Characterization of an aged alkali-activated slag roof tile after 30 years of exposure to Northern Scandinavian weather.

Alkali-activated materials (AAMs) have been known as an alternative cementitious binder in construction for more than 120 years. Several buildings utilizing AAMs were realized in Europe in the 1950s-1980s. During the last 30 years, the interest towards AAMs has been reinvigorated due to the potentially lower CO2 footprint in comparison to Portland cement. However, one often-raised issue with AAMs is the lack of long-term studies concerning durability in realistic conditions. In the present study, we examined a roof tile, which was prepared from alkali-activated blast furnace slag mortar and exposed to harsh Northern Scandinavian weather conditions in Turku, Finland, for approximately 30 years. Characterization of this roof tile provides unique and crucial information about the changes occurring during AAM lifetime. The results obtained with a suite of analytical techniques indicate that the roof tile had maintained excellent durability properties with little sign of structural disintegration in real-life living lab conditions, and thus provide in part assurance that AAM-based binders can be safely adopted in harsh climates. The phase assemblage and nanostructural characterization results reported here further elucidate the long-term changes occurring in AAMs and provide reference points for accelerated durability tests and thermodynamic modelling.

Exploring Mechanisms of Hydration and Carbonation of MgO and Mg(OH)2 in Reactive Magnesium Oxide-Based Cements.

Reactive magnesium oxide (MgO)-based cement (RMC) can play a key role in carbon capture processes. However, knowledge on the driving forces that control the degree of carbonation and hydration and rate of reactions in this system remains limited. In this work, density functional theory-based simulations are used to investigate the physical nature of the reactions taking place during the fabrication of RMCs under ambient conditions. Parametric indicators such as adsorption energies, charge transfer, electron localization function, adsorption/dissociation energy barriers, and the mechanisms of interaction of H2O and CO2 molecules with MgO and brucite (Mg(OH)2) clusters are considered. The following hydration and carbonation interactions relevant to RMCs are evaluated: (i) carbonation of MgO, (ii) hydration of MgO, carbonation of hydrated MgO, (iii) carbonation of Mg(OH)2, (iv) hydration of Mg(OH)2, and (v) hydration of carbonated Mg(OH)2. A comparison of the energy barriers and reaction pathways of these mechanisms shows that the carbonation of MgO is hindered by the presence of H2O molecules, while the carbonation of Mg(OH)2 is hindered by the formation of initial carbonate and hydrate layers as well as presence of excessed H2O molecules. To compare these finding to bulk mineral surfaces, the interactions of the CO2 and H2O molecules with the MgO(001) and Mg(OH)2 (001) surfaces are studied. Therefore, this work presents deep insights into the physical nature of the reactions and the mechanisms involved in hydrated magnesium carbonates production that can be beneficial for its development.

Nanostructured and Advanced Designs from Biomass and Mineral Residues: Multifunctional Biopolymer Hydrogels and Hybrid Films Reinforced with Exfoliated Mica Nanosheets.

Transforming potential waste materials into high-value-added sustainable materials with advanced properties is one of the key targets of the emerging green circular economy. Natural mica (muscovite) is abundant in the mining industry, which is commonly regarded as a byproduct and gangue mineral flowing to waste rock and mine tailings. Similarly, chitin is the second-most abundant biomass resource on Earth after cellulose, extracted as a byproduct from the exoskeleton of crustaceans, fungal mycelia, and mushroom wastes. In this study, exfoliated mica nanosheets were individualized using a mechanochemical process and incorporated into regenerated chitin matrix through an alkali dissolution system (KOH/urea) to result in a multifunctional, hybrid hydrogel, and film design. The hydrogels displayed a hierarchical and open nanoporous structure comprising an enhanced, load-bearing double-cross-linked polymeric chitin network strengthened by mica nanosheets possessing high stiffness after high-temperature curing, while the hybrid films (HFs) exhibited favorable UV-shielding properties, optical transparency, and dielectric properties. These hybrid designs derived from industrial residues pave the way toward sustainable applications for many future purposes, such as wearable devices and tissue engineering/drug delivery.

Alkali-Activation of Synthetic Aluminosilicate Glass With Basaltic Composition.

