innovative shapes can be hindered by technological limits. The article tackles the manufacturability by laser-based powder bed fusion (L-PBF) of aluminum-based lattice materials by varying the beam diameter and thus the relative density. The printing accuracy is evaluated against the distinctive building phenomena in L-PBF of metals. The main finding consists in identification of a feasibility window that can be used for development of lightweight industrial components. A relative density of 20% compared with fully solid material (aluminum alloy A357.0) is found as the lowest boundary for a 3-mm cell dimension for a body-centered cubic structure with struts along the cube edges (BCCXYZ) and built with the vertical edges parallel to the growth direction to account for the worst-case scenario. Lighter structures of this kind, even if theoretically compliant with technical specifications of the machine, result in unstable frameworks.

Solid-State Phase Transformations in Thermally Treated Ti-6Al-4V Alloy Fabricated via Laser Powder Bed Fusion.

Laser Powder Bed Fusion (LPBF) technology was used to produce samples based on the Ti-6Al-4V alloy for biomedical applications. Solid-state phase transformations induced by thermal treatments were studied by neutron diffraction (ND), X-ray diffraction (XRD), scanning transmission electron microscopy (STEM) and energy-dispersive spectroscopy (EDS). Although, ND analysis is rather uncommon in such studies, this technique allowed evidencing the presence of retained ß in α' martensite of the as-produced (#AP) sample. The retained ß was not detectable by XRD analysis, nor by STEM observations. Martensite contains a high number of defects, mainly dislocations, that anneal during the thermal treatment. Element diffusion and partitioning are the main mechanisms in the α ↔ ß transformation that causes lattice expansion during heating and determines the final shape and size of phases. The retained ß phase plays a key role in the α' → ß transformation kinetics.

Lime-cement textile reinforced mortar (TRM) with modified interphase.

BACKGROUND:: Lack of interphase compatibility between the fabric and the matrix significantly impairs the load-bearing capacity of textile reinforced mortar (TRM). In this study, we consider the application of two inorganic surface coatings for enhancing the interphase bond properties. METHODS:: Either of two silica-based coatings, namely nano- and micro-silica, were applied to alkali-resistant glass (ARG) and to hybrid carbon-ARG woven fabric. Mechanical performance of TRM reinforced with the uncoated and the coated fabric was compared in uniaxial tensile tests. RESULTS:: Mechanical testing provides evidence of a remarkable enhancement in terms of ultimate strength and deformability for the coated specimens. This effect can be ascribed to the improved hydrophilicity of the fibers' surface and to the activation of pozzolanic reaction at the interphase. In addition, penetration of nano- and microparticles in the bundle of the textile yarns reduces the occurrence of telescopic failure.

Development of solvent-casting particulate leaching (SCPL) polymer scaffolds as improved three-dimensional supports to mimic the bone marrow niche.

The need for new approaches to investigate ex vivo the causes and effects of tumor and to achieve improved cancer treatments and medical therapies is particularly urgent for malignant pathologies such as lymphomas and leukemias, whose tissue initiator cells interact with the stroma creating a three-dimensional (3D) protective environment that conventional mono- and bi-dimensional (2D) models are not able to simulate realistically. The solvent-casting particulate leaching (SCPL) technique, that is already a standard method to produce polymer-based scaffolds for bone tissue repair, is proposed here to fabricate innovative 3D porous structures to mimic the bone marrow niche in vitro. Two different polymers, namely a rigid polymethyl methacrylate (PMMA) and a flexible polyurethane (PU), were evaluated to the purpose, whereas NaCl, in the form of common salt table, resulted to be an efficient porogen. The adoption of an appropriate polymer-to-salt ratio, experimentally defined as 1:4 for both PMMA and PU, gave place to a rich and interconnected porosity, ranging between 82.1 vol% and 91.3 vol%, and the choice of admixing fine-grained or coarse-grained salt powders allowed to control the final pore size. The mechanical properties under compression load were affected both by the polymer matrix and by the scaffold's architecture, with values of the elastic modulus indicatively varying between 29 kPa and 1283 kPa. Preliminary tests performed with human stromal HS-5 cells co-cultured with leukemic cells allowed us to conclude that stromal cells grown associated to the supports keep their well-known protective and pro-survival effect on cancer cells, indicating that these devices can be very useful to mimic the bone marrow microenvironment and therefore to assess the efficacy of novel therapies in pre-clinical studies.

Development of Laser-Based Powder Bed Fusion Process Parameters and Scanning Strategy for New Metal Alloy Grades: A Holistic Method Formulation.

