Adding hydrated lime (CH) into blended cement incorporating high volume of Supplementary Cementitious Materials (SCMs) is a viable method to provide the necessary calcium hydroxide for the pozzolanic reaction, thereby improving the mechanical performance at later stages. However, the effects of relatively small dosages of CH on the rheological properties and resulting microstructure of limestone-calcined clay cement (LC3) remain unclear. This paper aims to investigate the influence of a small CH addition on the fresh and hardened properties of LC3 systems, in which Portland cement is largely replaced (80 wt%) by limestone and calcined clay. The results indicate that the additional CH notably reduces the water film thickness, leading to increased dynamic yield stress, plastic viscosity and re-flocculation. A delay in the elasticity development and static yield stress evolution within the first 1.5 h was observed with the addition of 2.5 wt% CH, attributed to the initial dissolution of CH, which is mitigated by using 10 wt% CH. Furthermore, additional CH accelerated early-age hydration and facilitated long-term pozzolanic reactions, resulting in the increased amount of C-(A)-S-H gel and AFm phases, and reduced porosities after 7 and 28 days. These chemical effects could well compensate the high air void content caused by the high viscosity, and therefore contributes to mortars with higher compressive strengths than plain LC3 at later ages.

Early-age cracking risk induced by autogenous deformation is high for cementitious materials of low water-binder ratios. The autogenous deformation, viscoelastic properties, and stress evolution are three important factors for understanding and quantifying the early-age cracking risk. This paper systematically reviewed the experimental and modelling techniques of the three factors. It is found that the Temperature Stress Testing Machine is a unified experimental method for all these three factors, with a strain-controlled mode for stress evolution, hourly-repeated loading scheme for viscoelastic properties, and free condition for autogenous deformation. Such unified method provides basis for developing various models. By coupling a hydration model for volume fractions of hydrates, a homogenization model for upscaling of viscoelastic properties, and capillary pressure theory for self-desiccation shrinkage, a unified model directly mapping the mix design to the early-age stress can be constructed, which can help optimize the mix design to reduce the early-age cracking risk.

Temperature Stress Testing Machine (TSTM) is a universal testing tool for many properties relevant to early-age cracking of cementitious materials. However, the complexity of TSTMs require heavy lab work and thus hinders a more thorough parametric study on a range of cementitious materials. This study presents the development and validation of a Mini-TSTM for efficiently testing the autogenous deformation (AD), viscoelastic properties, and their combined results, the early-age stress (EAS). The setup was validated through systematic tests of EAS, AD, elastic modulus, and creep. Besides, the heating/cooling capability of the setup was examined by tests of coefficient of thermal expansion by temperature cycles. The results of EAS correspond well to that of AD, which qualitatively validates the developed setup. To quantitatively validate the setup, a classical viscoelastic model was built, based on the scenario of a 1-D uniaxial restraint test, to predict the EAS results with the tested AD, elastic modulus, and creep of the same cementitious material as the input. The predicted EAS matched the testing results of Mini-TSTM with good accuracy in 6 different cases. The viscoelastic model also provided quantitative explanations for why variations in early AD do not influence the EAS results. The testing and modelling results together validate the developed Mini-TSTM setup as an efficient tool for studying early-age cracking of cementitious materials. At the end, the potential limitations of the Mini-TSTM are discussed and its applicability for concrete with aggregate size up to 22 mm is demonstrated.

The implementation of extrusion-based 3D concrete printing (3DCP) in large-scale constructions is currently limited by concerns regarding rheology control and the sustainability of this process. To address these issues, this study presents an approach to develop limestone-calcined clay-based cementitious (LC3) materials accelerated by Ca(NO₃)₂ solution in an inline static mixer-based 3DCP setup. Using this approach, a printable mixture containing only about 275 kg/m³ of Portland cement was formulated that can exhibit a good buildability performance and a 28-day compressive strength of over 30 MPa. Additionally, the effects of adding Ca(NO₃)₂ solution on the initial setting time, structural build-up, inline buildability, early-age hydration, and compressive strength of LC3 materials were investigated and discussed. Results show that the addition of Ca(NO₃)₂ solution improved the buildability and accelerated initial setting as well as the structuration due to the promoted ettringite precipitation and C–S–H nucleation. Furthermore, compressive strength at 7 and 28 days was improved through increasing the Ca(NO₃)₂ dosage, which can be attributed to the formation of NO₃-AFm and the increase in the amount of C–S–H gels.

