Title: Rheological, Chemical and Mechanical Properties of Cementitious Materials with Nanoclays and Diutan Gum
Description: Cement has three sequential states in most applications: fluid, setting and hardened. This thesis focuses on the effect of nanoclays and diutan gum on rheological, chemical and mechanical properties corresponding to the three states. Water transport properties are critically important in many applications, such as oil well cementing and 3D concrete printing. The effect of nanoclays and diutan gum on water transport properties of cement pastes were investigated. Bleeding, water retention under suction pressure, and evaporation under air flow were measured. The nanoclay was found to reduce bleeding but had no effect on water retention or evaporation. The diutan gum was found to reduce bleeding, improve water retention, and decrease evaporation loss. The rheological properties of the pastes and their interstitial solution were also characterized to resolve the mechanisms underlying the water transport behaviors. Good correlation between the measured rheological parameters and water transport properties was found.

In addition to water retention, the static yield stress build-up plays a major role in the successful oil well cementing and 3D concrete printing. Linear models are commonly used to describe the early structural build-up of cement-based materials. However, some studies have shown that there exists a faster non-linear phase before the linear phase. A simple non-linear thixotropy model is presented to describe the structural build-up process. It was quantified using static yield stress and storage modulus, which are measured through the stress growth protocol and small amplitude oscillatory shear (SAOS) tests, respectively. The effect of pre-shear, rest condition and nanoclay and diutan gum on the build-up behavior are studied. The results showed distinctly different trends between static yield stress and storage modulus. This may be attributed to the two different structures of fresh cement pastes, i.e. floc structures and C-S-H structures, measured by the stress growth protocol and SAOS test, respectively.

Phase characterization of cement paste was performed through synchrotron x-ray diffraction technique. This allowed for real-time, in-situ measurements of x-ray diffraction patterns to be obtained, and subsequently the continuous formation and decomposition of select phases over time (up to 8 hours). Phases of interest included alite, ferrite, portlandite, ettringite, monosulfate, and jaffeite (crystalline form of calcium silicate hydrate). The effects of elevated temperatures at elevated pressure, as well as the effect of nanomaterial addition were investigated. Rate of conversion of ettringite to monosulfate increased with increasing temperature, and monosulfate became unstable when temperatures reached 85ºC. The synchrotron x-ray diffraction setup appeared to have captured the seeding effect of nano-sized attapulgite clays at 0.5% addition by mass of cement, where acceleration in the rate of formation of portlandite and jaffeite was observed. Finally, the investigated system was upscaled from cement paste to cement mortar incorporating the fly ash and the slag.

The effect of the nanoclays on the mechanical properties was evaluated in comparison with the carbon nanotube. Compressive strength and tensile strength were evaluated. Results indicated that although the nanoclays are utilized primarily as a rheological modifier, they can also enhance mechanical properties.