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.

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Steel slag-based geopolymer foamed concrete (SSGFC) provide a promising value-added and carbon-neutral strategy for the re-utilization of SS, and the strength and physical properties of SSGFC are essential to its practical application. Therefore, this study proposes to use emulsified asphalt (EA) to improve the pore structure, compressive strength, water resistance and thermal insulation properties SSGFC. Firstly, different contents of EA were added into the foaming solution to prepare modified foam, and then SSGFC samples were prepared by using modified foam and steel slag-based geopolymer. The fresh properties, microstructure, pore structure, reaction products and physical properties of SSGFC samples were investigated. The results indicate that EA can reduce the fluidity and settlement value of the paste and increase the setting time. The addition of EA leads to a decrease in hydration products, but it can reduce the average pore diameter of the SSGFC and improve its pore diameter distribution. The SSGFC sample prepared by modified foam with 10 % EA showed the best physical properties. Compared with the control group, its compressive strength increased by 21.4 %, water absorption decreased by 16.5 %, and thermal conductivity decreased by 31.3 %. Therefore, EA shows significant potential to enhance the performance of SSGFC, thus providing reliable support for its practical applications.

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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.

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With growing concern for global warming, the electricity industry is actively promoting the transition from coal to renewable energy sources. Due to the carbon neutrality of wood biomass energy, it has become one of the most popular options of renewable energy sources. However, the by-products resulting from biomass combustion, particularly wood biomass fly ash (WBFA), have not received sufficient attention. Direct disposal of WBFA poses environmental threats and causes pollution. From the perspective of the construction industry, the energy transition has led to a scarcity of coal fly ash (CFA) that is intensively used as supplementary cementitious materials (SCMs) in construction industry. With the increasing demand for raw materials in construction industry, it is of great interest to explore whether WBFA can be integrated as a new material in construction industry. This motivates the initiative of this research, driven by significant industry demand.

This thesis aims to enlarge the utilization efficiency of WBFA by recirculating WBFA as a valuable mineral to develop sustainable low-carbon cementitious materials. Prior to the experiment, a literature review on the properties of WBFA and current WBFA utilization methodologies in cementitious materials are summarized. An application-oriented WBFA classification was proposed, providing a guideline for the utilization of WBFA in preparing cementitious materials.

For the experimental research, three types of WBFA were initially characterized and screened based on their physicochemical properties, i.e., the content of unfavoured metallic aluminum and reactive components. One type of WBFA with representative properties was selected as the most suitable candidate for further investigation. To remove the metallic aluminum in WBFA, a two-step pretreatment method is proposed. The feasibility of WBFA for binder formulation was then evaluated through dissolution tests.

Based on the characteristics of WBFA, two types of binders were proposed. In chapter 4, considering the high alkalinity of WBFA, WBFA was used to enhance the reaction of aluminosilicates. An innovative clinker-free binary binder with WBFA and blast furnace slag (BFS) was developed. The effects of different WBFA to BFS ratios on reaction kinetics, hydration products, and microstructure evolution were studied. Following this, WBFA was further used as a mineral additive for BFS replacement in BFS blended cement. The effects of WBFA on both BFS and cement reactions were comprehensively studied using different characterization techniques. These two chapters together provide new solutions for the valorization of WBFA in novel binder formulations.

The carbonation of WBFA-containing binders investigated in chapter 4 and 5 was studied in chapter 6. The carbonation kinetics of pastes were calculated based on the carbonation depth development. It was found that in WBFA-BFS binary pastes, mixture with 50% of WBFA and 50% of BFS showed the best carbonation resistance, although the carbonation coefficient was much larger than cement pastes. When WBFA was introduced in BFS blended cement, it was observed that there was a decreased carbonation resistance in pastes with more WBFA. By analysing the microstructure evolution, it was concluded that pore connectivity played the key role in governing the carbonation process of pastes. Further grinding of WBFA to reduce its porous structure was recommended to reduce the pore connectivity and improve the carbonation resistance of pastes with WBFA.
The environmental impact evaluation is of great significance for waste utilization in the construction industry, as it can, to a certain extent, help quantify the sustainability of specific products. In chapter 7, bio-ash bricks and bio-ash composite cement were developed based on the mixtures studied in Chapters 4 and 5, respectively. A cradle-to-gate life cycle analysis (LCA) was conducted to evaluate the contribution of integrating WBFA for the production of these construction products. Possible improvements regarding further reducing the environmental impact of these products are discussed.