Alkali-activated materials (AAMs) are a potential alternative to Portland cement because they can have high strength, good durability and low environmental impact. This paper reports on the structural and mechanical characteristics of aluminosilicate glass with basalt-like compositions, as a feedstock for AAMs. The alkali-activation kinetics, microstructure, and mechanical performance of the alkali activated glass were investigated. The results show that AAMs prepared from basalt glass have high compressive strength (reaching up to 90 MPa after 7 days of hydration) compared to those made using granulated blast furnace slag (GBFS). In addition, calorimetry data show that the hydrolysis of the developed glass and subsequent polymerization of the reaction product occur at a faster rate compared to GBFS. Furthermore, the obtained results show that the alkali activation of the developed glass formed sodium aluminosilicate hydrate (N-A-S-H) intermixed with Ca aluminosilicate hydrate gel (C-A-S-H), while the alkali activation of GBFS resulted in predominantly C-A-S-H gel. The developed glass can be formed from carbonate-free and abundant natural resources such as basalt rocks or mixtures of silicate minerals. Therefore, the glass reported herein has high potential as a new feedstock of AAMs.

Towards designing reactive glasses for alkali activation: Understanding the origins of alkaline reactivity of Na-Mg aluminosilicate glasses.

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.

Sustainable batching water options for one-part alkali-activated slag mortar: Sea water and reverse osmosis reject water.

Concrete production is globally a major water consumer, and in general, drinking-quality water is mixed in the binder. In the present study, simulated sea water and reverse osmosis reject water were used as batching water for one-part (dry-mix) alkali-activated blast furnace slag mortar. Alkali-activated materials are low-CO2 alternative binders gaining world-wide acceptance in construction. However, their production requires approximately similar amount of water as regular Portland cement concrete. The results of the present study revealed that the use of saline water did not hinder strength development, increased setting time, and did not affect workability. The salts incorporated in the binder decreased the total porosity of mortar, but they did not form separate phases detectable with X-ray diffraction or scanning electron microscopy. Leaching tests for monolithic materials revealed only minimal leaching. Furthermore, results for crushed mortars (by a standard two-stage leaching test) were within the limits of non-hazardous waste. Thus, the results indicated that high-salinity waters can be used safely in one-part alkali-activated slag to prepare high-strength mortars. Moreover, alkali-activation technology could be used as a novel stabilization/solidification method for reverse osmosis reject waters, which frequently pose disposal problems.

Surface Modification of Cured Inorganic Foams with Cationic Cellulose Nanocrystals and Their Use as Reactive Filter Media for Anionic Dye Removal.

In this work, a surface cationized inorganic-organic hybrid foam was produced from porous geopolymer (GP) and cellulose nanocrystals (CNCs). GPs were synthesized from alkali-activated metakaolin using H2O2 as a blowing agent and hexadecyltrimethylammonium bromide (CTAB) as a surfactant. These highly porous GPs were combined at pH 7.5 with cationic CNCs that had been synthesized from dissolving pulp through periodate oxidation followed by cationization in a deep eutectic solvent. The GP-CNC hybrid foams were employed as reactive filters in the removal of the anionic dye, methyl orange (MO; 5-10 mg/L, pH 7). The effects of a mild acid wash and thermal treatments on the structure, properties, and adsorption capacity of the GPs with CNCs and MO were investigated. The CNCs aligned as films and filaments on the surfaces of the neutralized GPs and the addition of CNCs improved MO removal by up to 84% compared with the reference sample. In addition, CTAB was found to disrupt the attachment of CNCs on the pores and improve adsorption of MO in the GPs with and without CNCs.

Production of Lightweight Alkali Activated Mortars Using Mineral Wools.

This experimental study aimed to develop a fiber-reinforced lightweight mineral wool-based alkali activated mortar. The lightweight mineral wool-based alkali activated mortars were produced using premade foam and reinforced by polypropylene (PP) fibers. They were assessed in terms of fresh and hardened-state properties. Fresh-state properties were investigated by mini-slump tests. Hardened-state characteristics were assessed by ultrasonic pulse velocity, dry density, compressive and flexural strengths, drying shrinkage, efflorescence, water absorption, and permeable porosity. For the first time, the resistance of the synthesized lightweight mineral wool-based alkali activated mortars against harsh conditions (carbonation, freeze and thaw, and high temperature) were evaluated. The porous structures of the developed lightweight alkali activated mortars were also analyzed using an X-ray micro-computed tomography (CT) technique. Lightweight mix compositions with densities in a range of 770-1510 kg/m3, compressive strengths of 1-9 MPa, and flexural strengths of 2.6-8 MPa were developed. Increases in both density and strength after carbonation were also recorded, while a decrease of strength was noticed after exposure to freeze/thaw and high temperatures of up to 500 °C.

Using Carbonated BOF Slag Aggregates in Alkali-Activated Concretes.

