This study investigates the effects of nano-metakaolin and fly ash contents, the water-to-binder ratio, and other factors on autogenous shrinkage, internal relative humidity, and resistivity. Hydration heat, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, mercury intrusion porosimetry, and other micro-testing techniques were employed to characterize the hydration process, phase composition, and pore structure of cementitious materials. The experimental results show that lower water-to-binder ratios lead to faster and more significant decreases in internal relative humidity within cement pastes. When nano-metakaolin and fly ash are combined, fly ash effectively mitigates the excessive autogenous shrinkage caused by nano-metakaolin under low water-to-binder ratios. Lower water-to-binder ratios result in faster resistivity growth in cement pastes. Specifically, when the water-to-binder ratio decreased from 0.35 to 0.30 and 0.25, the 28-day resistivity of nano-metakaolin–fly ash cement pastes increased by 8.08% and 7.33%, respectively. Additionally, the water-to-binder ratio has a relatively minor impact on the autogenous shrinkage and resistivity of fly ash cement pastes. Higher water-to-binder ratios accelerate the hydration rate and increase porosity, leading to the gradual coarsening of pore distributions. When the water-to-binder ratio increased from 0.25 to 0.35, the 28-day porosity increased by 50.31%. In hydration systems with lower water-to-binder ratios, internal relative humidity decreases more rapidly, pores become refined, capillary stresses increase, and autogenous shrinkage behavior becomes more pronounced. This research provides a practical foundation for studying the early-age autogenous shrinkage behavior of cementitious materials.

In order to study the influence of nano-clay on the crack resistance of cement-based materials, two kinds of nano-metakaolin (NMK) and two kinds of nano-attapulgite clay (NMA) were considered. The early cracking process and mechanical properties of nano-clay cement mortar (NCM) was studied by using a plate knife-edge constraint test. Based on fractal theory, the distribution characteristics of NCM surface cracks were revealed, and the calculation method forNCM maximum crack width was given. The results show that the cracking time of the NMK-3 specimen is 2 and 6 h later than that of NMK-1 and NMA-2, respectively; the smaller the particle size of nano-clay, the earlier the cracking time of the specimen. However, nano-clay effectively inhibited the expansion of mortar cracks, and the cracks on the surface of NCM were thin and sparse. At 28 days, the maximum crack width of NMK-3 was 46.7% and 33.3% lower than that of NMK-1 and NMA-2, respectively. NMK hadthe best improvement effect on the mechanical properties cement mortar. The smaller the particle size, the more pronounced the improvement effect.The flexural strength ratio and compressive strength ratio at 7 and 28 days are 76.7%, 67.4%, and 61.2%, respectively.The distribution of surface cracks on NCM has fractal characteristics, and the fractal dimension of surface cracks is smaller than that of ordinary cement mortar. The larger the particle size of nano-clay, the smaller the fractal dimension of cracks. The quantitative relationship between fracture fractal dimension and NCM elastic modulus and shrinkage tensile stress is established.

To explore the effect of nano-attapulgite clay (NAC) on the durability of concrete, two kinds of NAC (calcined raw ore and calcined high viscosity ore: calcination at 650 °C for 2 h) were used to study their effects on the durability of concrete, mainly discussing the changes of chloride ion permeability and the resistivity of concrete with NAC. The effect of NAC on the strength of concrete was analyzed by testing the compressive strength of concrete. The two-electrode method, four-electrode method, and concrete resistivity tester were used to analyze the relationship between the testing method and concrete resistivity, and the effect of NAC on concrete resistivity was analyzed. The influence of NAC on the chloride corrosion resistance of concrete was analyzed by measuring the chloride diffusion coefficient, and the relationship between the chloride diffusion coefficient and resistivity was established. The diffusion process of chloride ions in concrete was analyzed by theoretical derivation and numerical simulation. The results show that: calcining raw ore NAC can improve the compressive strength of concrete, while calcining high-viscosity ore reduces the compressive strength of concrete. At the age of 28 days, the strength of concrete mixed with calcined raw ore is about 7.10% higher than that of ordinary concrete, while the compressive strength of concrete mixed with calcined high-viscosity ore is about 4.32% lower than that of common concrete. The resistivity of concrete mixed with calcined raw ore increases the fastest, and the 56 days age is about 15.8% and 29.6% higher than that of ordinary concrete and calcined high-viscosity ore. There is a good negative correlation between concrete resistivity and chloride diffusion coefficient. At 28 days, the incorporation of calcined raw ore concrete decreased by about 19.9% and 49.4% compared with ordinary concrete and calcined high-viscosity ore, respectively. After 10 years of decline, the chloride ion content is 11.1% and 23.2% lower than that of ordinary concrete and concrete mixed with calcined high viscosity ore.

