This paper examines how extrusion-based 3D-printing technology is evolving, utilising geopolymers (GPs) as sustainable inorganic aluminosilicate materials. Particularly, the current state of 3D-printing geopolymers is critically examined in this study from the perspectives of the production process, printability need, mix design, early-age material features, and sustainability, with an emphasis on the effects of various elements including the examination of the fresh and hardened properties of 3D-printed geopolymers, depending on the matrix composition, reinforcement type, curing process, and printing configuration. The differences and potential of two-part and one-part geopolymers are also analysed. The applications of advanced printable geopolymer materials and products are highlighted, along with some specific examples. The primary issues, outlooks, and paths for future efforts necessary to advance this technology are identified.

With progress in the bone tissue engineering (BTE) field, there is an important need to develop innovative biomaterials to improve the bone healing process using reproducible, affordable, and low-environmental-impact alternative synthetic strategies. This review thoroughly examines geopolymers’ state-of-the-art and current applications and their future perspectives for bone tissue applications. This paper aims to analyse the potential of geopolymer materials in biomedical applications by reviewing the recent literature. Moreover, the characteristics of materials traditionally used as bioscaffolds are also compared, critically analysing the strengths and weaknesses of their use. The concerns that prevented the widespread use of alkali-activated materials as biomaterials (such as their toxicity and limited osteoconductivity) and the potentialities of geopolymers as ceramic biomaterials have also been considered. In particular, the possibility of targeting their mechanical properties and morphologies through their chemical compositions to meet specific and relevant requirements, such as biocompatibility and controlled porosity, is described. A statistical analysis of the published scientific literature is presented. Data on “geopolymers for biomedical applications” were extracted from the Scopus database. This paper focuses on possible strategies necessary to overcome the barriers that have limited their application in biomedicine. Specifically, innovative hybrid geopolymer-based formulations (alkali-activated mixtures for additive manufacturing) and their composites that optimise the porous morphology of bioscaffolds while minimising their toxicity for BTE are discussed.

Magnesium and its alloys are not normally used as bioresorbable temporary implants due to their high and uncontrolled degradation rate in a physiological liquid environment. The improvement of corrosion resistance to simulated body fluids (SBF) of a magnesium alloy (AZ31) coated with poly-β-hydroxybutyrate (PHB) was investigated. Scanning electron microscopy, Fourier transform infrared spectrometer, and contact angle measurements were used to characterize surface morphology, material composition, and wettability, respectively. pH modification of the SBF corroding medium, mass of Mg²⁺ ions released, weight loss of the samples exposed to the SBF solution, and electrochemical experiments were used to describe the corrosion process and its kinetics. The material’s biocompatibility was described by evaluating the effect of corrosion by products collected in the SBF equilibrating solution on hemolysis ratio, cytotoxicity, nitric oxide (NO), and total antioxidant capacity (T-AOC). The results showed that the PHB coating can diffusively control the degradation rate of magnesium alloy, improving its biocompatibility: the hemolysis rate of materials was lower than 5%, while in vitro human umbilical vein endothelial cell (HUVEC) compatibility experiments showed that PHB-coated Mg alloy promoted cell proliferation and had no effect on the NO content and that the T-AOC was enhanced compared with the normal group and bare AZ31 alloy. PHB-coated AZ31 magnesium alloy extraction fluids have a less toxic behavior due to the lower concentration of corrosion byproducts deriving from the diffusion control exerted by the PHB coating films both from the metal surface to the solution and vice versa. These findings provide more reference value for the selection of such systems as tunable bioresorbable prosthetic materials.

The paper compares and evaluates the influence of the presence of perforations on the sound absorption coefficient (SAC) of a negative stiffness metamaterial based on a foamed ceramic geopolymer. Chemical–physical, microstructural, dynamic–mechanical, and sound characterisations are presented. A rigid, lightweight geopolymeric porous material has been prepared using an inorganic/organic monomeric mixture containing oligomeric sialates and siloxanes foamed with aluminium powder. This process results in an amorphous rigid light foam with an apparent 180 Kg/m³ density and a 78% open-pore. The viscoelastic characterisation by dynamic mechanical analysis (DMA) carried out from 10⁻³ to 10³ Hz indicates the behaviour of a mechanical metamaterial with negative stiffness enabling ultrahigh energy absorption at straining frequencies from 300 to 1000 Hz. The material loss factor (the ratio of dissipative/elastic shear moduli) is about 0.03 (essentially elastic behaviour) for frequencies up to 200 Hz to suddenly increase up to a value of six at 1000 Hz (highly dissipative behaviour). The corresponding storage and loss moduli were 8.2 MPa and 20 MPa, respectively. Impedance tube acoustic absorption measurements on perforated and unperforated specimens highlighted the role of perforation-resonant cavities in enhancing sound absorption efficiency, particularly within the specified frequency band where the mass of the negative stiffness foamed geopolymer matrix magnifies the dissipation effect. In the limits of a still exploratory and comparative study, we aimed to verify the technological transfer potentiality of using architected metamaterials in sustainable building practices.

