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In this work, we compared the main characteristics of highly porous geopolymer components for water treatment applications manufactured by 3D printing, direct foaming, or granulation. Furthermore, different approaches to impregnate the materials with Ag or Cu were evaluated to obtain filters with disinfecting or catalytic properties. The results revealed that all of the investigated manufacturing methods enabled the fabrication of components that possessed mesoporosity, suitable mechanical strength, and water permeability, even though their morphologies were completely different. Total porosity and compressive strength values were 28 vol% and 16 MPa for 3D-printed, 70–79 vol% and 1 MPa for direct-foamed, and 27 vol% and 10 MPa for granule samples. Both the filter preparation and the metal impregnation method affected the amount, oxidation state, and stability of Ag and Cu in the filters. However, it was possible to prepare filters with low metal leaching between a pH of 3–7, so that the released Ag and Cu concentrations were within drinking water standards.

The upgradation of the ilmenite ore, using a pyrometallurgy method, is performed using a carbothermic reduction of the ilmenite. A high titania slag is obtained which is used as a feedstock for the TiO2 pigment production. The slag is cooled after tapping in big molds and can take ten days to cool. This cooling method has remained the same since the inception of ilmenite smelting and recently rapid cooling through granulation has been utilized. The work presented in this paper focuses on the microstructural study of the slags that were prepared using different techniques and cooled at different cooling rates. Various analytical techniques, such as X-ray powder diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and X-ray photoelectron spectroscopy (XPS) were used to exhibit the similarity of these synthetic slags to the properties of high titania ilmenite slag. The slag consisted mostly of pseudo-brookite phase with a M3O5 stoichiometry and smaller amounts of silicate and rutile phase. A glassy phase of silica was observed and most of the impurities were found to be present in the silicate phase. These silica phases were observed to be separate from the pseudo-brookite phase and along the phase boundaries. Micro-cracking of the slag surface, which is the characteristic of the M3O5 phase formed in the ilmenite slag, were observed under the SEM analysis. The XPS analysis revealed that faster cooling does result in lower amount of oxidation but the difference in the TiO2 and Ti2O3 composition can have larger impact on oxidation than the cooling speed.

This paper reports on the synthesis and characteristics of a novel aluminosilicate glass-based cementitious binder. We investigated the hydration kinetics, degree of reaction, and phase assemblage of the glass via XRD, DTG, ²⁷Al and ²⁹Si MAS NMR, FTIR, SEM/EDS and thermodynamic modelling. The glass exhibits hydraulic properties in which the binder developed impressive compressive strength at early age. The main hydration products are an intermixed of Na and/or Al incorporated in C–S–H gel. Hydrotalcite precipitated with slower rate and thus may generate crystallization pressure on the binder at late stage. The glass reached a high degree of hydration (ca. 73 % based on quantitative ²⁹Si NMR analysis) without using any activators or co-binding systems. Therefore, the developed glass reported herein has high potential as a new low-carbon cementitious binder since it can be synthesised from naturally occurring carbonate free silicate minerals.

One-part alkali-activated materials prepared with solid-form alkali activator are gaining attention in the construction industry, as they are an easier and safer approach for cast-in-situ applications in comparison with two-part approach (i.e., involving the use of alkali-activator solutions). The present study compares the one-part and conventional two-part mixing methods with two aluminosilicate precursors, metakaolin and ground granulated blast-furnace slag, using identical mix designs (in terms of molar ratios of SiO2, Al2O3, and Na2O) with both preparation methods. The results revealed that using one-part mix delays the setting time, increases the heat of reaction, decreases the shrinkage, and reaches between 80 and 85% of the compressive strength of the two-part mix. In addition, scanning electron microscopy, thermogravimetric analysis, and X-ray diffraction analysis showed no major differences between one- and two-part. However, energy-dispersive X-ray spectroscopy and magic angle spinning nuclear magnetic resonance experiments indicated that the extent of reaction in two-part alkali-activated mixes is higher than for one-part. Graphical Abstract