Corrosion of traditional cement mortar is a critical issue in karst areas. Composite salt, i.e., sulfate–chloride salt, represents a typical corrosion agent due to the abundance of Cl⁻ and SO₄²⁻ ions in such geological environments. In this study, we used nano-metakaolin to enhance the physical and mechanical properties of cement mortar in the early aging stages, simulating groundwater corrosion by a compound salt solution in the karst region. The appearance and the change in the flexural/compressive strength of cement mortar upon the nano-metakaolin addition in the early aging stages under dry and wet cycling conditions were analyzed and combined with the results of scanning electron microscopy, thermogravimetric analysis, and other methods, revealing the underpinning mechanism behind the function changes of nano-metakaolin-modified cement mortar. The results show that nano-metakaolin effectively promotes cement hydration in the early aging stages. The flexural/compressive strength after 7 days of aging with 1% of added nano-metakaolin increased by 10.38% and 4.41%, respectively, compared to ordinary cement mortar. Furthermore, adding 1–5% of nano-metakaolin under dry and wet cycling and the coupling effect of chloride and sulfate erosion effectively reduce the damage of harmful ions on the cement mortar, leading to evident corrosion inhibition. The generation of hydration products increased after adding the Ghanaian metakaolin, filling the microcracks and micropores, and increasing the overall microstructural compactness.

This study investigates the damage evolution mechanism affecting the fracture-bearing performance of fly ash cement paste under low-temperature curing conditions. Pre-cut cement paste specimens with fly ash contents of 0%, 15%, and 25% were prepared and subjected to both standard curing and low-temperature curing at 5 °C for 28 days. Three-point bending tests combined with acoustic emission (AE) monitoring were conducted to analyze peak flexural load, AE ring count, cumulative energy, RA-AF crack classification, and b-value evolution. Additionally, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) were employed to characterize micromorphology and relative changes in hydration product content. The results indicate that both fly ash incorporation and low-temperature curing significantly reduce the flexural bearing capacity of pre-notched specimens. Under low-temperature curing, the peak loads of LF15 and LF25 decrease by 34.83% and 47.19%, respectively, compared to LF0. At the same fly ash replacement level, all low-temperature-cured specimens exhibited lower peak loads than those cured under standard conditions. Overall AE activity was reduced in low-temperature-cured specimens, with crack propagation instability occurring at lower load levels. The addition of fly ash shifted the fracture mode toward a tensile-dominated type, whereas low-temperature curing increased the proportion of shear-type AE events. Fly ash incorporation increased the relative content of calcium silicate hydrate (C-S-H) gel and decreased that of calcium hydroxide (CH); however, this did not result in improved peak flexural load. This outcome is attributed to the insufficient reactivity of fly ash at low temperatures, leading to residual unreacted spherical particles, dilution of clinker, and inadequate interfacial bonding, which collectively weaken the continuous load-bearing skeleton of the matrix. This paper establishes a multi-scale interpretation of the damage mechanisms affecting the low-temperature fracture-bearing performance of fly ash cement paste by correlating macroscopic bearing response, AE damage evolution, crack types, and hydration product composition.