The conventional CaCl2-H2O phase diagram is often used to describe how calcium chloride behaves when it is used on a concrete pavement undergoing freeze-thaw damage. However, the chemistry of the concrete can alter the appropriateness of using the CaCl2-H2O phase diagram. This study shows that the Ca(OH)2 present in a hydrated portland cement can interact with CaCl2 solution creating a behavior that is similar to that observed in isoplethal sections of a ternary phase diagram for a Ca(OH)2-CaCl2-H2O system. As such, it is suggested that such isoplethal sections provide a reasonable model that can be used to describe the behavior of concrete exposed to CaCl2 solution as the temperature changes. Specifically, the Ca(OH)2 can react with CaCl2 and H2O resulting in the formation of calcium oxychloride. The formation of the calcium oxychloride is expansive and can produce damage in concrete at temperatures above freezing. Its formation can also cause a significant decrease in fluid ingress into concrete. For solutions with CaCl2 concentrations greater than about 11.3 % (by mass), it is found that calcium oxychloride forms rapidly and is stable at room temperature (23 °C).

Deicing salts are often applied to the surface of pavements and bridge decks in the winter to melt ice, thereby improving safety for the traveling public. In this paper, the influence of NaCl deicing salt on freezing and thawing temperatures of pore solution and corresponding damage of mortar specimens were investigated. A low-temperature longitudinal guarded comparative calorimeter (LGCC) was developed to cool down a mortar sample at a rate of 2°C/h and to re-heat the mortar at a rate of 4°C/h. Heat flux during freezing and thawing cycles was monitored, and the temperatures at which freezing and thawing events occurred were detected. During cooling and heating, acoustic emission (AE) activity was measured to quantify the damage (cracking) caused by aggregate/paste thermal mismatch and/or phase changes. The results show that NaCl solution in a mortar sample freezes at a lower temperature than the value expected from its bulk phase diagram because of under-cooling. Conversely, the frozen solution in mortar melts at the same melting temperature as the bulk frozen NaCl solution. As the salt concentration increases, the freezing temperature is lowered. For samples containing more highly concentrated solutions, an additional exothermic event is observed whose corresponding temperature is greater than the aqueous NaCl liquidus line in the phase diagram. Damage also begins to occur at this temperature. For mortar samples saturated by solutions with 5 % and 15 % NaCl by mass, greater freeze/thaw damage is observed. The AE calorimeter developed herein is applicable for investigating damage behavior during freezing and thawing of different phases in pore solution (in mortars).

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This paper describes a series of experiments that were performed to assess the freeze–thaw behavior of mortar specimens exposed to sodium chloride (NaCl) solutions. A low-temperature longitudinal guarded comparative calorimeter was used to perform cyclic freeze–thaw testing on mortar specimens saturated with NaCl solutions. Heat flow and acoustic emission activity were monitored during the freeze–thaw experiment to detect ice formation and cracking. Although the conventional water–NaCl phase diagram would suggest that no freezing or damage would occur in specimens saturated with 15% and 23.3% NaCl solution by mass within the applied freeze–thaw temperature range, damage was observed. For these specimens, an additional heat flow peak attributed to an unexpected phase change, accompanied by acoustic activity, was detected at a temperature higher than the expected freezing point. For better understanding of the source of this damage, a low-temperature differential scanning calorimeter was used to investigate the influence of NaCl on freeze–thaw behavior of water, two pore solutions, hydrated cement powder, and calcium hydroxide powder. The results showed that the pore solution alters the freeze–thaw behavior slightly; however, it does not exhibit the unexpected phase change at higher concentrations. The specimens made with hydrated cement powder showed the unexpected phase change in high concentrations of NaCl solution in a temperature range between 0°C and 8°C. Although the exact nature of this phase change is not definitively known, it appears to result in premature damage during freeze–thaw when high-concentration salt solutions are used, even if freezing of the solution is not occurring.

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The chemical interaction between calcium chloride (CaCl2) and cementitious binder may alter the transport properties of concrete which are important in predicting the service life of infrastructure elements. This paper presents a series of fluid and gas transport measurements made on cementitious mortars before and after exposure to various solutions with concentrations ranging from 0% to 29.8% CaCl2by mass. Fluid absorption, oxygen diffusivity, and oxygen permeability were measured on mortar samples prepared using Type I and Type V cements. Three primary factors influence the transport properties of mortar exposed to CaCl2: (1) changes in the degree of saturation, (2) calcium hydroxide leaching, and (3) formation of chemical reaction products (i.e., Friedel’s salt, Kuzel’s salt, and calcium oxychloride). It is shown that an increase in the degree of saturation decreases oxygen permeability. At lower concentrations (<~12% CaCl2at room temperature), the addition of CaCl2can increase calcium hydroxide leaching, thereby increasing mortar porosity (this is offset by the formation of Friedel’s salt and Kuzel’s salt that can block the pores). At higher concentrations (>~12%), the formation of chemical reaction products (mainly calcium oxychloride) is a dominant factor decreasing the fluid and gas transport in concrete.