In spite of the fast growth of laser-based powder bed fusion (L-PBF) processes as a part of everyday industrial practice, achieving consistent production is hampered by the scarce repeatability of performance that is often encountered across different additive manufacturing (AM) machines. In addition, the development of novel feedstock materials, which is fundamental to the future growth of AM, is limited by the absence of established methodologies for their successful exploitation. This paper proposes a structured procedure with a complete test plan, which defines step-by-step the standardized actions that should be taken to optimize the processing parameters and scanning strategy in L-PBF of new alloy grades. The method is holistic, since it considers all the laser/material interactions in different local geometries of the build, and suggests, for each possible interaction, a specific geometry for test specimens, standard energy parameters to be analyzed through a design of experiment, and measurable key performance indicators. The proposed procedure therefore represents a sound and robust aid to the development of novel alloy grades for L-PBF and to the definition of the most appropriate processing conditions for them, independent of the specific AM machine applied.

Increased production of bacterial cellulose as starting point for scaled-up applications.

Bacterial cellulose is composed of an ultrafine nanofiber network and well-ordered structure; therefore, it offers several advantages when used as native polymer or in composite systems.In this study, a pool of 34 acetic acid bacteria strains belonging to Komagataeibacter xylinus were screened for their ability to produce bacterial cellulose. Bacterial cellulose layers of different thickness were observed for all the culture strains. A high-producing strain, which secreted more than 23 g/L of bacterial cellulose on the isolation broth during 10 days of static cultivation, was selected and tested in optimized culture conditions. In static conditions, the increase of cellulose yield and the reduction of by-products such as gluconic acid were observed. Dried bacterial cellulose obtained in the optimized broth was characterized to determine its microstructural, thermal, and mechanical properties. All the findings of this study support the use of bacterial cellulose produced by the selected strain for biomedical and food applications.

Proposal of a Novel Natural Biomaterial, the Scleral Ossicle, for the Development of Vascularized Bone Tissue In Vitro.

Recovering of significant skeletal defects could be partially abortive due to the perturbations that affect the regenerative process when defects reach a critical size, thus resulting in a non-healed bone. The current standard treatments include allografting, autografting, and other bone implant techniques. However, although they are commonly used in orthopedic surgery, these treatments have some limitations concerning their costs and their side effects such as potential infections or malunions. On this account, the need for suitable constructs to fill the gap in wide fractures is still urgent. As an innovative solution, scleral ossicles (SOs) can be put forward as natural scaffolds for bone repair. SOs are peculiar bony plates forming a ring at the scleral-corneal border of the eyeball of lower vertebrates. In the preliminary phases of the study, these ossicles were structurally and functionally characterized. The morphological characterization was performed by SEM analysis, MicroCT analysis and optical profilometry. Then, UV sterilization was carried out to obtain a clean support, without neither contaminations nor modifications of the bone architecture. Subsequently, the SO biocompatibility was tested in culture with different cell lines, focusing the attention to the differentiation capability of endothelial and osteoblastic cells on the SO surface. The results obtained by the above mentioned analysis strongly suggest that SOs can be used as bio-scaffolds for functionalization processes, useful in regenerative medicine.

Role of magnesium oxide and strontium oxide as modifiers in silicate-based bioactive glasses: Effects on thermal behaviour, mechanical properties and in-vitro bioactivity.

The composition of a CaO-rich silicate bioglass (BG_Ca-Mix, in mol%: 2.3 Na2O; 2.3 K2O; 45.6 CaO; 2.6 P2O5; 47.2 SiO2) was modified by replacing a fixed 10mol% of CaO with MgO or SrO or fifty-fifty MgO-SrO. The thermal behaviour of the modified glasses was accurately evaluated via differential thermal analysis (DTA), heating microscopy and direct sintering tests. The presence of MgO and/or SrO didn't interfere with the thermal stability of the parent glass, since all the new glasses remained completely amorphous after sintering (treatment performed at 753°C for the glass with MgO; at 750°C with SrO; at 759°C with MgO and SrO). The sintered samples achieved good mechanical properties, with a Young's modulus ranging between 57.9±6.7 for the MgO-SrO modified composition and 112.6±8.0GPa for the MgO-modified one. If immersed in a simulated body fluid (SBF), the modified glasses after sintering retained the strong apatite forming ability of the parent glass, in spite of the presence of MgO and/or SrO. Moreover, the sintered glasses, tested with MLO-Y4 osteocytes by means of a multi-parametrical approach, showed a good bioactivity in vitro, since neither the glasses nor their extracts caused any negative effect on cell viability or any inhibition on cell growth. The best results were achieved by the MgO-modified glasses, both BGMIX_Mg and BGMIX_MgSr, which were able to exert a strong stimulating effect on the cell growth, thus confirming the beneficial effect of MgO on the glass bioactivity.

Functionally graded materials for orthopedic applications - an update on design and manufacturing.

