Yubo Sun
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Municipal solid waste incineration (MSWI) bottom ash, due to its high mineral content, presents great potential as supplementary cementitious material (SCM). Weathering, also known as aging, is a treatment process commonly employed in waste management to minimize the risk of heavy metal leaching from MSWI bottom ash. Using weathered MSWI bottom ash to produce blended cement pastes is considered as a high-value-added and sustainable waste disposal solution. However, a critical challenge arises from the metallic aluminum (Al) in weathered MSWI bottom ash, which is known to induce detrimental effects such as volume expansion and strength loss of blended cement pastes. While most metallic Al in weathered MSWI bottom ash can be removed with eddy current separators in metal recovery plants, the residual metallic Al, owing to its small particle size, cannot be removed with the same technique. This study is dedicated to addressing this issue. An in-depth analysis was conducted on residual metallic Al embedded in weathered MSWI bottom ash particles, aiming to guide the removal of this metal. This analysis revealed that mechanical removal was the most suitable method for extracting metallic Al. The specific processes and mechanisms underlying this method were elucidated. After reducing metallic Al content in weathered MSWI bottom ash by 77 %, a significant improvement in the quality of blended cement pastes was observed. This work contributes to the broader adoption of mechanical treatments for removing residual metallic Al from weathered MSWI bottom ash and facilitates the application of treated ash as SCM.
To properly control the reaction kinetics and fresh properties evolution in conventional alkali-activated materials (AAMs), a conceptual design of two-stream AAMs has been proposed in this study. This is achieved by dividing the solid and liquid components in AAMs, including blast furnace slag (BFS) and electric arc furnace slag (EFS) precursors, as well as aqueous sodium hydroxide and silicate activators into two separate streams A and B, where a very limited reactivity is expected in individual streams to ensure sufficient workability retention. Moreover, a final-stage intermixing is required to combine individual stream mixtures and trigger the major activation reaction. Fresh and hardened properties of combined mixtures were checked at different stages. The microstructure and reaction products were investigated to understand the strength development. Low dynamic rheological parameters and good workability retention have been detected in all individual stream mixtures, accompanied by limited exothermic heat flows after the initial dissolution confirmed by calorimetry tests. Further, Portland cement (PC) is partially blended into stream A to alter the early stiffening process in combined mixtures and meet various setting demands after intermixing. However, this might lead to a reduction in mechanical properties, associated with the formation of porous microstructures and an increase in the Ca/Si ratio in reaction products. Eventually, the conceptual design is validated in different scenarios including self-compacting and 3D-printing concrete applications.
Alkali-activated concrete (AAC) is regarded as a promising alternative construction material to reduce the CO2 emission induced by Portland cement (PC) concrete. Due to the diversity in raw materials and complexity of reaction mechanisms, a commonly applied design code is still absent to date. This study attempts to directly correlate the AAC mix design parameters to their performances through an artificial intelligence approach. To be specific, 145 fresh property data and 193 mechanical strength data were collected from laboratory tests on 52 AAC mixtures, which were used as inputs for the machine learning algorithm. Five independent random forest (RF) models were established, which are able to predict fresh and hardened properties (in terms of compressive strength, slump values, static/dynamic yield stress, and plastic viscosity) of AAC with equivalent accuracy reported in the literature. Moreover, an inverse optimization was performed on the RF model obtained to reduce the sodium silicate dosages, which may further mitigate the environmental impact of producing AAC. The present RF model gives practical information on AAC mix design cases.
Alkali-activated material (AAM) is developed as a green alternative binder to replace Portland cement (PC) in the construction field. However, the large-scale application with AAM concrete is limited so far, with the insufficient knowledge of rheological behavior being a major obstruct. Thixotropy of concrete is of great interest, which can be helpful to predict various early-age performances. The current study dedicates to evaluating the thixotropy of alkali-activated slag (AAS) concrete mixtures with different silicate and water content in activator solutions. In specific, the silicate modulus (Ms) and water to binder (w/b) ratio have been varied. The thixotropic index calculated by the initial and equilibrium shear stress from the stress growth test, as well as the breakdown area obtained by applying different shear speeds were used to evaluate the thixotropy of AAM concrete. Results indicate a good correlation between different approaches. It was found that an increase in Ms led to more pronounced thixotropic behaviors in AAS concrete due to the rapid nucleation and accumulation of early hydration products, resulting in significant increases in peak torque values and slight reductions of torque at equilibrium. Besides, the concrete thixotropy gradually declined by applying a higher w/b ratio.
