Alkali and alkali earth metal ions are normally present in the gels of alkali-activated materials as well as blended PC-based materials. Previous studies have revealed that the leaching of these cations can trigger the change in gel structure and even the gel decomposition. However, the dissolution of cations was rarely known and the underlying mechanisms remained unclear. To address this issue, five calcium-(sodium, potassium-)aluminum-silicate hydrates (C-(N,K-)A-S-H gels) with different Ca/Si ratios (0.8–1.2) and Al/Si ratios (0.1–0.3) were synthesized to investigate the leaching behaviour of Ca, Na and K. For the first time, the dissolution free energies of Ca, Na and K in C-(N,K-)A-S-H gels were calculated using molecular dynamics simulations with the metadynamics method. Experimental results showed that Na showed the highest leaching ratio, followed by K and Ca, attributed to the lowest dissolution free energy of Na. The gel with a higher Ca/Si ratio or a lower Al/Si ratio showed higher charge positivity on the surface, resulting in reduced leaching of the three cations. Additionally, the presence of K was found to promote the dissolution of Na in gels.

This research investigated the use of wood biomass fly ash (WBFA) as a key component in developing low-carbon cementitious materials. WBFA was first subjected to water pretreatment and grinding to remove metallic aluminum and free lime, reducing expansion and cracking risks. Characterization of WBFA showed its high calcium and alkali-bearing phases but limited aluminosilicates. Dissolution test showed WBFA had strong alkalinity, suggesting its role as an activator for aluminosilicate-bearing minerals. A novel cement- and chemical-free binary binder was developed using 50 % treated WBFA and 50 % blast furnace slag (BFS). Paste with a water-to-binder ratio of 0.4 achieved 40 MPa compressive strength at 60 days. The use of superplasticizer significantly improved flowability, allowing the water-to-binder ratio to be reduced to 0.25, which resulted in compressive strength up to 58 MPa at 60 days. Calcium aluminate silicate hydrates (C-A-S-H) gels and ettringite were identified as the main reaction products in the pastes.

Efflorescence is a significant aesthetic and structural issue for alkali-activated materials (AAMs). This study addressed this issue at the aggregate level for the first time. The results indicated that substituting sand with aluminosilicate-based lightweight fine aggregate (LWFA) by 20 % or 50 % in volume reduced the efflorescence of alkali-activated slag (AAS) mortars by 14.6 % or 43 %, respectively. The mitigation mechanisms of LWFA were proposed in terms of gels, pore solution and microstructure. Specifically, the pozzolanic reaction of LWFA provided gels with additional Si and Al, which contributed to binding Na⁺ in the pore solution, thereby reducing the available Na for efflorescence formation. Combined with its internal curing effect, LWFA densified the surrounding pastes, which hindered the transport of ions and water, thus limiting the formation of efflorescence products. Furthermore, the incorporation of LWFA enhanced the flexural strength of mortars without significantly compromising compressive strength.

While alkali-activated slag (AAS) has emerged as a promising alternative binder in construction engineering, a consensus on the optimal curing condition for this material has not been reached yet. It is well known that AAS can harden at ambient temperatures, but the influence of humidity on its properties remains poorly understood. Herein, we considered five curing conditions with different relative humidities (RH), including ambient/dry condition (RH=55 %), sealed condition (RH=80–95 %), fog condition (RH>95 %), water immersion condition (RH=100 %), and saturated limewater immersion condition (RH=100 %). Various properties have been examined, including flexural and compressive strengths, elastic modulus, shrinkage, pore structure, carbonation resistance, and freeze-thaw resistance of AAS mortars (AASM). Two types of activators, sodium hydroxide and sodium silicate (modulus at 1) solutions were used. The experimental results indicate that drying at early ages is detrimental to almost all the properties investigated. Sealed curing can deliver desirable mechanical properties and durability, but considerable shrinkage. Fog and water curings are highly effective at mitigating early shrinkage in AASM, but the problem of leaching adversely affects its long-term properties. Generally, limewater curing offers limited benefits compared to other high-humidity curing methods.

Wood biomass fly ash (WBFA) has emerged as one of the most dominant by-products in the biomass energy sector. Circulating WBFA for construction practice can mitigate the secondary pollution caused by improper ash management, and provide a new material source to compensate for the scarcity of raw materials in the construction industry. This paper reviewed the current research progress on recycling WBFA in cementitious materials. The physicochemical properties of WBFA were summarized based on the literature. Further, the implementations of WBFA for the development of cementitious materials were categorized into three binder systems: clinker, blended cement, and alkali-activated materials (AAMs). Owing to the large variation in chemical compositions of WBFA and strict requirements in clinkering parameters, employing WBFA in blended cement and AAMs seems to be more promising. A new classification approach for WBFA was proposed to divide WBFA into two categories. This helps to provide simple guidance for ash recycling in construction practice. Finally, the current research gaps in WBFA valorization in cementitious materials were summarized, outlining the research for further exploration.

