For the first time, this paper explores the role of hydration kinetics on microcrack development in cement mortars using the μ-CT technique with a resolution of 2.2 µm. Three binders were tested: fine-grained ordinary Portland cement (OPC) with Blaine fineness of 391 m²/kg, coarse-grained OPC made from the same clinker with Blaine fineness of 273 m²/kg, and H-cement as a representative of the alkali-activated binder. It was found that most microcracks have a width in the range of 5–10 µm, increasing their occurrence with the progress of sealed hydration. While H-cement and coarse-grained OPC showed a comparable number of microcracks, fine-grained OPC exhibited more than twice the number of microcracks. In this sense, high hydration kinetics induce more microcracks, promoting later coalescence into visible cracks and disintegration of concrete at the end. Therefore, durable concrete with minimum microcracks should be derived from slow hydration kinetics or alkali-activation processes.

Cementitious materials exhibit shrinkage strain on drying, leading easily to crack formation when internally or externally restrained. It is known that cements with a slow strength gain show higher crack resistance under external drying. The ring shrinkage test can be considered an accelerated method for cracking tendency due to existing historical correlations between ring cracking time and long-term surface concrete cracking. The experimental campaign used ring shrinkage tests on 25 mortars, covering 10 commercial cements and 15 cements produced on demand, covering Portland cements and blended cements up to a 30% slag substitution. The results show that the restrained ring cracking time generally increases with lower Blaine fineness and higher slag substitution in 6 to over 207 days’ span. Upper limits for crack-resistant cements were proposed for 2-day compressive strength and Blaine fineness, in the case of Portland cements: 27.7 MPa and 290 m²/kg, respectively. A hygro-mechanical model successfully replicated strain evolution with crack formation and brittle failure. Only two out of ten commercial cements were classified as crack-resistant, while the ratio increased to 10 out of 15 cements which were produced on demand.

Concrete exposure to high temperatures induces thermo-hygral phenomena, causing water phase changes, buildup of pore pressure and vulnerability to spalling. In order to predict these phenomena under various conditions, a three-phase transport model is proposed. The model is validated on X-ray CT data up to 320 °C, showing good agreement of the temperature profiles and moisture changes. A dehydration description, traditionally derived from thermogravimetric analysis, was replaced by a formulation based on data from neutron radiography. In addition, treating porosity and dehydration evolution as independent processes, previous approaches do not fulfil the solid mass balance. As a consequence, a new formulation is proposed that introduces the porosity as an independent variable, ensuring the latter condition.