Enabling Circular Economy: The Overlooked Role of Inorganic Materials Chemistry.

Circular economy is considered a new chance to build a more sustainable world from both the social and the economic point of view. In this Essay, the possible contribution of inorganic chemistry towards a smooth transition to circularity in inorganic materials design and production is discussed by adopting an interdisciplinary approach.

Osteogenic Properties of 3D-Printed Silica-Carbon-Calcite Composite Scaffolds: Novel Approach for Personalized Bone Tissue Regeneration.

Carbon enriched bioceramic (C-Bio) scaffolds have recently shown exceptional results in terms of their biological and mechanical properties. The present study aims at assessing the ability of the C-Bio scaffolds to affect the commitment of canine adipose-derived mesenchymal stem cells (cAD-MSCs) and investigating the influence of carbon on cell proliferation and osteogenic differentiation of cAD-MSCs in vitro. The commitment of cAD-MSCs to an osteoblastic phenotype has been evaluated by expression of several osteogenic markers using real-time PCR. Biocompatibility analyses through 3-(4,5-dimethyl- thiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT), lactate dehydrogenase (LDH) activity, hemolysis assay, and Ames test demonstrated excellent biocompatibility of both materials. A significant increase in the extracellular alkaline phosphatase (ALP) activity and expression of runt-related transcription factor (RUNX), ALP, osterix (OSX), and receptor activator of nuclear factor kappa-Β ligand (RANKL) genes was observed in C-Bio scaffolds compared to those without carbon (Bio). Scanning electron microscopy (SEM) demonstrated excellent cell attachment on both material surfaces; however, the cellular layer on C-Bio fibers exhibited an apparent secretome activity. Based on our findings, graphene can improve cell adhesion, growth, and osteogenic differentiation of cAD-MSCs in vitro. This study proposed carbon as an additive for a novel three-dimensional (3D)-printable biocompatible scaffold which could become the key structural material for bone tissue reconstruction.

Recycling of inorganic waste in monolithic and cellular glass-based materials for structural and functional applications.

The stabilization of inorganic waste of various nature and origin, in glasses, has been a key strategy for environmental protection for the last decades. When properly formulated, glasses may retain many inorganic contaminants permanently, but it must be acknowledged that some criticism remains, mainly concerning costs and energy use. As a consequence, the sustainability of vitrification largely relies on the conversion of waste glasses into new, usable and marketable glass-based materials, in the form of monolithic and cellular glass-ceramics. The effective conversion in turn depends on the simultaneous control of both starting materials and manufacturing processes. While silica-rich waste favours the obtainment of glass, iron-rich wastes affect the functionalities, influencing the porosity in cellular glass-based materials as well as catalytic, magnetic, optical and electrical properties. Engineered formulations may lead to important reductions of processing times and temperatures, in the transformation of waste-derived glasses into glass-ceramics, or even bring interesting shortcuts. Direct sintering of wastes, combined with recycled glasses, as an example, has been proven as a valid low-cost alternative for glass-ceramic manufacturing, for wastes with limited hazardousness. The present paper is aimed at providing an up-to-date overview of the correlation between formulations, manufacturing technologies and properties of most recent waste-derived, glass-based materials. © 2016 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Waste Glass Upcycling Supported by Alkali Activation: An Overview.

Alkali-activated materials are gaining much interest due to their outstanding performance, including their great resistance to chemical corrosion, good thermal characteristics, and ability to valorise industrial waste materials. Reusing waste glasses in creating alkali-activated materials appears to be a viable option for more effective solid waste utilisation and lower-cost products. However, very little research has been conducted on the suitability of waste glass as a prime precursor for alkali activation. This study examines the reuse of seven different types of waste glasses in the creation of geopolymeric and cementitious concretes as sustainable building materials, focusing in particular on how using waste glasses as the raw material in alkali-activated materials affects the durability, microstructures, hydration products, and fresh and hardened properties in comparison with using traditional raw materials. The impacts of several vital parameters, including the employment of a chemical activator, gel formation, post-fabrication curing procedures, and the distribution of source materials, are carefully considered. This review will offer insight into an in-depth understanding of the manufacturing and performance in promising applications of alkali-activated waste glass in light of future uses. The current study aims to provide a contemporary review of the chemical and structural properties of glasses and the state of research on the utilisation of waste glasses in the creation of alkali-activated materials.

Upcycling waste derived glass into high-performance photocatalytic scaffolds by alkali activation and direct ink writing.