Herein, different kinds of methods for buildability quantification of 3D concrete printing are reviewed, including experimental approaches, analytical modelling, and numerical simulations. A brief introduction on printing process is first given. This discusses the material properties in different stages. Material printability, which encompasses pumpability, extrudability and buildability, is then discussed. Subsequently, a brief review of the experimental and analytical models for buildability quantification is presented and they're discussed. An overview on the numerical tools for 3DCP is then given. These numerical models can quantify structural buildability and optimize the printing parameters, therefore, providing a more economical solution for buildability quantification. In the end, a summary and discussion on the limitations of numerical tools for buildability quantification are provided, as well as recommendations for their improvement.

This study investigates the microstructural changes of cement paste due to the inclusion of polymeric microfiber at different water-to-cement (w/c) ratios. A procedure to quantify the porosity of epoxy impregnated interfacial transition zone (ITZ) is also presented. Results show that the microstructures of the ITZ beneath and above a microfiber, with respect to the gravity direction, are largely different. Though the ITZ at both sides of the fiber are more porous than the bulk matrix, the porosity of the lower ITZ (i.e., the ITZ beneath a fiber) is significantly higher than the upper side (i.e., the ITZ above a fiber). This difference can be attributed to the combined effects of fiber on the initial packing of surrounding cement grains and on the settlement of the fresh mixture. The porosity gradients of the upper ITZs are found to be nearly identical for all the tested w/c ratios, while the porosity gradients of the lower ITZs become steeper when the w/c is higher. The lower side is also found to be the preferred location for the precipitation of calcium hydroxide crystals. Results of energy-dispersive X-ray spectroscopy (EDS) and nano-indentation analyses confirm that the chemical and mechanical properties of the ITZ are also asymmetric.

Cementitious materials may exhibit significant creep at very early age. This is potentially important for concrete 3D printing, where the material is progressively loaded even before it sets. However, does creep actually affect the buildability of 3D printed concrete? Herein, the influence of early-age creep on the buildability of 3D printed concrete is studied numerically. Creep is considered using the “local-force method”, which was developed in our previous work. This 3D printing model be used to quantify the influence of early-age creep on typical failure modes, i.e., structural instability due to buckling and plastic collapse resulting from material yielding. The green strength and early-age creep experiments are conducted to characterize early-age visco-elastic-plastic behaviors. The model is then validated with the comparison to printing experiment about buildability quantification and failure mode prediction. Parametric analyses are subsequently performed to quantify the influence of early-age creep on various printing geometries in which different failure modes are dominant. The numerical results highlight the significance of initial printing time and material mix design for predicting the buildability of 3D printing of concrete. Finally, a discussion on how creep affects structural buildability is given from the perspective of localized damage and element strain.

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.

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.

The current study investigates short-term and long-term crack-healing behaviour of mortars embedded with bacteria-based poly-lactic acid (PLA) capsules under both ideal and realistic environmental conditions. Two sets of specimens were prepared and subjected to different healing regimes, with the first set kept in a mist room for varying short durations (i.e., 1 week, 2 weeks, 3 weeks and 8 weeks) and the second set placed in an unsheltered outdoor environment for a long-term healing process (i.e., 1 year). Alteration of microstructure because of self-healing was characterized by backscattered electron (BSE) imaging and energy dispersive X-ray spectroscopy (EDS) via crack cross-sections. Results show that visible crack healing enabled by bacteria began after 2 weeks in a humid environment. The healing products initially precipitated at crack mouths and gradually moved deeper into cracks, with the precipitated calcium carbonate crystals growing larger over time. After 8 weeks, healing products can be found even a few millimetres deep inside cracks. Observations of crack healing in a realistic environment revealed significant differences compared to healing under controlled conditions. While no healing products can be found at crack mouths, a substantial healing process was observed throughout the entire crack depth. It is likely that the environmental actions such as rainfall and/or freeze and thaw cycles may have worn away the healing products at crack mouths and thus led to a deeper ingress of oxygen into cracks, which promoted the activation of healing agents and associated calcium carbonate precipitation deep inside a crack.

