Due to the gradual diffusion of CO₂ under natural exposure, areas with varied degrees of carbonation exist at different depths from the surface of slag-rich cement paste. While extensive research has been dedicated to investigating the fully carbonated zone as identified by phenolphthalein spray, the transitional zone, located between the fully carbonated and the uncarbonated regions, has received comparatively less attention. This study thus aims to address this research gap by exploring its microstructural, micromechanical, and mineralogical properties. The results reveal that carbonation-induced damage extends beyond the fully carbonated zone as identified by phenolphthalein. Particularly in the transitional area close to the carbonated zone, nanoindentations results reveal that micromechanical properties of this area are even lower to that of the fully carbonated zone. In addition, mineralogical investigation suggest that the depth of carbonation stays within the range where slag-containing blends loses its green coloration. By comparing specimens with different slag composition, it was found that the depth of this faded green area can be an important indicator to assess the carbonation resistance of slag-containing blends.

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.

In this paper, the authors characterized two types of zonation within slag rims in aged alkali-activated slag (AAS) systems through SEM and TEM technology. These two elemental zonation were closely related to the pore structure of AAS pastes, thus providing strong implication for the transport- and durability-related performance of AAS systems. The first type of zonation occurred in the rims of AAS specimens under sealed curing. It was found that lath-like hydrotalcite-like phase accumulated near the boundary while a generally homogeneous and foil-like C-(N-)A-S-H gel phases precipitated in the following sub-zone. When slag rims were thick enough, a new Mg-rich region occurred. The second type of zonation was noticed in the carbonated AAS pastes. For this kind of distribution pattern, C-(N-)A-S-H gel phases were observed near the boundary. Following, the accumulation of Mg and Ca occurred alternatively. Additionally, transformation mechanism between these two types of zonation was also proposed.

This study aims to experimentally investigate the autogenous deformation and the stress evolution in restrained high-volume ground granulated blast furnace slag (GGBFS) concrete. The Temperature Stress Testing Machine (TSTM) and Autogenous Deformation Testing Machine (ADTM) were used to study the macro-scale autogenous deformation and stress evolution of high-volume GGBFS concrete with w/b ratios of 0.35, 0.42, and 0.50. The early-age cracking (EAC) risk (quantified by stress-strength ratio) and stress relaxation were analyzed extensively based on ADTM and TSTM results. Furthermore, Environmental Scanning Electron Microscopy (ESEM), X-ray Diffraction (XRD), and Mercury Intrusion Porosimetry (MIP) were conducted to explore the micro-scale origin of the autogenous deformation of high-volume GGBFS concrete, which supports the observations on the macroscale measurement of TSTM/ ADTM tests. This study finds that the ettringite formation in the first two days results in autogenous expansion, which can delay the appearance of tensile stress. The magnitude of autogenous expansion depends on the compatibility of ettringite content and pore size. The w/b ratio of 0.42 turns out to be optimal because it produces the highest amount of ettringite and results in the highest autogenous expansion. In comparison, the w/b ratio of 0.35 introduces significant autogenous shrinkage after the expansion peak and therefore corresponds to a high early-age cracking risk.

This study investigated the evolution process of high-volume slag cement (HVSC) paste from a chemo-mechanical standpoint. HVSC specimens with a 70 w.t. % slag replacement rate were studied at various ages. Evolution of phase assemblage, microstructure development, and micromechanical properties were analyzed using TGA/XRD/MIP/SEM-EDS and nano-/micro-indentation techniques. A two-scale micromechanical model was built to predict the effective elastic modulus based on the nanoindentation results. Key findings include: 1) Between 7 and 28 days, the formation of calcium silicate hydrate (C-S-H) gel phase improves the effective elastic modulus by filling capillary pores; 2) From 28 to 90 days, the phase assemblage and microstructure remain stable, with a transition from low-density to high-density C-S-H; 3) Between 90 days and 2 years, slag rims produced by slag grains result in increased elastic modulus; 4) The two-scale micromechanical model, combined with nanoindentation data, accurately predicts the effective modulus of HVSC composites, although the unhydrated slag grains-hydrated cement matrix interface may cause an overestimation at an early age. With longer curing time, this interface disappears owing to the continuous hydration of large slag particles and therefore a good match is found between the modelling and experimental results.