In summary, this thesis offers novel options for the utilization of WBFA in the construction sector as a binder component. Binary paste containing up to 70% WBFA demonstrates satisfactory mechanical properties for low-strength applications. In BFS-blended cement, substituting up to 30% of BFS with WBFA enhances early compressive strength, only a 7.67% reduction in compressive strength after 90 days. These findings indicate high utilization efficiency for WBFA. The investigations in the reaction kinetics and microstructure evolution of pastes with different WBFA to BFS ratios in the binders yield valuable insights into the function of WBFA in binder reaction. This knowledge can serve as a valuable reference for engineering practitioners seeking to customize the properties of these binders. The development of building products such as bio-ash bricks and bio-ash cement exemplifies the conversion of WBFA into construction materials. This emphasizes the notable ecological advantages of WBFA as a resource for the construction sector, highlighting the academic and industrial interests in utilizing WBFA for the development of sustainable low-carbon cementitious materials.@en

Using solid waste to replace limestone filler in asphalt concrete can not only reduce the cost of road construction, but also improve the utilization rate of solid waste. In this study, PHC pile waste concrete (PPWC) was innovatively used to replace limestone filler in asphalt mixture and its effect on the physical and rheological properties of asphalt mastics was studied. Firstly, PPWC was ground into filler particles with a diameter less than 0.075 mm. The physical properties, particle characteristics and chemical composition of PPWC filler and limestone filler were compared. Asphalt mastics were prepared with different filler-asphalt volume ratios (20%, 30% and 40%) and the physical properties, high-temperature rheological properties and low-temperature cracking resistance of asphalt mastics were tested. The experimental results showed that the surface of PPWC filler is rougher and has lower density and smaller particle size than limestone filler. When the filler content is the same, PPWC filler asphalt mastics have lower penetration and ductility, higher softening point than limestone filler asphalt mastics, and the viscosity of PPWC filler asphalt mastics is more sensitive than limestone filler asphalt mastics. PPWC filler asphalt mastics demonstrated superior high-temperature stability, but poorer low-temperature cracking resistance compared to limestone filler asphalt mastics. In conclusion, PPWC fillers can be used to replace limestone fillers in asphalt mixtures. The finding of this study will provide a new solution for the construction of eco-friendly roads.

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This paper develops a kind of molded disc samples to investigate the carbonation and related behaviors of hardened cement pastes under different previous hydration degrees. Weight and length changes of cement pastes over time are monitored during a multistep process including carbonation, drying, rewetting, and redrying. The combination of X-ray diffraction (XRD) and thermogravimetric analysis (TGA) is used to identify and quantify the mineral compositions of carbonated cement pastes. An exponential function between CO₂ uptake capacity and hydration time of cement pastes is established, which shows that the CO₂ uptake capacity of cement pastes decreases dramatically at the very beginning days of hydration and then remaining relatively stable as hydration time is prolonged. Two reasons for this finding are revealed: i) the equilibrium between the carbonation and the post-carbonation reaction of carbonation product, i.e., silica-alumina gel; ii) refining of pore structures by hydration products which hinders carbonation. A clearer zonation of carbonation areas is proposed, and the spatial distribution equations of CO₂ absorption are initially established. By monitoring carbonation and drying behavior of cement pastes with different hydration ages, it is revealed that carbonation reduces drying shrinkage of cement pastes especially for early-age samples, whereas drying increases carbonation shrinkage. By investigating the water changes during the multistep process, it is found that water is little released during the carbonation of C–S–H gels. New insight into mechanism of carbonation shrinkage is provided by a newly proposed model.

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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.