Carbonation of alkali-activated slag (AAS) materials has been primarily concerned in atmospheres with gaseous CO₂. This study, by contrast, highlights that AAS pastes would also be carbonated under tap water immersion. Calcite is the main CO₂-bear phase in both sodium hydroxide- and sodium silicate-activated AAS pastes, and the paste pre-cured for a longer curing period shows more severe carbonation. Additionally, calcium carbonate can densify the deteriorated microstructure of sodium hydroxide-activated paste caused by long-term leaching. The indentation modulus of pastes subjected to tap water immersion is higher than those under deionized water immersion. The uptake of CO₃^2- by hydrotalcite (Ht) and gels is also detected, resulting in the formation of Ht-CO₃ and decalcification of gels. Due to the synergistic effect of leaching and carbonation, a characteristic layered distribution of pastes close to the exposure front is observed, comprising the carbonated layer, transitional (carbonated + leached) layer, and leached layer, progressing from the outermost to the inner regions. Eventually, the kinetics of underwater carbonation, as well as the discrepancy between dry and underwater carbonation, is revealed.

Efflorescence presents not only as a cosmetic concern but also as a structural issue, which impacts the performance of alkali-activated materials (AAMs). In this study, the mechanisms of efflorescence of alkali-activated slag (AAS) pastes are investigated. First, the efflorescence of AAS pastes with different alkali dosages (3 %, 5 % and 7 %), activator types (sodium hydroxide (NH) and sodium silicate (NS)), exposure atmospheres (ambient, N₂ and 0.2 vol% CO₂), and relative humidities (40 %, 60 % and 80 %) was observed. Subsequently, leaching tests were performed and the impacts of efflorescence on AAS pastes at different heights were studied. It was found that a lower relative humidity facilitated more rapid and severe efflorescence. The positioning of efflorescence products was dependent on the porosity of the matrix. Compared to NH pastes, NS pastes subjected to semi-contact water conditions were more vulnerable to cracking problems, which turned out to be exacerbated by the formation of efflorescence products. A new method to quantify efflorescence was developed and it corresponded well with both efflorescence observations and leaching experiments. Furthermore, a competitive reaction between Ca and Na in the presence of carbonate ions was identified. CaCO₃, a representative product of natural carbonation, was rarely found in the regions where efflorescence products (sodium carbonate) formed. Regarding compressive strength, NS pastes were more adversely affected by efflorescence than NH pastes.

Previously, the lack of a thermodynamic database for N-(C-)A-S-H gel limited the application of thermodynamic modeling to alkali-activated fly ash (AAFA). This study pioneers thermodynamic modeling of AAFA using a recently developed thermodynamic dataset for N-(C-)A-S-H gel. The reaction products, pore solutions and reaction kinetics of AAFA pastes were experimentally determined. Based on the reaction kinetics, the composition of the solid phases and the pore solution of AAFA were modeled over time. The results showed that the simulated compositions of the solid reaction products and pore solution match closely with the experimental results, especially for the sodium hydroxide-activated system. Moreover, modeling results point out the potential presence of minor reaction products (e.g., C-(N-)A-S-H gel, microcrystalline ferrihydrite, Mg-containing phases) undetectable by experimental techniques. The study also demonstrated that thermodynamic modeling accurately captured the amount of bound water in reaction products, highlighting its robustness in both qualitative and quantitative analysis.

The early-age viscoelasticity of alkali-activated slag concrete (AASC) is critical for its early-age cracking proneness and long-term performance, particularly regarding creep and internal stress development. This study employs an innovative approach to quantify the early-age viscoelastic behavior of AASC, utilizing a Temperature Stress Testing Machine to conduct compressive, repeated and minutes-long creep tests, covering the curing age from 6 h till 28 days. This study is based on the linear theory of viscoelasticity and the Boltzmann superposition principle. A double power law function is employed to model creep and to further predict the internal stress of restrained AASC. It is demonstrated that the double power law function accurately captures the short-term creep of AASC, enabling reliable predictions of early-age stress accumulation and relaxation. Overall, this study highlights the pronounced viscoelasticity of AASC and the effectiveness of the experimental and modelling approaches used to quantify it.

Two synthesis pathways (one- and two-part) in alkali-activated binders were compared using ground granulated blast furnace slag (GGBFS), mineral wool (MW) activated using dry and liquid alkali activators with similar Na₂O/SiO₂ modulus. The effect of activator type on reaction kinetics, strength development, setting times, and durability shows that one-part synthesis does not only improve early strength, but also provide better durability properties. While the highest compressive strength (56 MPa, 90 days) was achieved for the one-part mix (DM), the reaction products (presence of Mg–Al layered double hydroxide and C–S–H-like phases) observed for both mortar mixes were similar. The DM mortars showed better resistance to sulfate attack than two-part mix (WM) mortars and sets faster. The results highlight the significance of the one-part pathways in the synthesis of alkali-activated materials.