To understand the influence of slag chemistry on the carbonation resistance of slag-rich cement, this paper explored the carbonation characteristics of blended cement systems with different Al₂O₃ contents in slag through accelerated carbonation test. Irrespective of slag chemistry, three main CO₂ binding phases were identified during accelerated carbonation test, i.e. carbonated Ca-Al AFm phases (amorphous or nano-crystalline), carbonated hydrotalcite-like phase, and calcium carbonate (amorphous calcium carbonate, vaterite, and calcite). Additionally, it was noted that the classification employed for slag reactivity (based on slag chemistry) cannot be extended to predict carbonation resistance of slag-rich cement directly. The main challenge occurred for slag with high alumina content. The experimental results showed that Al₂O₃-rich slag exhibited a high reactivity and can be considered as a reactive component in the blended mixture; however, it did not contribute to carbonation resistance of the mixture. Especially for CO₂ binding capacity, it was similar for systems with varied alumina content in slag (from 3.69 to 18.19 wt.%) in the completely carbonated area.

Through the integration of SEM-BSE and TEM, we gained a comprehensive 3-dimensional understanding of different distribution patterns of inner hydration products of slag. For fully hydrated small slag grains, two distinct sub-zones were formed in the rims. Lath-like, well-crystalline hydrotalcite-like crystals were found to precipitate, grow, and accumulate near the boundary, forming a layer with a thickness slightly exceeding 0.5 μm. In the center, entrapped calcium and silicon played roles in the formation of a homogeneous and fibrous C−(A)–S–H gel phase. The concentration equilibrium between cement matrix and grain core led to the establishment of a similar grey pixel value and Ca/Si atomic ratio of gel phase at ~1.10. As the size of slag grains increased, three sub-zones became visible. Hydrotalcite-like phase was enriched near the boundary, followed by a sandwiched area abundant in C–(A)–S–H gel phase. Due to the low mobility and increased migration distance, newly released magnesium from reaction front accumulated locally to form a new Mg-rich region.

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.

Additively manufactured vascular networks have great potential for use in autonomous self-healing of cementitious composites as they potentially allow multiple healing events to take place. However, the existence of a vascular tube wall may impede with the healing efficiency if it does not rupture timely to release the healing agent. The issue of vascular material design has therefore been a major topic of research. To overcome this, dissolvable Polyvinyl Alcohol (PVA) filament is adopted in this study to fabricate the vascular networks. Fabricated networks are coated with wax, placed in cementitious mortar and removed upon hardening, thereby leaving a network of hollow channels. Different printing directions were expected to affect the dissolvability of printed structures and were therefore fabricated and tested. Different shapes (i.e., 2D and 3D) of vascular networks were printed and embedded in the cementitious mortar. Four-point bending tests and permeability tests were performed to investigate the healing efficiency. Multiple healing cycles were applied in the cracked specimens. The results show that the vertically printed PVA tubes with wax coating have good dissolution behaviour. As expected, the existence of vascular networks decreases the initial flexural strength of the specimens. In terms of healing efficiency, excellent mechanical and water tightness recovery were achieved when using epoxy resin as the healing agent. The mechanical recovery after the first healing process is higher than the following healing process. The watertightness of the cracked samples keeps decreasing with the increase of healing cycles. Specimens embedded with 3D vascular networks have higher healing potential than those utilizing 2D vascular networks.

Limestone-calcined clay-cement (LC3), as one of the most promising sustainable cements, has been under development over the past decade. However, many uncertainties remain regarding its rheological behaviors, such as the metakaolin content of calcined clay. This study aims to investigate the effect of increasing the content of fine-grained metakaolin in calcined clay on the rheology of LC3 pastes. Rheological behaviors and early-age hydration of studied mixtures were characterized using flow curve, constant shear rate, small amplitude oscillatory shear and isothermal calorimetry tests. Results show that increasing the content of fine-grained metakaolin decreased flowability but promoted structural build-up and early-age hydration. These phenomena can be attributed to the decrease of mean interparticle distance caused by the increased amount of fine-grained metakaolin, which may enhance colloidal interactions, C-S-H nucleation and direct contact between particles. Overall, modifying the fine-grained metakaolin content is a feasible approach to control the rheology of LC3 pastes.