This experimental study aimed to develop alkali-activated concretes containing carbonated basic oxygen furnace (BOF) slag aggregates. In the first stage, the impacts of replacing normal aggregates with carbonated BOF slag aggregates in different alkali-activated concretes were determined by assessing mechanical properties (compressive and flexural strengths), morphology, thermogravimetric analyses (TGA), differential thermogravimetry (DTG) and the crystalline phases using X-ray diffraction analysis. Second, the developed plain alkali-activated concrete was reinforced by different fibre types and dosages to limit the negative impacts of the drying shrinkage and to improve strength. Therefore, the effects of using different fibre contents (1% and 1.5% in Vol.) and types (Polyvinyl alcohol [PVA], Polypropylene [PP], basalt, cellulose and indented short-length steel) on hardened state properties were evaluated. These evaluations were expressed in terms of the compressive and flexural strengths, ultrasonic pulse velocity, mass changes, drying shrinkage and efflorescence. Then, the impacts of aggressive conditions on the hardened properties of fibre-reinforced alkali-activated concretes were evaluated under carbonation, high temperature and freeze/thaw tests. The results showed that using carbonated BOF slag aggregates led to obtain higher strength than using normal aggregates in alkali activated concretes. Moreover, the maximum enhancement due to reinforcing the mixtures was recorded in alkali-activated concretes with steel fibres.

Utilization of Mineral Wools as Alkali-Activated Material Precursor.

Mineral wools are the most common insulation materials in buildings worldwide. However, mineral wool waste is often considered unrecyclable because of its fibrous nature and low density. In this paper, rock wool (RW) and glass wool (GW) were studied as alkali-activated material precursors without any additional co-binders. Both mineral wools were pulverized by a vibratory disc mill in order to remove the fibrous nature of the material. The pulverized mineral wools were then alkali-activated with a sodium aluminate solution. Compressive strengths of up to 30.0 MPa and 48.7 MPa were measured for RW and GW, respectively, with high flexural strengths measured for both (20.1 MPa for RW and 13.2 MPa for GW). The resulting alkali-activated matrix was a composite-type in which partly-dissolved fibers were dispersed. In addition to the amorphous material, sodium aluminate silicate hydroxide hydrate and magnesium aluminum hydroxide carbonate phases were identified in the alkali-activated RW samples. The only crystalline phase in the GW samples was sodium aluminum silicate. The results of this study show that mineral wool is a very promising raw material for alkali activation.

Self-assembled magnetic bead biosensor for measuring bacterial growth and antimicrobial susceptibility testing.

Bacterial antibiotic resistance is one of the major concerns of modern healthcare worldwide, and the development of rapid, growth-based, antimicrobial susceptibility tests is key for addressing it. The cover image shows a self-assembled asynchronous magnetic bead rotation (AMBR) biosensor developed for rapid detection of bacterial growth. Using the biosensors, the minimum inhibitory concentration of a clinical E. coli isolate can be measured within two hours, where currently tests take 6-24 hours. A 16-well prototype is also constructed for simple and robust observation of the self-assembled AMBR biosensors.

Asynchronous magnetic bead rotation microviscometer for rapid, sensitive, and label-free studies of bacterial growth and drug sensitivity.

The long turnaround time in antimicrobial susceptibility testing (AST) endangers patients and encourages the administration of wide spectrum antibiotics, thus resulting in alarming increases of multidrug resistant pathogens. A method for faster detection of bacterial proliferation presents one avenue toward addressing this global concern. We report on a label-free asynchronous magnetic bead rotation (AMBR) based viscometry method that rapidly detects bacterial growth and determines drug sensitivity by measuring changes in the suspension's viscosity. With this platform, we observed the growth of a uropathogenic Escherichia coli isolate, with an initial concentration of 50 cells per drop, within 20 min; in addition, we determined the gentamicin minimum inhibitory concentration (MIC) of the E. coli isolate within 100 min. We thus demonstrated a label-free, microviscometer platform that can measure bacterial growth and drug susceptibility more rapidly, with lower initial bacterial counts than existing commercial systems, and potentially with any microbial strains.

Asynchronous magnetic bead rotation (AMBR) biosensor in microfluidic droplets for rapid bacterial growth and susceptibility measurements.

Inappropriate antibiotic use is a major factor contributing to the emergence and spread of antimicrobial resistance. The long turnaround time (over 24 hours) required for clinical antimicrobial susceptibility testing (AST) often results in patients being prescribed empiric therapies, which may be inadequate, inappropriate, or overly broad-spectrum. A reduction in the AST time may enable more appropriate therapies to be prescribed earlier. Here we report on a new diagnostic asynchronous magnetic bead rotation (AMBR) biosensor droplet microfluidic platform that enables single cell and small cell population growth measurements for applications aimed at rapid AST. We demonstrate the ability to rapidly measure bacterial growth, susceptibility, and the minimum inhibitory concentration (MIC) of a small uropathogenic Escherichia coli population that was confined in microfluidic droplets and exposed to concentrations above and below the MIC of gentamicin. Growth was observed below the MIC, and no growth was observed above the MIC. A 52% change in the sensor signal (i.e. rotational period) was observed within 15 minutes, thus allowing AST measurements to be performed potentially within minutes.