Novel and eco-friendly solutions are extensively needed for wastewater treatment. This work capitalizes on the combination of waste vitrification and additive manufacturing to produce an efficient photocatalyst for the specific purpose. Fine powders of waste-derived glass, containing Fe3O4 inclusions, by simple suspension (for a solid loading of 65 wt %) in alkaline solution (5 M NaOH), were transformed into pastes for direct ink writing. 3D-printed reticulated scaffolds were stabilized by the progressive hardening of a zeolite-like gel, formed by glass/solution interaction, at nearly room temperature. The printed scaffolds were successfully tested for the removal of methylene blue, realized by combining the high sorption capacity of the gel with the catalytic activity of magnetite inclusions, under UV light. A complete degradation of methylene blue is achieved by 90 min exposure, comparing favorably with other reported photocatalytic materials, requiring from 60 to 360 min. The photocatalytic activity was tested for several cycles, with no significant degradation. In other words, a waste-derived material can be reused for multiple times, to remediate wastewaters, with evident benefits on waste minimization.

Environmental performance of glass foam as insulation material from waste glass with the alkali activation process.

Glass foams is an interesting option for the use of fractions of glass cullet otherwise destined to landfills. As building insulation materials, glass foams obtained by conventional processes have still some drawbacks in the purity of starting feedstock, which can be avoided by implementing an alkali activation process. Using the life cycle assessment methodology, the research analyses the potential impacts associated to the glass foam obtained from waste glass through the alkali activation in a laboratory scale plant with 'cradle to grave' perspective. The main phases included in the system boundaries are the downstream activities related to the transportation of glass waste and avoided landfill disposal, the production process to obtain the glass foam, and the upstream activities related to the transportation to potential use phase and the end of life. The life cycle environmental profile of glass foam is calculated starting from primary data integrated with the Ecoinvent database, and using the ReCiPe 2016 impact assessment method and the SimaPro software. Results demonstrate the greatest contribution on the overall environmental impacts due to the production, in which the main impacts are linked to electricity consumption for drying and firing and surfactant for the foaming. Sensitivity analyses clarify that consistent improvement in overall environmental impacts can be obtain with minimization of distances both between glass waste and production site, and between glass foam production and use; otherwise, different energy-mix and lower temperature in chemical processes have negligible effects in the environmental profile. The research reveals useful information to optimize the upcycling of glass foam production before moving on the industrialization: future investigations should involve the selection of biodegradable surfactants, from renewable sources.

Novel glass-based membranes for Cu adsorption: From alkali activation to sintering.

A porous membrane was developed through alkali activation of pharmaceutical boro-alumino-silicate glass powders suspended in diluted NaOH and KOH aqueous solutions (2.5 M). A consolidated porous structure was obtained by the binding of unreacted particles mediated by a surface gel, developed upon drying of the suspensions and their curing at 40 °C for 14 days. The binding phase was sufficiently stable to resist immersion in boiling water and in acidic solutions. Copper adsorption tests were carried out under acidic pH, immersing the membranes in a Cu(NO3)2 solution for different periods of time. To determine the effect of surface washing on capture of copper ions, adsorption experiments with washed and unwashed membranes were also carried out, at varying pH. It was determined that the adsorption kinetics follow the pseudo-second-order kinetic model. The main adsorption mechanism observed is the electrostatic interaction between the negative surface charge of the washed membrane and the Cu2+ ions present in solution. An adsorption higher than 60% was observed at pH = 5, while at pH = 2 the efficiency decreased due to the presence of H3O+ ions. To ensure immobilization of copper, the membranes were densified by viscous flow sintering at a moderate temperature (700 °C). Leaching tests on membranes demonstrated the efficiency of the process in terms of copper ions immobilization.

Modeling Materials Coextrusion in Polymers Additive Manufacturing.

Material extrusion additive manufacturing enables us to combine more materials in the same nozzle during the deposition process. This technology, called material coextrusion, generates an expanded range of material properties, which can gradually change in the design domain, ensuring blending or higher bonding/interlocking among the different materials. To exploit the opportunities offered by these technologies, it is necessary to know the behavior of the combined materials according to the materials fractions. In this work, two compatible pairs of materials, namely Polylactic Acid (PLA)-Thermoplastic Polyurethane (TPU) and Acrylonitrile Styrene Acrylate (ASA)-TPU, were investigated by changing the material fractions in the coextrusion process. An original model describing the distribution of the materials is proposed. Based on this, the mechanical properties were investigated by analytical and numerical approaches. The analytical model was developed on the simplified assumption that the coextruded materials are a set of rods, whereas the more realistic numerical model is based on homogenization theory, adopting the finite element analysis of a representative volume element. To verify the deposition model, a specific experimental test was developed, and the modeled material deposition was superimposed and qualitatively compared with the actual microscope images regarding the different deposition directions and material fractions. The analytical and numerical models show similar trends, and it can be assumed that the finite element model has a more realistic behavior due to the higher accuracy of the model description. The elastic moduli obtained by the models was verified in experimental tensile tests. The tensile tests show Young's moduli of 3425 MPa for PLA, 1812 MPa for ASA, and 162 MPa for TPU. At the intermediate material fraction, the Young's modulus shows an almost linear trend between PLA and TPU and between ASA and TPU. The ultimate tensile strength values are 63.9 MPa for PLA, 35.7 MPa for ASA, and 63.5 MPa for TPU, whereas at the intermediate material fraction, they assume lower values. In this initial work, the results show a good agreement between models and experiments, providing useful tools for designers and contributing to a new branch in additive manufacturing research.