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 paper presents the influence of P₂O₅ incorporated in slag on the hydration characteristics of cement-slag system. It was found that the gradual addition of phosphorus oxide in slag did not change overall mineralogy of the hydration products. Except hydration retardation in the dormant stage, chemically bound water and portlandite contents, hydration degree of slag, and pore structure at all investigated ages were similar among cement-slag pastes with different P₂O₅ percentages. Furthermore, significantly higher amount of monosulfate was observed as the P₂O₅ content in slag increased. In addition, a higher Al/Si atomic ratio was measured in the C-S(A)-H gel phase formed in the cement matrix. However, similar Ca/Si atomic ratio of C-S(A)-H gel phase and Mg/Al atomic ratio of hydrotalcite-like phase were determined in all slag pastes, irrespective of the addition of P₂O_5. In contrast to magnesium ion which was retained within the original slag boundary, phosphorus ions could migrate into cement matrix. Therefore, P/Si atomic ratio of the C-S-H gel phase increased with the increasing phosphorus oxide content in slag, reaching up to ∼0.08.

Cracking is one of the main causes for deterioration of concrete structures. Self-healing concrete with 3D-printed vascular networks has excellent potential for autonomous self-healing. This approach is scarcely investigated: no studies have been devoted to the influence of printing parameters on the properties of vascular based self-healing concrete. In this work, three-dimensional vascular structures with complex geometry were designed and printed with 4 different sets of printing parameters. First, the influence of the four, nominally identical, vascular networks on the initial flexural strength of self-healing concretes was experimentally investigated. In parallel, numerical modeling with a concrete damaged plasticity model (CDPM) in Abaqus software is used to simulate the influence of vascular networks on the mechanical properties of the self-healing composite. After the 4-point bending tests, epoxy resin is injected into the vascular networks as the healing agent to seal the cracks. Then, flexural strength regain and watertightness recovery were also measured. Based on the obtained results, we found that vascular based self-healing concretes have lower initial flexural strengths than the reference sample, as expected. The magnitude of the strength drop is shown to depend strongly on the printing parameters: the specimens with horizontally-printed vascular networks have higher flexural strength than the vertically-printed counterparts. Furthermore, vascular networks with a smaller printing layer-height have less influence on the initial flexural strength of vascular-based self-healing concrete compared to those with the larger printing layer-height. In terms of watertightness recovery, all tested vascular based self-healing samples showed a full (100%) recovery, which means that the printing direction and printing layer-height do not have an obvious effect on the watertightness recovery in this study. Numerical simulations of the mechanical performance of the composites with the CDPM show good agreement with the experiments, although printing quality of the vascular network influences the simulation accuracy. These simulations show great potential of using numerical simulations to design vascular based self-healing concrete in order to minimize a drop in mechanical properties, without compromising the healing efficiency. Overall, the designed 3D-printed vascular self-healing concretes show remarkable strength regain and watertightness recovery and provide a good basis for further research.

In this paper, the authors investigated the correlation between slag chemistry and CO₂ binding capacity of the blended system. To simplify the composition of mixture, model paste containing C₃S, slag covering the common composition range and gypsum was employed. After accelerated carbonation test, three CO₂-binding phases were identified in the system as: carbonated Ca-Al AFm phases, carbonated hydrotalcite-like phase, and calcium carbonate, irrespective of slag chemistry and the addition of gypsum. On the other hand, carbonated Ca-Al AFm phases played a minor role in absorbing CO₂, sharing less than 5% of CO₂ among all carbonate phases. Hydrotalcite-like phase was able to bind up to ∼10% CO₂, depending on the Mg/Al atomic ratio of raw slag. CaCO₃, originated from the carbonation of portlandite and C−S−H gel phase, took up more than 85% CO₂ after carbonation. Moreover, the carbonation degree of C−S−H gel phase was found to be negatively related with the Al₂O₃ content and Ca/Si ratio of raw slag.

In this study, the flexural strength and fatigue properties of interfacial transition zone (ITZ) were experimentally investigated at the micrometre length scale. The hardened cement paste cantilevers (150 × 150 × 750 μm³) attached to a quartzite aggregate surface were prepared and tested under the monotonic and cyclic load using a nanoindenter. The measured flexural strength of the ITZ (10.49–14.15 MPa) is found to be one order of magnitude higher than the macroscopic strength of ITZ reported in literature. On the other hand, the fatigue strength of the ITZ is lower than that of bulk cement paste at same length scale, measured previously by the authors. The microscopic mechanical interlocking and the electrostatic interaction between aggregate surface and hydration products are thought to contribute to the bond strength of ITZ. This study provides an experimental basis for the development of multiscale analysis of concrete subjected to both static and fatigue loading.