There is some ambiguity regarding the fate of Mg during the alkali activation of Mg-rich precursors within the broader field of alkali activated materials (AAMs). The present work addresses this issue by studying the reaction products in AAMs synthesized from (Na-Mg) aluminosilicate glasses. Here, instead of magnesium silicate hydrate (M-S-H) phase, Mg exclusively forms an amorphous magnesium silicate (AMS) phase. Compared to M-S-H, AMS is a more depolymerized phase, which has not previously been well documented. The formation of AMS seems to be driven by the high charge density of the Mg cation which effectively stabilizes the depolymerized silicate species. We also show that the lack of hydrotalcite-group phases is due to aluminum depletion by zeolite formation. This work highlights the need to consider the existence of the AMS phase in Mg-containing AAMs, especially in complex systems, where its identification may be difficult.

Alkali-activated materials (AAMs), sometimes called geopolymers, are eco-friendly cementitious materials with reduced carbon emissions when compared to ordinary Portland cement. However, the availability of most precursors used for AAM production may decline in the future because of changes in industrial sectors. Thus, new precursors must be developed. Recently there has been increased interest in synthetic glass precursors. One major concern with using synthetic glasses is ensuring that they react sufficiently under alkaline conditions. Reactivity is a necessary, although not sufficient, requirement for a suitable precursor for AAMs. This work involves the synthesis, characterization, and estimation of alkaline reactivity of Na-Mg aluminosilicate glasses. Structural characterization showed that replacing Na with Mg led to more depolymerization. Alkaline reactivity studies indicated that, as Mg replaced Na, reactivity of glasses increased at first, reached an optimal value, and then declined. This trend in reactivity could not be explained by the conventional parameters used for estimating glass reactivity: the non-bridging oxygen fraction (which predicts similar reactivity for all glasses) and optical basicity (which predicts a decrease in reactivity with an increase in Mg replacement). The reactivity of the studied glasses was found to depend on two main factors: depolymerization (as indicated by structural characterization) and optical basicity. Depolymerization dominated initially, which led to an increase in reactivity, while the effect of optical basicity dominated later, leading to a decrease in reactivity. Hence, while designing reactive synthetic glasses for alkali activation, structural study of glasses should be given due consideration in addition to the conventional factors.

Aluminosilicate glasses are materials with a wide range of technological applications. The field strength of network-modifying cations strongly influences the structure of aluminosilicate glasses and their suitability for various applications. In this work, we study the influence of the field strength of network-modifying cations on the structure of [(Na₂O)1–x(MgO)ₓ(Al₂O₃)0·25(SiO₂)1·25] glasses. Due to the higher cation field strength of magnesium than sodium, magnesium prefers the role of network modifier, while sodium preferentially acts as a charge compensator. When magnesium replaces sodium as network modifier, Q³ silicon species are converted into Q² species. The replacement of sodium with magnesium as charge compensator leads to the following changes: (1) the proportion of aluminum-rich Q⁴ species [Q⁴(4Al) and Q⁴(3Al)] decreases, while the proportion of aluminum-deficient Q⁴ species [Q⁴(2Al) and Q⁴(1Al)] increases; and (2) there is an increased tendency for phase separation between silica-rich and alumina-rich glasses.

The present study valorized Finnish mining tailings waste to identify opportunities for the use of ceramics technologies. On the basis of their mineralogical and chemical contents, the five selected tailings wastes represented felsic mining tailings (FMT) rich in quartz and alkali feldspars, mining tailings dominated by Mg- and Fe-bearing minerals (MgFeMT), and mining tailings rich in carbonate minerals (CMT). Preliminary pilot studies indicated that the FMT materials are potential secondary raw materials for mullite-type ceramics. An Al additive was needed, since the Al₂O₃ content of the studied tailings was too low for mullitization. In addition, carbonate-bearing tailings with Ca silicates can be applicable for chemically bonded phosphate ceramic (CBPC) synthesis. Based on a literature review, FMT are viable source materials for the production of geopolymers, but a high initial Si:Al ratio (in quartz-rich FMT) may lead to partial geopolymerization. Preliminary results from the geopolymerization of pre-heated phlogopite mica mixed with metakaolin gave promising findings, with the formation of a geopolymer having good compressive strength. The findings support the viability of MgFeMT materials rich in phlogopite mica for the production of alkali-activated ceramics