Innovative tissue engineering biomimetic hydrogels based on hydrophilic polymers have been investigated for their physical and mechanical properties. 5% to 25% by volume loading PHEMA-nanosilica glassy hybrid samples were equilibrated at 37 °C in aqueous physiological isotonic and hypotonic saline solutions (0.15 and 0.05 M NaCl) simulating two limiting possible compositions of physiological extracellular fluids. The glassy and hydrated hybrid materials were characterized by both dynamo-mechanical properties and equilibrium absorptions in the two physiological-like aqueous solutions. The mechanical and morphological modifications occurring in the samples have been described. The 5% volume nanosilica loading hybrid nanocomposite composition showed mechanical characteristics in the dry and hydrated states that were comparable to those of cortical bone and articular cartilage, respectively, and then chosen for further sorption kinetics characterization. Sorption and swelling kinetics were monitored up to equilibrium. Changes in water activities and osmotic pressures in the water-hybrid systems equilibrated at the two limiting solute molarities of the physiological solutions have been related to the observed anomalous sorption modes using the Flory-Huggins interaction parameter approach. The bulk modulus of the dry and glassy PHEMA-5% nanosilica hybrid at 37 °C has been observed to be comparable with the values of the osmotic pressures generated from the sorption of isotonic and hypotonic solutions. The anomalous sorption modes and swelling rates are coherent with the difference between osmotic swelling pressures and hybrid glassy nano-composite bulk modulus: the lower the differences the higher the swelling rate and equilibrium solution uptakes. Bone tissue engineering benefits of the use of tuneable biomimetic scaffold biomaterials that can be “designed” to act as biocompatible and biomechanically active hybrid interfaces are discussed.

Alkaline sodium hydroxide/sodium silicate-activating high-purity metakaolin geopolymerization is described in terms of metakaolin deconstruction in tetrahedral hydrate silicate [O[Si(OH)₃]]⁻ and aluminate [Al(OH)₄]⁻ ionic precursors followed by their reassembling in linear and branched sialates monomers that randomly copolymerize into an irregular crosslinked aluminosilicate network. The novelty of the approach resides in the concurrent thermo-calorimetric (differential scanning calorimetry, DSC) and rheological (dynamic mechanical analysis, DMA) characterizations of the liquid slurry during the transformation into a gel and a structural glassy solid. Tests were run either in temperature scan (1 °C/min) or isothermal (20 °C, 30 °C, 40 °C) cure conditions. A Gaussian functions deconvolution method has been applied to the DSC multi-peak thermograms to separate the kinetic contributions of the oligomer’s concurrent reactions. DSC thermograms of all tested materials are well-fitted by a combination of three overlapping Gaussian curves that are associated with the initial linear low-molecular-weight (Mw) oligomers (P1) formation, oligomers branching into alumina-rich and silica-rich gels (P2), and inter- and intra-molecular crosslinking (P3). The loss factor has been used to define viscoelastic behavioral zones for each DMA rheo-thermogram operated in the same DSC thermal conditions. Macromolecular evolution and viscoelastic properties have been obtained by pairing the deconvoluted DSC thermograms with the viscoelastic behavioral zones of the DMA rheo-thermograms. Two main chemorheological behaviors have been identified relative to pre- and post-gelation separation of the viscoelastic liquid from the viscoelastic solid. Each comprises three behavioral zones, accounting for the concurrently occurring linear and branching oligomerization, aluminate-rich and silica-rich gel nucleations, crosslinking, and vitrification. A “rubbery plateau” in the loss factor path, observed for all the testing conditions, identifies a large behavioral transition zone dividing the incipient gelling liquid slurry from the material hard setting and vitrification.