Although concrete is one of the most widely used construction materials, it is characterized by substantially low tensile strength in comparison to its compression strength, and the occurrence of cracks is unavoidable. In addition, cracks progress due to environmental conditions including damage by freezing, neutralization, and salt, etc. Moreover, detrimental damage can occur in concrete structures due to the permeation of deteriorating elements such as Cl⁻ and CO₂. Meanwhile, under an environment in which moisture is being supplied and if the width of the crack is small, a phenomenon of self-healing, in which a portion of the crack is filled in due to the rehydration of the cement particles and precipitation of CaCO₃, is been confirmed. In this study, cracks in cementitious composite materials are effectively dispersed using synthetic fibers, and for cracks with a width of more than 0.1 mm, a review of the optimal self-healing conditions is conducted along with the review of a diverse range of self-healing performance factors. As a result, it was confirmed that the effective restoration of watertightness through the production of the majority of self-healing products was achieved by CaCO₃ and the use of synthetic fibers with polarity, along with the effect of inducing a multiple number of hairline cracks. In addition, it was confirmed that the self-healing conditions of saturated Ca(OH)₂ solution, which supplied CO₂ micro-bubbles, displayed the most effective self-healing performance in the surface and internal sections of the cracks.

Recently, there has been increased use of calcium-nitrite and calcium-nitrate as the main components of chloride- and alkali-free anti-freezing agents to promote concrete hydration in cold weather concreting. As the amount of nitrite/nitrate-based accelerators increases, the hydration of tricalcium aluminate (C₃A phase) and tricalcium silicate (C₃S phase) in cement is accelerated, thereby improving the early strength of cement and effectively preventing initial frost damage. Nitrite/nitrate-based accelerators are used in larger amounts than usual in low temperature areas below −10 °C. However, the correlation between the hydration process and strength development in concrete containing considerable nitrite/nitrate-based accelerators remains to be clearly identified. In this study, the hydrate composition (via X-ray diffraction and nuclear magnetic resonance), pore structures (via mercury intrusion porosimetry), and crystal form (via scanning electron microscopy) were determined, and investigations were performed to elucidate the effect of nitrite/nitrate-based accelerators on the initial strength development and hydrate formation of cement. Nitrite/nitrate-AFm (aluminate-ferret-monosulfate; AFm) was produced in addition to ettringite at the initial stage of hydration of cement by adding a nitrite/nitrate-based accelerator. The amount of the hydrates was attributed to an increase in the absolute amounts of NO₂⁻ and NO₃⁻ ions reacting with Al₂O₃ in the tricalcium aluminate (C₃A phase). Further, by effectively filling the pores, it greatly contributed to the enhancement of the strength of the hardened cement product, and the degree of the contribution tended to increase with the amount of addition. On the other hand, in addition to the occurrence of cracks due to the release of a large amount of heat of hydration, the amount of expansion and contraction may increase, and it is considered necessary to adjust the amount used for each concrete work.

There has recently been an increased use of anti-freezing agents that are primarily composed of salt- and alkali-free calcium nitrite (Ca(NO₂)₂) and calcium nitrate (Ca(NO₃)₂) to promote the hydration reaction of concrete in cold weather concreting. Nitrite–nitrate based accelerators accelerate the hydration of C₃A and C₃S in cement more quickly when their quantities are increased, thereby boosting the concrete’s early strength and effectively preventing early frost damage. However, the connection between the hydrate formation behavior and the strength development characteristic over time has yet to be clearly identified. Therefore, in this study, a wide range of physicochemical reviews were carried out to clarify the relationship between the hydrate formation behavior and the strength development characteristics, both at an early age and at later ages, which results from the addition of nitrite–nitrate based accelerators to concrete in varying amounts. These accelerators also act as anti-freezing agents. The results show that an increased quantity of nitrite–nitrate based accelerators caused an increase in the early strength of the concrete. This was due to the formation of nitrite and nitrate hydrates in large amounts, in addition to ettringite containing SO₄², which is generated during the hydration reaction of normal Portland cement at an early age. On the other hand, at later ages, there was a rise in nitrite and nitrate hydrates with needle crystal structures exhibiting brittle fracture behavior. A decrease in C–S–H gel and Ca(OH)₂ hydrates, deemed to have caused a decline in strength on Day 3 and thereafter, was also observed.