As an industrial by-product containing pozzolanic components, recycled ferronickel slag (FNS) has the potential to be supplementary cementitious materials (SCMs) to reduce the massive carbon footprint of the cement industry, however, the main limitation of ferronickel slag as SCMs is the low hydration rate at an early age. In this study, the pozzolanic activity property results indicate that if the proportion is more than 10 %, FSN can hardly participate in the cement hydration reaction during the early stage, even the mechanical strength of FNS-mortar decreases obviously with the higher proportion of ferronickel slag. Therefore, mechanical grinding and steam curing at an early age are applied to promote the reaction activity of the recycled ferronickel slag tailing in this study. Compared with standard curing, the compressive strength of hardened FNS-cement paste with steam curing at 60 °C or 80 °C increased by 8.2 % or 33.8 %, and the connected porosity decreased by 18.9 % or 17.3 %. And MgO in the ferronickel slag exists as Mg₂SiO₄ in raw materials and enters the C-S-H gel with the formation of M-S-H gel during the secondary hydration stage. This study provides a theoretical basis for solid waste-based concrete and promotes the recycling, conservation, and resources of solid waste in building materials.

This study experimentally investigated the effects of surfactants and water-repelling agents on the hydration process, relative humidity, and mechanical properties of Portland cement pastes. Based on the measurement results, the degree of hydration, degree of saturation, capillary tension of autogenous shrinkage, and magnitude of autogenous shrinkage were simulated using a numerical model. In the numerical model, the elastic and creep components of autogenous shrinkage were calculated separately, and the creep component was simulated based on the solidification theory. The simulation results indicated that adding admixtures led to lower degrees of hydration and saturation. The capillary tension of the pure Portland cement was larger than that of the other mixtures. This can be attributed to several factors, including the smaller surface tension of mixtures with surfactants, larger contact angle of mixtures with water-repelling agents, and a lower degree of hydration of mixtures with both admixtures. Analyses of the simulated and measured results for different mixtures also show that creep plays an indispensable role in autogenous shrinkage. Adding a surfactant and a water-repelling agent can effectively mitigate autogenous shrinkage. However, when an excessive amount of water-repelling agent was added, its influence on the mitigation of autogenous shrinkage was insignificant.

In this study, the impacts of tap water immersion on the pore solution, phase assemblages, gel chemistry and structure, and pore structure of alkali-activated slag (AAS) pastes were studied. AAS degrades under such condition and the potential mechanisms can be concluded as lower reaction rates, gel decomposition and carbonation. The leaching of Na⁺ and OH⁻ at early stages hinders the reaction of slag, which leads to a slower formation of reaction products. Long-term leaching can result in gel decomposition after 90 d. Coarsened gel pores and capillary pores are both identified in water-immersed samples. Additionally, the leached Ca²⁺ can react with the dissolved CO₂ in tap water to form calcium carbonate. A calcium carbonate layer is observed surrounding the paste while the inner matrix is free of carbonation. The insights provided by this paper contribute to understanding the behaviors and durability of AAS in underwater conditions.

Autogenous shrinkage may be a critical issue concerning the use of limestone-calcined clay-cement (LC3) in high-performance concrete and 3D printable cementitious materials, which have relatively low water to binder (W/B) ratio. Adding an internal curing agent, i.e., superabsorbent polymer (SAP), could be a viable solution in this context. However, employing SAP (without adding additional water) may also influence the fresh properties of LC3 composites by increasing yield stress and viscosity, which may be beneficial for 3D printability. Therefore, this study attempts to use SAP as a rheology modifying admixture with the aim of investigating the impact of SAP on flow behavior, structural build-up, hydration kinetics, compressive strength, and autogenous shrinkage of LC3 pastes with a fixed W/B (0.3). In addition, hydroxypropyl methylcellulose (a typical rheology/viscosity modifier in 3D printable cementitious materials) was also employed in two mixtures to compare their effects. Results show that adding SAP increases the dynamic yield stress and the apparent viscosity, as well as structural build-up and hydration, but decreases the compressive strength at 3, 7 and 28 days. Furthermore, using SAP (especially 0.2 wt% SAP) not only promotes the early-age expansion but also effectively mitigates the autogenous shrinkage of LC3 pastes for up to 7 days. Overall, the obtained results indicated that SAP could act as a promising rheology modifier for the development of 3D printable cementitious materials.