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This work evaluated the reactivity and leaching potential of municipal solid waste incineration (MSWI) bottom ash as supplementary cementitious material (SCM) and precursor for alkali-activated materials (AAM). The chemical composition of the amorphous phase in MSWI bottom ash was found to be in the same range as that of Class F coal fly ash. The reactivity of MSWI bottom ash as SCM and AAM precursor was tested to be much lower than that of blast furnace slag, but similar to that of Class F coal fly ash. The method of thermodynamic modeling was found useful in providing references for the mix design of MSWI bottom ash-based AAM. Grinding MSWI bottom ash into powder for the application of SCM and AAM precursor increased its leaching potential. Based on the findings of this study, recommendations were provided on how to use MSWI bottom ash to prepare blended cement pastes and AAM.

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Cementitious materials are well acknowledged as one of the most adaptable materials for immobilizing heavy metals. Belite calcium sulfoaluminate cement (BCSA), one of the low-carbon alternative binders to cement with superior properties regarding chemical resistance and mechanical properties, is found with a desirable capability for waste immobilization. In this study, BCSA was used for Co(II) immobilization with a dosage of up to 2.5% by weight of BCSA. The results showed that Co(II) could promote the hydration of BCSA pastes, specifically accelerated the hydration of ye'elimite. More hydration products could be generated in the Co(II)-doped BCSA pastes, leading to the construction of a denser microstructure. The compressive strength of BCSA pastes would be slightly improved when BCSA was used for Co(II) immobilization, and the electrical resistivity would decrease. In terms of Co(II) immobilization, BCSA cement exhibited a desirable capacity for Co(II) immobilization. The majority of the Co(II) could be immobilized within the first 100 min of mixing BCSA with Co(II) solutions. The immobilization degrees of Co(II) in hardened BCSA pastes could approach about 99.99% after 7d. The acquired results indicated that BCSA cement is effective for Co(II) immobilization. Therefore, BCSA has a low-carbon advantage with superior strength development over time and prospective capacity of heavy metals immobilization.

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In 3D concrete printing, fast structuration is a prerequisite for ideal buildability. This paper aims to study the impact of inorganic additives, i.e., CaCl₂ and gypsum, on structural build-up and very early-age hydration of limestone-calcined clay-cement (LC3) pastes within the first 70–80 min. Results show that, increasing the dosage of CaCl₂ or gypsum can accelerate storage modulus G' and static yield stress evolution with time, as well as increase chemically bound water (H) content and total specific surface area (SSA_total). Furthermore, good correlations were found between G' and H content, as well as static yield stress and the ratio of free water content to SSA_total. The acceleration by CaCl₂ can be attributed to stimulating C₃S and C₃A hydration and promoting crystal formation, i.e., ettringite, portlandite, and Friedel's salt. Additionally, the increase in gypsum percentage led to a large amount of unreacted gypsum in the system, resulting in an increase in SSA_total.

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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.

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This paper investigates the influence of temperature on autogenous deformation and early-age stress (EAS) evolution in ordinary Portland cement paste using a recently developed Mini Temperature Stress Testing Machine (Mini-TSTM) and Mini Autogenous Deformation Testing Machine (Mini-ADTM). In the Mini-TSTM/ ADTM, CEM I 42.5 N paste with a water-cement ratio of 0.30 was tested under a curing temperature of 10, 15, 20, 25, 30, and 40 °C. X-Ray diffraction (XRD) tests were conducted to measure the amount of ettringite and calcium hydroxide, which reveals the micro-scale mechanisms of autogenous expansion. The applicability of the Maturity Concept (MC) for the prediction of autogenous deformation and relaxation modulus under different temperatures was also examined by the experimental data and the viscoelastic model. This paper leads to the following findings: 1) The autogenous deformation of ordinary Portland cement paste is a four-stage process comprising the initial shrinkage, autogenous expansion, plateau, and autogenous shrinkage; 2) Higher temperature leads to higher early-age cracking (EAC) risk because it accelerates the transitions through the first three stages and causes the autogenous shrinkage stage to start earlier. Moreover, higher temperatures also result in increased rates of autogenous shrinkage and EAS in the autogenous shrinkage stage; 3) Autogenous expansion and plateau are attributed to the crystallization pressure induced by CH. Temperature-dependent CH formation rates determine the duration of the plateau stage; 4) Low-temperature curing can delay but not completely prevent the EAC induced by autogenous deformation; 5) The MC cannot predict the autogenous deformation at different temperatures but can be used to calculate the relaxation modulus, which in turn aids in EAS prediction based on autogenous deformation data.