Functionally graded materials (FGMs) are innovative materials whose composition and/or microstructure gradually vary in space according to a designed law. As a result, also the properties gradually vary in space, so as to meet specific non-homogeneous service requirements without any abrupt interface at the macroscale. FGMs are emerging materials for orthopedic prostheses, since the functional gradient can be adapted to reproduce the local properties of the original bone, which helps to minimize the stress shielding effect and, at the same time, to reduce the shear stress between the implant and the surrounding bone tissue, two critical prerequisites for a longer lifespan of the graft. After a brief introduction to the origin of the FGM concept, the review surveys some representative examples of graded systems which are present in nature and, in particular, in the human body, with a focus on bone tissue. Then the rationale for using FGMs in orthopedic devices is discussed more in detail, taking into account both biological and biomechanical requirements. The core of the paper is dedicated to two fundamental topics, which are essential to benefit from the use of FGMs for orthopedic applications, namely (1) the computational tools for materials design and geometry optimization, and (2) the manufacturing techniques currently available to produce FGM-based grafts. This second part, in its turn, is structured to consider the production of functionally graded coatings (FGCs), of functionally graded 3D parts, and of special devices with a gradient in porosity (functionally graded scaffolds). The inspection of the literature on the argument clearly shows that the integration of design and manufacturing remains a critical step to overpass in order to achieve effective FGM-based implants.

Hydroxyapatite and tricalcium phosphate composites with bioactive glass as second phase: State of the art and current applications.

Calcium phosphates are among the most common biomaterials employed in orthopaedic and dental surgery. The efficacy of such systems as bone substitutes and bioactive coatings on metallic prostheses has been proved by several clinical studies. Among these materials, hydroxyapatite (HA) and tricalcium phosphate (TCP) play a prominent role in medical practice since the '80s. In the last years, numerous attempts to combine HA or TCP with bioactive glasses have been made. There are two main motivations for sintering calcium phosphates with a glassy phase: on the one hand, it is possible to tune the dissolution of the final system and to enhance its biological response through the synergistic combination of two bioactive phases; on the other hand, the glass acts as a sintering aid with the aim to increase the densification of the composite and thus its mechanical strength. In this sense, TCP and HA are penalized by their relatively poor fracture toughness and tensile strength compared to natural bone, which makes it impossible to use them in load-bearing applications. Moreover, the bioactivity index of pure calcium phosphates is typically lower with respect to that of many bioactive glasses. In this review, the state of the art and current applications of composites, based on HA or TCP with bioactive glass as second phase, are presented and discussed. A special emphasis is given to the processing and mechanical behaviour of these systems, together with their biological implications, as a function of the composition of the glass employed as second phase.

Bioactive glass/hydroxyapatite composites: mechanical properties and biological evaluation.

Bioactive glass/hydroxyapatite composites for bone tissue repair and regeneration have been produced and discussed. The use of a recently developed glass, namely BG_Ca/Mix, with its low tendency to crystallize, allowed one to sinter the samples at a relatively low temperature thus avoiding several adverse effects usually reported in the literature, such as extensive crystallization of the glassy phase, hydroxyapatite (HA) decomposition and reaction between HA and glass. The mechanical properties of the composites with 80wt.% BG_Ca/Mix and 20wt.% HA are sensibly higher than those of Bioglass® 45S5 reference samples due to the presence of HA (mechanically stronger than the 45S5 glass) and to the thermal behaviour of the BG_Ca/Mix, which is able to favour the sintering process of the composites. Biocompatibility tests, performed with murine fibroblasts BALB/3T3 and osteocites MLO-Y4 throughout a multi-parametrical approach, allow one to look with optimism to the produced composites, since both the samples themselves and their extracts do not induce negative effects in cell viability and do not cause inhibition in cell growth.

Composite scaffolds for controlled drug release: role of the polyurethane nanoparticles on the physical properties and cell behaviour.

Localised delivery of appropriate biomolecule/drug(s) can be suitable to prevent postoperative infections and inflammation after scaffold implantation in vivo. In this study composite shell scaffolds, based on an internally produced bioactive glass and a commercial hydroxyapatite, were surface coated with a uniform polymeric layer, embedded with thermo-stable polyesterurethane (PU)-based nanoparticles (NPs), containing an anti-inflammatory drug (indomethacin; IDCM). The obtained functionalised scaffolds were subjected to physico-mechanical and biological characterisations. The results indicated that NPs incorporation into the gelatin coating of the composite scaffolds: 1) not changed significantly the micro-architecture of the scaffolds in terms of mean pore diameter and pore size distribution; 2) increased the compressive modulus; and 3) allowed to a sustained IDMC release (65-70% of the loaded-drug) within the first week of incubation in physiological solution. On the other hand, the NPs incorporation did not affect the biocompatibility of composite scaffolds, as evidenced by viability and alkaline phosphatase (ALP) activity of MG63 human osteoblast-like cells.

Sol-gel derived bioactive glasses with low tendency to crystallize: synthesis, post-sintering bioactivity and possible application for the production of porous scaffolds.