This study aims to understand the effects and mechanisms of length, diameter, and functional group of carbon nanotubes (CNTs) on rheological behaviors of cementitious composites. The experimental results show that the addition of CNTs decreases the flow index and increases the critical shear rate of cementitious composites. CNTs with a sub-micrometer length and small diameter endow cementitious composites with high yield stresses and minimum viscosities. Influenced by the high water absorption of hydroxylic groups, the minimum viscosity of cementitious composites with hydroxyl functionalized CNTs is larger than that of composites with pristine carbon nanotubes (p-CNTs). By contrast, the yield stress and minimum viscosity of cementitious composites with carboxyl functionalized CNTs are smaller than that of cementitious composites with p-CNTs at most contents due to the high dispersion induced by carboxyl groups. The effect mechanisms of CNTs on rheological behaviors can be attributed to adsorption effect and entanglement effect, which are closely related to length, diameter and functionalization groups of CNTs. The established minimum viscosity prediction model considering the influence of CNT physicochemical features can provide guidance for regulating the workability and hardened performance of CNTs modified cementitious composites.

This paper provides a critical review on autogenous shrinkage of alkali-activated slag (AAS). It is reported that AAS paste, mortar, and concrete generally show larger autogenous shrinkage than Portland cement (PC) counterparts. Self-desiccation is the main driving force of the autogenous shrinkage of hardened AAS, but other mechanisms also play roles, particularly at early age. Existing models developed for PC do not give satisfactory estimations of the autogenous shrinkage of AAS, unless the pronounced viscoelasticity of AAS is considered. The susceptibility of AAS concrete to extensive cracking is not necessarily high due to the effects of stress relaxation, but local creep can exacerbate the development of microcracks. Various strategies have been proposed to mitigate the autogenous shrinkage of AAS, but many exhibit side effects, e.g., strength reduction. Existing testing methods for autogenous shrinkage of PC seem applicable to AAS, but the starting time and test duration need to be reconsidered.

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 investigates the effects of nanofillers on the interfacial transition zone (ITZ) between aggregate and cement paste by using nanoindentation and statistical nanoindentation techniques. Moreover, the underlying mechanisms are revealed through micromechanical modeling. The nanoindentation results indicate that incorporating nanofillers increases the degree of hydration in the ITZ, reduces the content of micropores and low-density calcium silicate hydrate (LD C–S–H), and increases the content of high-density C–S–H (HD C–S–H) and ultrahigh-density C–S–H (UHD C–S–H). In particular, a new phase, namely nano-core-induced low-density C–S–H (NCILD C–S–H), with a superior hardness of 2.50 GPa and an indentation modulus similar to those of HD C–S–H or UHD C–S–H was identified in this study. The modeling results revealed that the presence of nanofillers increased the packing density of LD C–S–H and significantly enhanced the interaction (adhesion and friction) among the basic building blocks of C–S–H gels owing to the formation of nano-core–shell elements, thereby facilitating the formation of NCILD C–S–H and further improving the performance of the ITZ. This study provides insight into the effects of nanofillers on the ITZ in concrete at the nanoscale.

In this study, the impact of water-to-cement (w/c) ratios of belite calcium sulfoaluminate cement (BCSA) on the hydration kinetics and the electrochemical impedance spectroscopy (EIS) parameters is studied. According to the analysis of classic hydration measurements, such as calorimetry tests, chemical shrinkage content, and chemically bound water content, it can be concluded that a higher w/c ratio clearly accelerates the hydration of BCSA cement paste. The electrical resistivity of BCSA0.35 cement paste is more than 4.5 times that of BCSA0.45 and BCSA0.5, due to the gradually densified micropore structure blocking the electrical signal transmission rather than the free charged-ion content. The porosity of BCSA0.5 is 27.5% higher than that of BCSA0.35 and 7.8% higher than that of BCSA0.45, which proves the resistivity is clearly related to the variation in microstructure, especially for the porosity and pore size distribution. The novelty of this study is the linear regression with logarithm terms of electrical resistivity and classic hydration parameters such as chemical shrinkage, cumulative hydration heat, and chemically bound water is established to extend the classical expression of cement hydration degree. It indicates that the electrochemical impedance spectroscopy can be taken as a nondestructive testing measurement to real-time monitor the cement hydration process of cement-based materials.

In this research, the effects of natural seawater (SW) on the properties of alkali-activated slag/fly ash (AASF) are studied. AASF prepared with deionized water is set as the reference mixture. The results showed that the use of natural SW resulted in a prolonged setting time and lower heat release, but no obvious impact on the flowability of AASF specimens. The long-term compressive strength became higher when SW was used, whereas the corresponding flexural strength and fractural toughness turned lower. The use of SW induced the formation of new products that were not identified in the reference mixture, such as Cl–hydrocalumite and gypsum. In addition, it is evidenced that the dissolution of fly ash (FA) particles was significantly delayed with the incorporation of SW. All these results were related to the various ions introduced by the natural SW and their interactions with the alkaline activator as well as the precipitation of salts on slag and FA surfaces or in the matrix.