Title: Effects of Curing Temperature and Pressure on the Chemical, Physical, and Mechanical Properties of Portland Cement
Description: This dissertation mainly focuses on studying the fundamental hydration kinetics and mechanisms of Portland cement as well as the effects of curing temperature and pressure on its various properties. An innovative test apparatus has been developed in this study to cure and test cement paste specimens under in-situ conditions, such as down-hole in oil wells with high temperature and high pressure. Two series of tests were performed using cement pastes prepared with four different classes of oilwell cement (namely Class A, C, G, and H cements). Specimens in groups of four were cured at temperatures ranging from ambient to 60°C and pressures ranging from 0.69 to 51.7 MPa for a period of 48 or 72 hours. The density and w/c ratio of the specimens at the time of casting as well as at the end of the curing period were recorded. Total chemical shrinkage of the cement paste was measured continuously during the entire hydration period while tensile strength was obtained at the end of the curing period using both water pressure and splitting tension test methods.

Due to capacity limitations of the test equipment, in-situ tensile strength was obtained for only one test series with a highest curing pressure of 13.1 MPa. Specimens from the other test series were depressurized before the tensile strength tests. Chemical shrinkage test is an important method of measuring cement hydration kinetics in that the normalized total chemical shrinkage is approximately equal to the degree of cement hydration. By studying the correlations between the chemical shrinkage and the non-evaporable water content of cement during hydration, a multi-linear model is first proposed to estimate the normalization factors for different types of cement under different curing conditions. Based on the hydration kinetics data obtained from chemical shrinkage test results, a new approach of modeling the effect of curing temperature and pressure on cement hydration kinetics is proposed. It is found that when a hydration kinetics curve is represented by an unknown function, the effect of curing condition on the curve can be modeled by incorporating a simple scale factor in this function.

The relationship between this scale factor and curing condition is described by chemical kinetics laws. While the proposed new approach of modeling cement hydration kinetics has the advantage of being widely applicable to different types of cement, it only explains one influence factor of cement hydration (i.e. the curing condition). In order to take into account other influence factors and to further understand the fundamental mechanisms of cement hydration, a more complex particle-based numerical hydration model is developed by combining the two well-known cement hydration mechanisms, namely the nucleation and growth controlled mechanism and the diffusion controlled mechanism. The model is applied to experimental data of both C3S hydration in dilute suspensions and Class H cement paste hydration. Excellent agreement is observed between experimental and modeled results. Three rate-controlling parameters with clear physical meanings can be identified from the proposed model. Fitted model parameters are found to be in reasonable agreement with experimental observation.

The dependencies of these parameters on particle size, cement composition, w/c ratio, and curing condition are also investigated. Finally, the importance of cement hydration kinetics is illustrated by showing their close correlations with the physical and mechanical properties. The various influence factors, including the curing temperature and pressure, of physical and mechanical property test results (particularly density and tensile strength) are evaluated. Potential damage mechanisms of cement paste specimens during depressurization are studied by analyzing the deformation behavior of the entire system consisting of the cement paste and pressurizing water.