Although the application of blast furnace slag and fly ash-based alkali-activated concrete (BFS/FA-AAC) has both economic and environmental benefits, it is limited by the lack of a straightforward mix design method. In this paper, an experiment was conducted to investigate the effect of control factors, including the Na2O/binder ratio, the SiO2/Na2O ratio, the BFS/binder ratio, the water/binder ratio, and the water content on the workability (slump and rheology) of BFS/FA-AAC, and the effect of control factors include the Na2O/binder ratio, the SiO2/Na2O ratio, the BFS/binder ratio, the water/binder ratio, and the curing time on the compressive strength of BFS/FA-AAC. As a result, the influence degree and mechanism of each control factor on the performance of BFS/FA-AAC were quantitively explored and the accuracy of an empirical compressive strength formula was validated. Based on that, a practical mix design method of BFS/FA-AAC was eventually established. It is found that the mixture composition and content of paste can significantly influence the workability of BFS/FA-AAC. The compressive strength of BFS/FA-AAC is determined by control factors when the water content is within 160–195 kg/m3. The mechanical predictive method of BFS/FA-AAC is proven of high accuracy. The mixture designed by this methodology exhibits satisfied fresh and hardened performance as well as high environmental benefits.
To better understand early stiffening of AAS pastes, distinctive microstructural features by varying the silicate modulus (Ms) have been visualized with in-situ microscopy. In addition, the activation reaction was monitored with multiple approaches, while solid and liquid phases in hydrating AAS were characterized separately. In silicate-activated AAS, it was found fine granules of reaction products are intensively dispersed in the activator solution, leading to a less flocculated system. Compared to hydroxide-activated AAS, the development of interparticle connections was limited at early ages, whereas reaction products were detected with much smaller grain size, less crystalline phase, and higher Al incorporation. Results indicate that the stiffening of hydroxide-activated AAS is attributed to the formation of a well-percolated network through solid reaction products. Instead, massive fine granules of reaction products dispersed in the pore solution continuously develop, which may intensify the interparticle interactions and macroscopically results in the stiffening of a silicate-activated AAS.
This study provides a detailed investigation on the reproducibility of two groups of alkali-activated slag (AAS) mixtures, from both fresh properties and strength development perspectives. Three different commercial sodium silicate solutions and one lab-produced silicate activator (made of silica fume and sodium hydroxide) were used to prepare AAS pastes with the same nominal composition in each group. The reaction process of each AAS mixture was monitored by calorimetry and ultrasonic pulse velocity (UPV) measurements. Meanwhile, mini-slump and flow curve tests measured by rheometer were conducted in the first hour to characterize the evolution of fresh properties. The compressive and flexural strength of hardened AAS mortars were measured at different curing ages. The results revealed that AAS pastes prepared with three different sodium silicate solutions exhibited almost identical reaction kinetics, as well as the evolution of fresh properties and strength development. However, the reaction took place rather fast in AAS pastes made of silica fume. These mixtures showed worse rheology and less strength than the corresponding mixtures prepared with sodium silicate solutions. Furthermore, the present study also showed the feasibility of making the same AAS paste through different class commercial sodium silicate solutions.
The rapid workability loss of alkali-activated materials (AAM) has been a major obstacle limiting its onsite application. In this study, two conventional SPs (made of polynaphthalene sulfonate (PNS) and lignosulfonate (LS) salts), which have been reported to be effective in some specific AAM mixtures were separately applied in alkali-activated slag (AAS) concretes. A comprehensive testing program was performed to study their effect on reaction kinetics, rheology evolution, and strength development. Results showed sodium silicate-activated AAS mixtures exhibited lower yield stress than those activated by sodium hydroxide. In hydroxide media, PNS and LS remained effective to reduce yield stress and increase slump value, while they both failed to improve the rheological behavior of AAS activated by silicate. Moreover, the inclusion of 2% admixtures did not result in much strength reduction in both activators although LS showed a retardation effect and subsequent increase in the setting time in the fresh state.