In vitro evaluation of granules obtained from 3D sphene scaffolds and bovine bone grafts: chemical and biological assays.

Sphene is an innovative bone graft material. The aim of this study was to investigate and compare the physicochemical and biological properties of Bio-Oss® (BO) and in-lab synthesized and processed sphene granules. BO granules of 1000-2000 µm (BO-L), 250-1000 µm (BO-S) and 100-200 µm (BO-p) for derived granules, and corresponding groups of sphene granules obtained from 3D printed blocks (SB-L, SB-S, SB-p) and foams (SF-L, SF-S and SF-p) were investigated. The following analyses were conducted: morphological analysis, specific surface area and porosity, inductively coupled plasma mass spectrometry (ICP-MS), cytotoxicity assay, Alizarin staining, bone-related gene expression, osteoblast migration and proliferation assays. All pulverized granules exhibited a similar morphology and SF-S resembled natural bone. Sphene-derived granules showed absence of micro- and mesopores and a low specific surface area. ICP-MS revealed a tendency for absorption of Ca and P for all BO samples, while sphene granules demonstrated a release of Ca. No cellular cytotoxicity was detected and osteoblastic phenotype in primary cells was observed, with significantly increased values for SF-L, SF-S, BO-L and BO-p. Further investigations are needed before clinical use can be considered.

Proteolytically Resistant Bioactive Peptide-Grafted Sr/Mg-Doped Hardystonite Foams: Comparison of Two Covalent Functionalization Strategies.

Hardystonite-based (HT) bioceramic foams were easily obtained via thermal treatment of silicone resins and reactive oxide fillers in air. By using a commercial silicone, incorporating strontium oxide and magnesium oxide precursors (as well as CaO and ZnO), and treating it at 1100 °C, a complex solid solution (Ca1.4Sr0.6Zn0.85Mg0.15Si2O7) that has superior biocompatibility and bioactivity properties compared to pure hardystonite (Ca2ZnSi2O7) can be obtained. Proteolytic-resistant adhesive peptide mapped on vitronectin (D2HVP), was selectively grafted to Sr/Mg-doped HT foams using two different strategies. Unfortunately, the first method (via protected peptide) was unsuitable for acid-sensitive materials such as Sr/Mg-doped HT, resulting in the release of cytotoxic levels of Zinc over time, with consequent negative cellular response. To overcome this unexpected result, a novel functionalization strategy requiring aqueous solution and mild conditions was designed. Sr/Mg-doped HT functionalized with this second strategy (via aldehyde peptide) showed a dramatic increase in human osteoblast proliferation at 6 days compared to only silanized or non-functionalized samples. Furthermore, we demonstrated that the functionalization treatment does not induce any cytotoxicity. Functionalized foams enhanced mRNA-specific transcript levels coding IBSP, VTN, RUNX2, and SPP1 at 2 days post-seeding. In conclusion, the second functionalization strategy proved to be appropriate for this specific biomaterial and was effective at enhancing the material's bioactivity.

Advanced Dye Sorbents from Combined Stereolithography 3D Printing and Alkali Activation of Pharmaceutical Glass Waste.

Additive manufacturing (AM) technologies enable the fabrication of objects with complex geometries in much simpler ways than conventional shaping methods. With the fabrication of recyclable filters for contaminated waters, the present work aims at exploiting such features as an opportunity to reuse glass from discarded pharmaceutical containers. Masked stereolithography-printed scaffolds were first heat-treated at relatively low temperatures (680 and 730 °C for 1 h) and then functionalized by alkali activation, with the formation of zeolite and sodium carbonate phases, which worked as additional adsorbing centers. As-sintered and activated scaffolds were characterized in terms of the efficiency of filtration and removal of methylene blue, used as a reference dye. The adsorption efficiency of activated printed glass was 81%. The 3D-printed adsorbent can be easily separated from the solution for reuse.