Direct ink writing of cementitious materials can be an alternative way for creating vascular self-healing concrete by intentionally incorporating hollow channels in the cementitious matrix. In this study, a 3D-printable fibre reinforced mortar was first developed. Three groups of specimens were fabricated using direct ink writing, where the two top and bottom printing layers were printed with different printing directions. The macrostructure of the hardened specimens was studied using CT scanning. Four-point bending tests were carried out to investigate the initial flexural strength and the strength recovery after healing with injected epoxy resin. Furthermore, water permeability test was used to evaluate the healing potential of the samples. The results from CT scanning show that printing direction influences the actual volumes of hollow channels and the volume of small pores which are a consequence of the deposition process. The hollow channels of all samples were squeezed by the upper layers during the printing process, and the longitudinally printed samples were the most affected. When printing direction changes from longitudinal to transverse, the initial flexural strength decreases. Similarly, the average permeability of the cracked samples increases when the printing direction changes from longitudinal to transverse. Although the healing effectiveness regarding flexural strength is remarkable for all specimens, it was only possible to perform a single healing process as hollow channels were then blocked by the epoxy resin. The rough surface of the hollow channels is inferred to make it difficult to extract the epoxy resin out of the specimens.

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.

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.

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.

In this paper, both synthetic slag and commercial slag covering the common composition range were employed to estimate the correlation between slag chemistry and reactivity through hydraulicity and dissolution tests. It was found that slag reactivity was favorably affected by increasing Al₂O₃ and MgO contents, while the adverse effect of decreasing CaO/SiO₂ ratio could be compensated by higher amounts of Al₂O₃ and/or MgO. When calorimetric measurement was used to assess the reactivity of slag, the effect of sulfur species incorporated in commercial slag should be taken into consideration as a small quantity of it could lead to a major difference of cumulative heat release due to the formation of ettringite. Moreover, a novel graphical method was proposed to estimate the reactivity of slag considering its chemical composition from a new perspective, i.e. a cartesian coordinate system based on (CaO/SiO₂)−(MgO + Al₂O₃).

Remarkable attention from both academia and industry has been attracted to extrusion-based 3D concrete printing (3DCP) during the last decade. Many companies in the Netherlands, e.g., Royal BAM Group, CyBe, Twente Additive Manufacturing, and Bruil, are attempting to implement this technology in practice. 3DCP is the focused digital concrete manufacturing technique in this study. The development of printable cementitious composites is possibly the most critical aspect in 3DCP. Compared to mold-cast concrete process, several essential material parameters need to be controlled in 3DCP process, i.e., pumpability, extrudability, buildability, and others. Conventional materials technology appears to have limited resources to offer for further enhancing the capabilities of 3D printing. Therefore, there is a dire need for adopting non-conventional materials solutions for which nanomaterials can play a vital role. Controlling the rheology is the key to successful 3DCP, as achieving dimensional stability and the minimum required mechanical properties in green state are the main challenges. Furthermore, achieving a required strength development rate and enabling smart monitoring of the 3DCP are the other goals that are desired in designing such materials. Recent research shows that successful modification of cementitious materials can be achieved by incorporating nanomaterials in the materials design for the enhanced fresh and hardened state properties. In this chapter, a summary of these developments is compiled in the light of potential applications, safety issues, and technological challenges.

This paper proposes the use of desalination brine as a setting and hydration activator in set-on-demand 3D concrete printing. A series of tests were conducted to investigate the effect of adding different concentrations of desalination brine on stiffness evolution and early-age hydration of Portland cement mortars (PC mixtures) and limestone-calcined clay-based cementitious materials (LC mixtures). Results show that, increasing brine concentration decreased slump, flowability and initial setting time, as well as enhanced buildability, and stimulated the stiffness development within the first hour. Furthermore, the addition of desalination brine resulted in an acceleration of cement hydration, a higher amount of chemically bound water and a higher 1st day compressive strength. The abovementioned behaviors were further promoted by doubling the brine concentration. Due to the presence of reactive aluminates in calcined clay, the acceleration of first-day hydration was slightly diminished and a higher intensity of Friedel's salt was observed in LC mixtures compared to that of PC mixtures with the same desalination brine addition.