The retardant effects of citric acid on the properties of ettringite binders are not yet fully understood. This investigation provides insights into the effects of citric acid on both the fresh and hardened state properties of the binder produced from the hydration between ladle slag and gypsum (LSG). The results revealed that LSG's initial setting time could be controlled via different citric acid contents and could range from 20 min to 2 h. Citric acid is effective at relatively high dosages; in its absence, ettringite formed almost immediately directly following exposure to water. The presence of citric acid alters the hydration reactions in LSG. AFm was found to be one of main hydration products; citric acid promoted the conversion from ettringite to monosulfate, detected by using solid-state 27Al magic-angle spinning nuclear magnetic resonance spectroscopy. In addition, citric acid increased the compressive strength of LSG mortars by up to 45%. This work was done as part of the FLOW project (project number 8904/31/2017) funded by Business Finland in the ERA-MIN 2 Innovation program (EU Horizon 2020 program) and industrial partners including SSAB Europe Oy, Saint-Gobain Finland Oy, Kiertokaari Oy, and Destaclean Oy. The authors appreciate support from Prof. Yiannis Pontikes (KU Leuven, Belgium) for in situ XRD measurements and Samppa Hyvarinen for lab work. Hoang Nguyen gratefully acknowledges financial support from the Tauno Tonning Research Foundation. A.M.K. and V.-V.T. acknowledge financial support from the Kvantum Institute (University of Oulu) and the Academy of Finland (grant numbers 289649 and 294027).

Use of mine tailings as an aluminosilicate precursor in alkali activation is becoming an interesting alternative to manage the high-volume of waste generated from mining industries. However, very few tailings have so far been studied for their mineralogical properties and alkali activation potential. This study aims at understanding the ability of mine tailings from phosphate, kaolinite and lithium mines for their efficient participation in alkali activation. Biotite, muscovite, kaolinite, albite, and quartz were found to be the major minerals present in them. The impact of variation in mineralogy on silica and alumina solubility of these tailings was analyzed. The solubility was found to be high in impure kaolinite compared to the other two. Effectiveness of thermal treatment (750 °C and 900 °C) on improving the reactivity of these tailings in alkaline condition was also investigated. It was observed from the results that the effect of thermal treatment on the crystalline structure and solubility of an aluminosilicate material mainly depends on the mineral structure of the material, as well as the treatment temperature. Interestingly, thermal treatment reduced the solubility of lithium tailings with albite and quartz mineral. Effort has been made to relate the strength attained by alkali activation of mine tailings to their solubility values. However, despite of the higher solubility offered by impure kaolinite, phosphate tailings gives the maximum strength improvement by 62%. This can be due to the presence of calcium compounds in phosphate tailings that resulted in additional hydration products.

Geopolymers are emerging construction materials with lower carbon dioxide emissions compared to the conventional cementitious materials. The knowledge of the curing process and the related pore structures are important for optimizing the properties of these materials for different applications. The curing process and final pore structure are sensitive to the amount of used water, however the specifics are unclear. The curing process and pore structures of metakaolin-based geopolymers with a narrow water-to-solid (w/s) ratio (0.59–0.66) were monitored by nuclear magnetic resonance (NMR) relaxometry and cryoporometry. The 14-day curing process was investigated by monitoring the change of T2 and T1 relaxation times and water signal intensity. After the curing, the pore structures were characterized by 2D T1-T2 correlation and T2-T2 exchange measurements of absorbed water. The pore size distributions (PSDs) were measured with NMR cryoporometry and compared to nitrogen physisorption and mercury intrusion porosimetry (MIP) results. We found that the relaxation times decreased as the pore structure of the geopolymers matured during the curing while the dissolution and the condensation periods of the curing were distinguished by the changes in signal amplitude reflecting the proton density. After the curing, three distinct pore sizes and connectivity between pores were identified from T1-T2 and T2-T2 spectra. Their PSDs were measured, and they were found to correspond to two different pore sizes originating from the arrangement of clusters and defective pores. In the narrow w/s ratio (0.59–0.66), the curing times were the same for all samples when cured at 24 °C while the pore sizes were observed to increase as a function of the w/s ratio.