In this study, supercooling effects on the hygrothermal behavior of fired clay materials under various experimental conditions, such as water content, cooling rates, and size of specimens were investigated using experimental methods and hygrothermal simulations. We report results of the differential scanning calorimetry (DSC) and temperature distribution changes during a freeze–thaw (FT) experiment using unsaturated specimens. Also, we developed a numerical model of the freezing and thawing processes including the supercooling processes. The DSC results show the freezing of the supercooled water in a fired clay material is considerably faster than that in cement-based materials. It was also found that the dependency of the supercooling effects on the cooling rates seemed to be small. When the water saturation of a material decreases, the rate of the ice saturation increase during the freezing of the supercooled water is decreased while the freezing points of the supercooled water was not changed considerably. The comparison of the results of the FT experiment and hygrothermal simulations show that the combination of the existed hygrothermal model and a modified kinetic equation can reproduce the rapid temperature rise during the freezing of the supercooling water in the FT experiment. Finally, the size effects of specimens on the supercooling phenomenon was discussed based on the experimental and calculation results. The freezing points got higher when a specimen was larger. Due to differences in the ratio of the surface area to the volume, hygrothermal behavior in small specimens and relatively large specimens like that of the DSC and the FT experiment, respectively were markedly different. Water in a relatively large specimen with a small ratio of surface area to volume can achieve the thermodynamic equilibrium in a short period after the freezing starts.

This paper investigates the hydration rate in fly ash blended cement paste and self-healing ability in mortar incorporating fly ash for long-term period. The hydration rate of fly ash and consumption of calcium hydroxide in fly ash paste containing calcium hydroxide reagents were examined at different ages and curing temperatures. Five types of fly ash blended cement paste, each of which with 10% by mass fly ash replacement ratio, were prepared for the acceleration test at 80 o C. Four fly ash cement pastes, with two types of fly ash and with fly ash replacement ratios by mass 10% and 30%, were tested to measure the rate of reaction of fly ash in the mixtures. Ten mixtures were tested to evaluate the self-healing ability of mortar incorporating fly ash, considering different types of cement and fly ash. Compressive strength, bending strength, accelerated carbonation depth, after applying freeze/thaw cycling until 60% and 80% relative dynamic modulus of elasticity, and porosity were examined. The experimental results revealed that incorporating fly ash in cement paste would affect the hydration rate of fly ash and consumption of calcium hydroxide. Curing temperature can affect hydration rate, acceleration rate and velocity of reaction rate in fly ash cement paste. Moreover, it is confirmed that self-healing ability, carbonation rate coefficient and the pore volume modification in mortar incorporating fly ash rely on the curing conditions. Finally, it is suggested that the practical fly ash replacement ratio in concrete could be 10% to 15% and 11% to 20% for water to cement ratios 0.50 to 0.55 and 0.55 to 0.60, respectively.

To investigate the supercooling phenomenon in fired clay materials, low-temperature differential scanning calorimetry (DSC) and a one-dimensional freeze-thaw (FT) experiment were performed on saturated specimens. The rate of increase in ice saturation during freezing was calculated from the DSC result. Rapid ice growth over a relatively narrow temperature range (within about 0.2 K) was observed at a cooling rate of 0.25 K/min. In the FT experiment, the temperature distribution of a specimen was measured with inserted thermocouples. According to the results of the FT experiment, a rapid temperature increase was observed at sub-zero temperatures accompanied by freezing of the supercooled water. When the supercooled water began to freeze, the released latent heat was found to strongly prevent the specimen temperature from dropping even during the cooling period. Finally, a hygrothermal model of freezing and thawing including a non-equilibrium supercooling process was developed. The freezing rate of the supercooled water was modelled based on the DSC result. The validity of the model was verified by comparing the results of the FT experiment and calculations. The model was found to be able to replicate the rapid temperature rise during the cooling period of the FT experiment.

Frost action is one of the main causes for deterioration of porous building materials under defined hygrothermal conditions. For an accurate assessment of the frost damage risk under various environmental conditions, thermal, moisture, and mechanical properties should be considered; the hygrothermal properties affect the distribution of temperature and amount of frozen water in the material, whereas the mechanical properties are necessary to predict deformation and damage. Moreover, the dependency of these properties on the moisture content should be understood. Therefore, in this study, thermal, moisture, and mechanical properties of wet and dry fired clay materials were measured. The fired clay materials were sintered at two different temperatures, 1000 °C and 1100 °C (samples T10 and T11, respectively) for comparison. The measured thermal and mechanical properties are considerably different in the wet state compared to the dry state. Freeze–thaw tests were conducted to investigate the relation between the material properties and the frost resistance under a simple experimental condition. As expected, based on the pore structure and obtained mechanical properties, T10 exhibited lower frost resistance than T11 in the freeze–thaw test. Finally, frost damage risk was assessed under various environmental conditions based on the obtained hygrothermal and mechanical properties.