3D Printing of Hierarchically Porous Lattice Structures Based on Åkermanite Glass Microspheres and Reactive Silicone Binder.

The present study illustrates the manufacturing method of hierarchically porous 3D scaffolds based on åkermanite as a promising bioceramic for stereolithography. The macroporosity was designed by implementing 3D models corresponding to different lattice structures (cubic, diamond, Kelvin, and Kagome). To obtain micro-scale porosity, flame synthesized glass microbeads with 10 wt% of silicone resins were utilized to fabricate green scaffolds, later converted into targeted bioceramic phase by firing at 1100 °C in air. No chemical reaction between the glass microspheres, crystallizing into åkermanite, and silica deriving from silicone oxidation was observed upon heat treatment. Silica acted as a binder between the adjacent microspheres, enhancing the creation of microporosity, as documented by XRD, and SEM coupled with EDX analysis. The formation of 'spongy' struts was confirmed by infiltration with Rhodamine B solution. The compressive strength of the sintered porous scaffolds was up to 0.7 MPa with the porosity of 68-84%.

Robocasting of advanced ceramics: ink optimization and protocol to predict the printing parameters - A review.

Direct-Ink-Writing (or robocasting) is a subset of extrusion-based additive manufacturing techniques that has grown significantly in recent years to design simple to complex ceramic structures. Robocasting, relies on the use of high-concentration powder pastes, also known as inks. A successful optimization of ink rheology and formulation constitutes the major key factor to ensure printability for the fabrication of self-supporting ceramic structures with a very precise dimensional resolution. However, to date achieving a real balance between a comprehensive optimization of ink rheology and the determination of a relevant protocol to predict the printing parameters for a given ink is still relatively scarce and has been not yet standardized in the literature. The current review reports, in its first part, a detailed survey of recent studies on how ink constituents and composition affect the direct-ink-writing of ceramic parts, taking into account innovative ceramic-based-inks formulations and processing techniques. Precisely, the review elaborates the major factors influencing on ink rheology and printability, specifically binder type, particle physical features (size, morphology and density) and ceramic feedstock content. In the second part, this review suggests a standardized guideline to effectively adapt a suitable setting of the printing parameters, such as printing speed and pressure, printing substrate, strut spacing, layer height, nozzle diameter in function of ink intrinsic rheology.

Novel Functional Glass-Ceramic Coatings on Titanium Substrates from Glass Powders and Reactive Silicone Binders.

'Silica-defective glasses', combined with a silicone binder, have been already shown as a promising solution for the manufacturing of glass-ceramics with complex geometries. A fundamental advantage is the fact that, after holding glass powders together from room temperature up to the firing temperature, the binder does not completely disappear. More precisely, it converts into silica when heat-treated in air. A specified 'target' glass-ceramic formulation results from the interaction between glass powders and the binder-derived silica. The present paper is dedicated to the extension of the approach to the coating of titanium substrates (to be used for dental and orthopedic applications), with a bioactive wollastonite-diopside glass-ceramic layer, by the simple airbrushing of suspensions of glass powders in alcoholic silicone solutions. The interaction between glass and silica from the decomposition of the binder led to crack-free glass-ceramic coatings, upon firing in air; in argon, the glass/silicone mixtures yielded novel composite coatings, embedding pyrolytic carbon. The latter phase enabled the absorption of infrared radiation from the coating, which is useful for disinfection purposes.

Upcycling of Pharmaceutical Glass into Highly Porous Ceramics: From Foams to Membranes.

The present COVID-19 emergency has dramatically increased the demand for pharmaceutical containers, especially vials. End-of-life containers, however, cannot be easily recycled in the manufacturing of new articles. This paper presents some strategies for upcycling of pharmaceutical glass into various porous ceramics. Suspensions of a fine glass powder (70 vol%) are used as a starting material. Highly uniform cellular structures may be easily prepared by vigorous mechanical stirring of partially gelified suspensions with added surfactant, followed by drying and firing at 550-650 °C. Stabilization of the cellular structures at temperatures as low as the glass transition temperature (Tg) of the used glass is facilitated by thermal decomposition of the gel phase, instead of viscous flow sintering of glass. This finding enabled the preparation of glass membranes (∼78 vol% open porosity), by direct firing of hardened suspensions, avoiding any surfactant addition and mechanical stirring. The powders obtained by crushing of hardened suspensions, even in unfired state, may be used as a low-cost sorbent for dye removal.

Electrical Properties of Aluminum Nitride Thick Films Magnetron Sputtered on Aluminum Substrates.