Experimental system for one-dimensional rotational brownian motion.

We present here an experimental, strictly one-dimensional rotational system, made by using single magnetic Janus particles in a static magnetic field. These particles were half-coated with a thin metallic film, and by turning on a properly oriented external static magnetic field, we monitor the rotational brownian motion of single particles, in solution, around the desired axis. Bright-field microscopy imaging provides information on the particle orientation as a function of time. Rotational diffusion coefficients are derived for one-dimensional rotational diffusion, both for a single rotating particle and for a cluster of four such particles. Over the studied time domain, up to 10 s, the variation of the angle of rotation is strictly brownian; its probability distribution function is gaussian, and the mean squared angular displacement is linear in time, as expected for free diffusion. Values for the rotational diffusion coefficients were also determined. Monte Carlo and hydrodynamic simulations agree well with the experimental results.

Label-acquired magnetorotation for biosensing: An asynchronous rotation assay.

This paper presents a novel application of magnetic particles for biosensing, called label-acquired magnetorotation (LAM). This method is based on a combination of the traditional sandwich assay format with the asynchronous magnetic bead rotation (AMBR) method. In label-acquired magnetorotation, an analyte facilitates the binding of a magnetic label bead to a nonmagnetic solid phase sphere, forming a sandwich complex. The sandwich complex is then placed in a rotating magnetic field, where the rotational frequency of the sandwich complex is a function of the amount of analyte attached to the surface of the sphere. Here, we use streptavidin-coated beads and biotin-coated particles as analyte mimics, to be replaced by proteins and other biological targets in future work. We show this sensing method to have a dynamic range of two orders of magnitude.

Monitoring the growth and drug susceptibility of individual bacteria using asynchronous magnetic bead rotation sensors.

Continuous growth of individual bacteria has been previously studied by direct observation using optical imaging. However, optical microscopy studies are inherently diffraction limited and limited in the number of individual cells that can be continuously monitored. Here we report on the use of the asynchronous magnetic bead rotation (AMBR) sensor, which is not diffraction limited. The AMBR sensor allows for the measurement of nanoscale growth dynamics of individual bacterial cells, over multiple generations. This torque-based magnetic bead sensor monitors variations in drag caused by the attachment and growth of a single bacterial cell. In this manner, we observed the growth and division of individual Escherichia coli, with 80-nm sensitivity to the cell length. Over the life cycle of a cell, we observed up to a 300% increase in the rotational period of the biosensor due to increased cell volume. In addition, we observed single bacterial cell growth response to antibiotics. This work demonstrates the non-microscopy limited AMBR biosensor for monitoring individual cell growth dynamics, including cell elongation, generation time, lag time, and division, as well as their sensitivity to antibiotics.

High frequency asynchronous magnetic bead rotation for improved biosensors.

Biosensors with increasingly high sensitivity are crucial for probing small scale properties. The asynchronous magnetic bead rotation (AMBR) sensor is an emerging sensor platform, based on magnetically actuated rotation. Here the frequency dependence of the AMBR sensor's sensitivity is investigated. An asynchronous rotation frequency of 145 Hz is achieved. This increased frequency will allow for a calculated detection limit of as little as a 59 nm change in bead diameter, which is a dramatic improvement over previous AMBR sensors and further enables physical and biomedical applications.

Pulsed-laser creation and characterization of giant plasma membrane vesicles from cells.

Femtosecond-pulsed laser irradiation was found to initiate giant plasma membrane vesicle (GPMV) formation on individual cells. Laser-induced GPMV formation resulted from intracellular cavitation and did not require the addition of chemical stressors to the cellular environment. The viscosity, structure, and contents of laser-induced GPMVs were measured with fluorescence microscopy and single-particle tracking. These GPMVs exhibit the following properties: (1) GPMVs grow fastest immediately after laser irradiation; (2) GPMVs contain barriers to free diffusion of incorporated fluorescent beads; (3) materials from both the cytoplasm and surrounding media flow into the growing GPMVs; (4) the GPMVs are surrounded by phospholipids, including phosphatidylserine; (5) F-actin is incorporated into the vesicles; and (6) caspase activity is not essential for GPMV formation. The effective viscosity of 65 nm polystyrene nanoparticles within GPMVs ranged from 32 to 434 cP. The nanoparticle diffusion was commonly affected by relatively large, macromolecular structures within the bleb.