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This paper employs PVA, PE, steel fibers, as well as the hybrids of two of the three fibers to reinforce alkali-activated slag (AAS) material, aiming to prepare strain-hardening and clinker-free composites. The flexural strength, compressive strength, uniaxial tensile performance of the composites and bond behavior between fibers and the matrix were tested to clarify the reinforcement effects of different fibers on the matrix. Strain-hardening AAS materials are obtained with compressive strengths of 116 MPa − 137 MPa (with fibers contributions of 17%−38%) and strain capacities over 0.8% at 60 d. The results indicate that there are several kinds of reinforcement effects of fibers on the matrix, namely bridging effect, lapping effect (for steel fibers), synergetic effect (for hybrid fibers) and static effect (for flexible fibers). Deterioration of PVA and PE fibers are found, indicating that these two fibers have poor adaptability in AAS material with a high alkalinity. This paper specially distinguishes the difference of the crack numbers during the strain-hardening stage only with the ones during the whole period including the following strain-softening stage. A new relationship is established between the crack numbers and the strain-stress curves, which provides a more reasonable way to characterize the strain-hardening property of fiber-reinforced composites.

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This study investigates the deformation of free and stress of restrained alkali-activated slag concrete (AASC), respectively, under semi-adiabatic condition. The concrete shows first thermal expansion, which is compensated soon by autogenous shrinkage. The subsequent cooling down of the concrete aggravates shrinkage and development of tensile stress, which eventually results in early cracking of the concrete. The results show that semi-adiabatic condition is severer for AASC than isothermal condition in view of cracking tendency. The evolutions of coefficient of thermal expansion (CTE) and elastic modulus are measured by elaborated experimental methods. Simulating the deformation of AASC by summing thermal and autogenous deformations appears feasible. With the consideration of relaxation, the stress evolution in restrained AASC can be predicted pretty well by the model used in this paper. This study provides insights into the thermal deformation and cracking tendency of AASC in practical circumstances.

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This paper investigated the feasibility of using biomass fly ash (BFA) to prepare alkaliactivated slag and fly ash paste. The reference mixture was alkali-activated slag and coal fly ash (CFA) paste with a slag-to-coal fly ash ratio of 50/50. In other mixtures, coal fly ash was replaced at 40% and 100% with BFA, respectively. The results showed that the incorporation of BFA accelerated the setting of the paste, while its impact on the compressive strength was minor. XRD and FTIR results indicated that the BFA participated in the reaction process. BFA showed potential use as CFA replacement in synthesizing alkali-activated materials, which would pave a way for the valorisation of BFA.@en

The high autogenous shrinkage of alkali-activated materials made from slag and fly ash is recognised as a major drawback with regard to the use as construction materials. In this study, metakaolin was introduced into the alkali-activated slag-fly ash (AASF) paste to mitigate the autogenous shrinkage. The shrinkage mitigation mechanism of metakaolin was explained by studying the influences of metakaolin on the microstructure, shrinkage related properties, and mechanical properties of AASF paste. It was found that adding metakaolin could significantly reduce the chemical and autogenous shrinkage of AASF paste. This shrinkage mitigation is accompanied by a decrease in the alkalinity of AASF paste pore solution, a reduced drop in internal relative humidity, and an increase in porosity of AASF paste. Moreover, the incorporation of metakaolin does not change the type of the reaction products, but greatly delays the formation of the reaction products of AASF paste. The addition of metakaolin, above 5% of the binder, results in lower 28-day compressive and flexural strength of AASF paste.