Cracking is an inherent development in reinforced concrete structures and can lead to serious damages during their service period. The repeated occurrence of such damages can enlarge the cracks, thereby allowing other deteriorating elements such as CO₂ and Cl⁻ to further infiltrate the concrete, which can seriously compromise the concrete structure. This study focuses on the type of calcium carbonate (CaCO₃) crystals generated by the self-healing phenomenon. Owing to polymorphism, CaCO₃ has three types of crystal forms—calcite, vaterite, and aragonite—whose formation can be controlled by the temperature and pH. Vaterite has the highest density among these crystals, and it is expected to be capable of self-healing. Therefore, experiments were conducted to establish the conditions required to promote the generation of vaterite. A saturated Ca(OH)₂ solution with CO₂ nanobubbles (CN) was employed for effective self-healing. The temperature was controlled at 20, 40, and 60 °C, and the pH was controlled at 9.0, 10.5, and 12.0. The results showed that the self-healing of cracks occurred both on the surface and internally, and the main product of the self-healing phenomenon was vaterite in CaCO₃ crystals at a pH of 9.0 and a temperature of 40 °C. Furthermore, the addition of a saturated Ca(OH)₂ solution with CO₂ nanobubbles (CN) resulted in the most effective self-healing of the surface and internal cracks.

Concrete has a remarkably low ratio of tensile strength to compressive strength, and is widely used in construction. However, the occurrence of cracks in a concrete structure is inevitable. Nevertheless, in the presence of adequate moisture, small cracks in the concrete structure exhibit a propensity to self-heal by getting filled due to the rehydration of cement particles and the subsequent precipitation of calcium carbonate (CaCO₃). According to previous studies, the self-healing performance can be maximized by optimizing the temperature and pH to control the crystal formation of CaCO₃. This study focused on the crystal form of CaCO₃ generated in the self-healing of a cement-based composite material. To evaluate the self-healing performance depending on the type of aqueous solution and the temperature, the weight change, the weight change rate, and the porosity reduction in each case were evaluated. Moreover, to increase the generation of CaCO₃ (which is a self-healing precipitate), nanosized ultrafine CO₂ bubbles using CO₂ gas were used, along with an adequate supply of Ca²⁺ by adjusting the aqueous solution (Ca(OH)₂, CaO + ethanol). For greater pore-filling effects by controlling the CaCO₃ crystal forms in the cement matrix, the change in the crystal form of the precipitated CaCO₃ in the hardened cement paste with changing temperature was analyzed by scanning electron microscopy and X-ray diffraction. As a result, the possibility of the effective generation and control of vaterite with a dense pore structure together with calcite was confirmed by adjusting the temperature to approximately 40 °C at a pH of 12.

Recently, calcium nitrite (Ca(NO₂)₂) and calcium nitrate (Ca(NO₃)₂) have been increasingly used as the main components of salt- and alkali-free anti-freezing agents, for promoting concrete hydration in cold-weather concreting. With an increase in the amount of nitrite-based accelerator, the hydration of C₃A, C₃S, and βC₂S in the cement is accelerated, thereby improving its early strength and effectively preventing the initial frost damage. Meanwhile, with an increase in the amount of nitrite-based accelerator, the expansion and shrinkage of the concrete—and, therefore, the crack occurrence—are expected to increase. In this study, various experiments were conducted on shrinkage, crack initiation, and the development of mortar containing a considerable amount of a nitrite-based accelerator. The result confirmed that, as the amount of nitrite-based accelerator was increased, the shrinkage was increased, and cracking in early age was more likely to occur, compared to the cases without the addition of this accelerator.