Future perspectives for alkali‐activated materials
From existing standards to structural applications
The production of cement and concrete contributes significantly to global greenhouse gas emissions. Alkali‐activated concretes (AACs) are a family of existing alternative construction materials that could reduce the current environmental impact of Portland cement (PC) production and utilisation. Successful applications of AACs can be found in Europe and the former USSR since the 1950s and more recently in Australia, China and North America, proving their potential as construction materials. However, their utilisation is limited presently by the lack of normative and construction guidelines. Raw materials’ non‐uniform global availability and variable intrinsic properties, coupled with the lack of specific testing methods, raise questions regarding reproducibility and reliability. The mechanical and chemical behaviour of AACs has been investigated extensively over the past decades, strengthening its potential as a sustainable substitute for traditional PC‐based concrete. Although a wide amount of studies demonstrated that AACs could meet and even exceed the performance requirements provided by European design standards, a classification of these broad spectra of materials, as well as new analytical models linking the chemistry of the system components to the mechanical behaviour of the material, still need further development. This report gives an overview of the potential of alkali‐activated systems technology, focusing on the limitations and challenges still hindering their standardisation and wider application in the construction field.
Rheology of alkali-activated slag pastes
New insight from microstructural investigations by cryo-SEM
This study aims to interpret the early-stage rheology of alkali-activated slag (AAS) paste from microstructure perspectives. The microstructures visualized by cryogenic scanning electron microscopy (cryo-SEM) revealed the essential distinction between hydroxide and silicate-activated slag pastes. The hydroxide-based mixture showed typical suspension features, where slag particles were dispersed in the hydroxide activators. In the hydroxide media, even at very early ages (5 min), the solid grains were attached to each other through rigid connections of reaction products, which resulted in high yield stress. As for the silicate-based mixtures, an emulsion phase has been observed between slag particles, which consists of discontinuous water droplets and continuous silicate gels. Fine emulsions with smaller water droplets were observed as the silicate modulus of activators increased, which dispersed the slag particles but on the other hand improved the viscosity of the paste. With increasing water to binder ratio, both yield stress and viscosity of AAS pastes significantly reduced.
In this paper, a series of experiments were conducted to systematically and quantitively explore the effects of control factors on the early age properties, i.e., workability and strength of slag and fly ash-based alkali-activated paste (BFS/FA-AAP). The control factors on the workability (flowability and setting time) of BFS/FA-AAP include the Na2O/b ratio, the SiO2/Na2O ratio, the w/b ratio, and the BFS/b ratio. The control factors on strength (compressive strength and flexural strength) of BFS/FA-AAP further also include the curing condition and the curing age. The results show that a higher BFS/b ratio and Na2O/b ratio could increase the strength while decreasing the workability. A higher w/b ratio could increase the workability while slightly decreasing the strength. Higher SiO2/Na2O ratio increases both strength and workability. Despite that, higher Na2O/b ratio and SiO2/Na2O ratio could hinder the strength development. Sealed curing condition is proved to be a simple but efficient way to assure the steady strength development of BFS/FA-AAP. Although the strength of BFS/FA-AAP could generally stabilize after 90 days, the strength development rate varies with different mix proportions. In addition, a general methodology have been proposed to predict the compressive strength of BFS/FA-AAP and verified with experiments. Finally, a mix design table is proposed for the preliminary design of BFS/FA-AAP according to the principle of satisfying early age requirements.
Fresh and hardened properties of alkali-activated slag concrete
The effect of fly ash as a supplementary precursor
The present study explores the possibility of replacing blast furnace slag (BFS) with coal fly ash (FA) to produce alkali-activated material (AAM) concrete with hybrid precursors. With an increased FA replacement ratio, the reaction kinetics, fresh and hardened properties of AAM mixtures have been investigated. The retardation effect on the reaction kinetics with an increased FA content has been observed, which not only extended the induction period along with the heat flow evolution but also reduced the cumulative heat release up to 24 h. Spherical FA particles can provide a ball-bearing effect to improve the workability of the hybrid AAM mixtures, while FA also slows down the deterioration of fresh properties since they are less reactive compared to BFS particles. Regarding the strength development, FA results in the reduction at all curing ages in the mixtures with a low silicate modulus (Ms0.25). Similarly, reduction in 1-day compressive strength has been detected in high silicate modulus mixtures (Ms0.5) with FA replacement, while the mixture with 10% FA exhibits the highest compressive strength among Ms0.5 concretes at later curing ages. Bigger capillary pores have been detected in AAM mixtures with an increase in FA content. However, AAM with 10% FA shows the lowest porosity in Ms0.5 mixtures, which is in agreement with the compressive strength results.