The realization of a c-axis oriented aluminum nitride thick film on aluminum substrates is a promising step in the development of transducers for applications with a working temperature up to about 600 °C. The present paper deals with the realization of AlN thick films by means of reactive magnetron sputtering with a pulsed DC power supply, operating in continuous mode for 50 h. Two values (0.4 and 0.8) of nitrogen concentration were used; operative pressure and power were set at 0.3 Pa and 150 W, respectively. The thickness of the obtained aluminum nitride films on the aluminum substrate, assessed with a profilometer, varied from 20 to 30 µm. The preferential orientation of AlN crystals was verified by X-ray diffraction. Finally, as the main focus of the investigation, the films underwent electrical characterization by means of an LCR-meter used on a parallel plate capacitor set-up and a test system based on a cantilever beam configuration. AlN conductivity and ε33 permittivity were derived in the 100 Hz-300 kHz frequency range. Magnetron sputtering operation with nitrogen concentration equal to 0.4 resulted in the preferred operative condition, leading to a d31 piezoelectric coefficient, in magnitude, of 0.52 × 10-12 C/N.

Porous Glass Microspheres from Alkali-Activated Fiber Glass Waste.

Fiber glass waste (FGW) was subjected to alkali activation in an aqueous solution with different concentrations of sodium/potassium hydroxide. The activated materials were fed into a methane-oxygen flame with a temperature of around 1600 °C. X-ray diffraction analysis confirmed the formation of several hydrated compounds, which decomposed upon flame synthesis, leading to porous glass microspheres (PGMs). Pore formation was favored by using highly concentrated activating alkali solutions. The highest homogeneity and yield of PGMs corresponded to the activation with 9 M KOH aqueous solution.

Polymer-Derived Biosilicate®-like Glass-Ceramics: Engineering of Formulations and Additive Manufacturing of Three-Dimensional Scaffolds.

Silicone resins, filled with phosphates and other oxide fillers, yield upon firing in air at 1100 °C, a product resembling Biosilicate® glass-ceramics, one of the most promising systems for tissue engineering applications. The process requires no preliminary synthesis of parent glass, and the polymer route enables the application of direct ink writing (DIW) of silicone-based mixtures, for the manufacturing of reticulated scaffolds at room temperature. The thermal treatment is later applied for the conversion into ceramic scaffolds. The present paper further elucidates the flexibility of the approach. Changes in the reference silicone and firing atmosphere (from air to nitrogen) were studied to obtain functional composite biomaterials featuring a carbon phase embedded in a Biosilicate®-like matrix. The microstructure was further modified either through a controlled gas release at a low temperature, or by the revision of the adopted additive manufacturing technology (from DIW to digital light processing).

Up-Cycling of LCD Glass by Additive Manufacturing of Porous Translucent Glass Scaffolds.

Additive manufacturing technologies, compared to conventional shaping methods, offer great opportunities in design versatility, for the manufacturing of highly porous ceramic components. However, the application to glass powders, later subjected to viscous flow sintering, involves significant challenges, especially in shape retention and in the achievement of a substantial degree of translucency in the final products. The present paper disclosed the potential of glass recovered from liquid crystal displays (LCD) for the manufacturing of highly porous scaffolds by direct ink writing and masked stereolithography of fine powders mixed with suitable organic additives, and sintered at 950 °C, for 1-1.5 h, in air. The specific glass, featuring a relatively high transition temperature (Tg~700 °C), allowed for the complete burn-out of organics before viscous flow sintering could take place; in addition, translucency was favored by the successful removal of porosity in the struts and by the resistance of the used glass to crystallization.

Biofunctionalization of bioactive ceramic scaffolds to increase the cell response for bone regeneration.

Biofunctionalization was investigated for polymers and metals considering their scarce integration ability. On the contrary few studies dealt with ceramic biofunctionalization because the bioactive and bioresorbable surfaces of ceramics are able to positively interact with biological environment. In this study the cell-response improvement on biofunctionalized wollastonite and diopside-based scaffolds was demonstrated. The ceramics were first obtained by heat treatment of a silicone embedding reactive oxide fillers and then biofunctionalized with adhesive peptides mapped on vitronectin. The most promisingin vitroresults, in terms of h-osteoblast proliferation and bone-related gene expression, were reached anchoring selectively a peptide stable toward proteolytic degradation induced by serum-enriched medium. Inin vivoassays the anchoring of this protease-stable adhesive peptide was combined with self-assembling peptides, for increasing cell viability and angiogenesis. The results demonstrated external and internal cell colonization of biofunctionalized scaffolds with formation of new blood vessels (neoangiogenesis) and stimulation of ectopic mineralization.