A new sol-gel (SG) method is proposed to produce special bioactive glasses (BG_Ca family) characterized by a low tendency to devitrify. These formulations, derived from 45S5 Bioglass®, are characterized by a high content of CaO (45.6 mol%) and by a partial or complete substitution of sodium oxide with potassium oxide (total amount of alkaline oxides: 4.6 mol%), which increases the crystallization temperature up to 900°C. In this way, it is possible to produce them by SG preserving their amorphous nature, in spite of the calcination at 850°C. The sintering behavior of the obtained SG powders is thoroughly investigated and the properties of the sintered bodies are compared to those of the melt-derived (M) counterparts. Furthermore, the SG glass powders are successfully used to produce scaffolds by means of a modified replication technique based on the combined use of polyurethane sponges and polyethylene particles. Finally, in the view of a potential application for bone tissue engineering, the cytotoxicity of the produced materials is evaluated in vitro.

Mg- and/or Sr-doped tricalcium phosphate/bioactive glass composites: synthesis, microstructure and biological responsiveness.

Presently, there is an increasing interest towards the composites of calcium phosphates, especially ß-tricalcium phosphate (TCP), and bioactive glasses. In the present contribution, the recently developed BG_Ca/Mix glass has been used because its low tendency to crystallize allows to sinter the composites at relatively low temperature (i.e. 850°C), thus minimizing the glass devitrification and the interaction with TCP. A further improvement is the introduction of lab-produced TCP powders doped with specific ions instead of non-doped commercial powders, since the biological properties of materials for bone replacement can be modulated by doping them with certain metallic ions, such as Mg and Sr. Therefore, novel binary composites have been produced by sintering the BG_Ca/Mix glass with the addition of pure, Mg-substituted, Sr-substituted or Mg/Sr bisubstituted TCP powders. After an accurate characterization of the starting TCP powders and of the obtained samples, the composites have been used as three-dimensional supports for the culture of mouse calvaria-derived pre-osteoblastic cells. The samples supported cell adhesion and proliferation and induced promising mechanisms of differentiation towards an osteoblastic phenotype. In particular, the Mg/Sr bi-doped samples seemed to better promote the differentiation process thus suggesting a combined stimulatory effect of Mg(2+) and Sr(2+) ions.

Microstructural design of functionally graded coatings composed of suspension plasma sprayed hydroxyapatite and bioactive glass.

Various bioactive glass/hydroxyapatite (HA) functional coatings were designed by the suspension plasma spraying (SPS) technique. Their microstructure, scratch resistance, and apatite-forming ability in a simulated body fluid (SBF) were compared. The functional coatings design included: (i) composite coating, that is, randomly distributed constituent phases; (ii) duplex coating with glass top layer onto HA layer; and (iii) graded coating with a gradual changing composition starting from pure HA at the interface with the metal substrate up to pure glass on the surface. The SPS was a suitable coating technique to produce all the coating designs. The SBF tests revealed that the presence of a pure glass layer on the working surface significantly improved the reactivity of the duplex and graded coatings, but the duplex coating suffered a relatively low scratch resistance because of residual stresses. The graded coating therefore provided the best compromise between mechanical reliability and apatite-forming ability in SBF. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 102B: 551-560, 2014.

Suspension thermal spraying of hydroxyapatite: microstructure and in vitro behaviour.

In cementless fixation of metallic prostheses, bony ingrowth onto the implant surface is often promoted by osteoconductive plasma-sprayed hydroxyapatite coatings. The present work explores the use of the innovative High Velocity Suspension Flame Spraying (HVSFS) process to coat Ti substrates with thin homogeneous hydroxyapatite coatings. The HVSFS hydroxyapatite coatings studied were dense, 27-37µm thick, with some transverse microcracks. Lamellae were sintered together and nearly unidentifiable, unlike conventional plasma-sprayed hydroxyapatite. Crystallinities of 10%-70% were obtained, depending on the deposition parameters and the use of a TiO2 bond coat. The average hardness of layers with low (<24%) and high (70%) crystallinity was ≈3.5GPa and ≈4.5GPa respectively. The distributions of hardness values, all characterised by Weibull modulus in the 5-7 range, were narrower than that of conventional plasma-sprayed hydroxyapatite, with a Weibull modulus of ≈3.3. During soaking in simulated body fluid, glassy coatings were progressively resorbed and replaced by a new, precipitated hydroxyapatite layer, whereas coatings with 70% crystallinity were stable up to 14days of immersion. The interpretation of the precipitation behaviour was also assisted by surface charge assessments, performed through Z-potential measurements. During in vitro tests, HA coatings showed no cytotoxicity towards the SAOS-2 osteoblast cell line, and surface cell proliferation was comparable with proliferation on reference polystyrene culture plates.