If concrete made with Portland cement or blast furnace slag cement is subjected to heat, a number of transformations and reactions occur, even if there is only a moderate increase in temperature.5,6 As aggregate materials normally occupy 65 to 75% of the concrete volume, the behavior of concrete at elevated temperature is strongly influenced by the aggregate type. Commonly used aggregate materials are thermally stable up to 300°C–350°C. Aggregate characteristics of importance to behavior of concrete at elevated temperature include physical properties (e.g., thermal conductivity and thermal expansion), chemical properties (e.g., chemical stability at temperature), and thermal stability/integrity. Aggregate materials may undergo crystal transformations leading to significant increases in volume [e.g., crystalline transformation of α-quartz (trigonal) to β-quartz (hexagonal) between 500 and 650°C with an accompanying increase in volume of ~5.7%]. Some siliceous or calcareous aggregates with some water of constitution exhibit moderate dehydration with increasing temperature that is accompanied by shrinkage (i.e., opal at 373°C exhibits shrinkage of ~13% by volume).7 Most nonsiliceous aggregates are stable up to about 600°C. At higher temperatures, calcareous aggregates (calcite – CaCO3), magnesite (MgCO3), and dolomite (MgCO3/CaCO3) dissociate into an oxide and CO2 (CaO + CO2). Calcium carbonate dissociates completely at 1 atm pressure at 898°C with partial dissociation occurring at temperatures as low as 700°C (Ref. 8). Above 1200°C and up to 1300°C some aggregates, such as igneous rocks (e.g., basalt), show degassing and expansion. Refractory aggregates can be utilized to produce significant improvements in the heat resistance of Portland cement concretes. It has been noted that the thermal stability of aggregates increases in order of gravel, limestone, basalt, and lightweight.9
Apart from the crystalline transformations occurring mainly in the aggregate materials during heating, a number of degradation reactions occur, primarily in the cement paste, that result in a progressive breakdown in the structure of the concrete. An increase in temperature produces significant changes in the chemical composition and microstructure of the hardened Portland cement paste. At low temperatures these reactions mainly take the form of dehydration and water expulsion reactions. Changes in the chemical composition and microstructure of the hardened Portland cement paste occur gradually and continuously over a temperature range from room temperature to 1000°C. At room temperature, between 30 and 60% of the volume of saturated cement paste and between 2 and 10% of the volume of saturated structural concrete are occupied by evaporable water. As the temperature to which the cement paste is subjected increases, evaporable water is driven off until at a temperature of about 105°C all evaporable water will be lost, given a sufficient exposure period. At temperatures above 105°C, the strongly absorbed and chemically combined water (i.e., water of hydration) are gradually lost from the cement paste hydrates, with the dehydration essentially complete at 850°C. Dehydration of the calcium hydroxide is essentially zero up to about 400°C, increases most rapidly around 535°C, and becomes complete at about 600°C (Ref. 10). Figures 1 and 2 indicate the influence of temperature on the ultimate compressive strength and modulus of elasticity of a Portland cement paste (Type I Portland cement; water/cement = 0.33) (Ref. 11).
A good summary of the degradation reactions that occur in Portland cement concrete is provided in
Ref. 4. Upon first heating, substantial water evaporation occurs from the larger pores close to the concrete surface. Then, from 100°C onward, the evaporation proceeds at a faster rate with water being expelled from concrete near the surface as a result of above-atmospheric vapor pressure (i.e., steam flow). At 120°C the expulsion of water physically bound in the smaller pores, or chemically combined, initiates and continues up to about 500°C where the process is essentially complete. From 30°C to 300°C, in conjunction with evaporation, dehydration of the hardened cement paste occurs (first stage) with the maximum rate of dehydration occurring at about 180°C [Tobermorite gel is stable up to a temperature of 150°C (Ref. 12)]. In the temperature range from 450°C to 550°C there is decomposition of the portlandite [i.e., Ca(OH)2 → CaO + H2O) (Ref. 12)]. At 570°C the α → β inversion of quartz takes place with the transformation being endothermic and reversible. A further process of decomposition of the hardened cement paste takes place between 600°C and 700°C with the decomposition of the calcium-silicate- hydrate phases and formation of β-C2S. Between 600°C and 900°C the limestone begins to undergo decarbonation (i.e., CaCO3 → CaO + CO2). The rate of decomposition and the temperature at which it occurs are not only dependent on temperature and pressure, but also by the content of SiO2 present in the limestone. Above 1200°C and up to 1300°C, some components of the concrete begin to melt. Above 1300°C to 1400°C concrete exists in the form of a melt. Apparently liquifaction of the concrete commences with melting of the hardened cement paste followed by melting of the aggregates.13–15 The melting points of aggregates vary greatly. At 1060°C basalt is at the lower limit of all types of rock, with quartzite not melting below 1700°C (Ref. 5).