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Alkali activated concrete (AAC) has not received broader industry acceptance, one reason of which lies in the uncertainties in the durability against shrinkage and potential cracking. Many studies reported that AAC exhibit larger autogenous shrinkage than OPC concrete. However, it is unable to deduce that AAC should show higher cracking potential than OPC concrete only based on the higher autogenous shrinkage of AAC. The cracking potential of concrete is determined by multiple factors including autogenous shrinkage, creep/relaxation, elastic modulus, and tensile properties of the concrete. However, very few studies have considered these parameters. Furthermore, the influence of precursors (e.g. slag or fly ash) on the cracking potential of AAC induced by autogenous shrinkage is also rarely studied. The aim of this study, therefore, is to investigate the autogenous shrinkage-induced cracking potential of slag and fly ash-based AAC. The free autogenous shrinkage of the specimens is measured by Autogenous Deformation Testing Machine (ADTM). The autogenous shrinkage-induced stress and cracking of the concrete under restraint condition is tracked by Thermal Stress Testing Machine (TSTM). Additionally, the influence of precursors on the autogenous shrinkage induced cracking potential is discussed.

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This study investigates the influences of internal curing on reducing the autogenous shrinkage of alkali-activated slag/fly ash (AASF) paste. The influences of internal curing with superabsorbent polymers (SAPs) on the reactions and microstructure of AASF paste are investigated. It is found that the SAPs absorb liquid mainly before the initial setting time of the paste. Afterwards, the liquid is gradually released, keeping the internal relative humidity of the paste close to 100%. The internal curing with SAPs can significantly mitigate the autogenous shrinkage of AASF paste, especially after the acceleration period of the reaction. The mitigating effect of internal curing is due to the mitigated self-desiccation in the paste, rather than the formation of a denser microstructure or expansive crystals. The cracking potential of AASF under restrained condition is also greatly mitigated by internal curing. Despite the slight reductions in the elastic modulus and the compressive strength, great improvement is obverted in the flexural strength of the paste. This work confirms the effectiveness of internal curing of AASF with SAPs and further provides a promising way to reduce the autogenous shrinkage of AASF without compromising its mechanical properties.

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This study aims to investigate the cracking potential of alkali-activated slag (AAS) and alkali-activated slag-fly ash (AASF) concrete subjected to restrained autogenous shrinkage. Temperature Stress Testing Machine (TSTM) is utilized, for the first time, to monitor the stress evolution and to measure the cracking time of alkali-activated concrete (AAC) under restraint condition. The stresses in AAS and AASF concrete are calculated based on the experimental results while taking into consideration the influence brought by creep and relaxation. It is found that AAS and AASF concrete showed lower autogenous shrinkage-induced stress and later cracking compared to ordinary Portland cement (OPC) based concrete with similar compressive strength, despite the higher autogenous shrinkage of AAS and AASF concrete. The low autogenous shrinkage-induced stress in the AAC is mainly attributed to the pronounced stress relaxation. A good prediction of the stress evolution in AAC is obtained by taking into account the elastic part of the autogenous shrinkage and the stress relaxation. In contrast, calculations ignoring the creep and relaxation would lead to a significant overestimation of the stress in AAC.

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This study aims to provide a better understanding of the autogenous shrinkage of slag and fly ash-based alkali-activated materials (AAMs) cured at ambient temperature. The main reaction products in AAMs pastes are C-A-S-H type gel and the reaction rate decreases when slag is partially replaced by fly ash. Due to the chemical shrinkage and the fine pore structure of AAMs pastes, drastic drop of internal relative humidity is observed and large pore pressure is generated. The pore pressure induces not only elastic deformation but also a large creep of the paste. Besides the pore pressure, other driving forces, like the reduction of steric-hydration force due to the consumption of ions, also cause a certain amount of shrinkage, especially in the acceleration period. Based on the mechanisms revealed, a computational model is proposed to estimate the autogenous shrinkage of AAMs. The calculated autogenous shrinkage matches well with the measured results.

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