Title: Durability of Cement Composites Reinforced with Sisal Fiber
Description: This dissertation focuses mainly on investigating the aging mechanisms and degradation kinetics of sisal fiber, as well as the approaches to mitigate its degradation in the matrix of cement composites. In contrast to previous works reported in the literature, a novel approach is proposed in this study to directly determine the fiber's degradation rate by separately studying the composition changes, mechanical and physical properties of the embedded sisal fibers. Cement hydration is presented to be a crucial factor in understanding fiber degradation behavior. The degradation mechanisms of natural fiber consist of mineralization of cell walls, alkali hydrolysis of lignin and hemicellulose, as well as the cellulose decomposition which includes stripping of cellulose microfibrils and alkaline hydrolysis of amorphous regions in cellulose chains. Two mineralization mechanisms, CH-mineralization and self-mineralization, are proposed. The degradation kinetics of sisal fiber in the cement matrix are also analyzed and a model to predict the degradation rate of cellulose for natural fiber embedded in cement is outlined.

The results indicate that the time needed to completely degrade the cellulose in the matrix with cement replacement by 30wt.% metakaolin is 13 times longer than that in pure cement. A novel and scientific method is presented to determine accelerated aging conditions, and to evaluating sisal fiber's degradation rate and durability of natural fiber-reinforced cement composites. Among the static aggressive environments, the most effective approach for accelerating the degradation of natural fiber in cement composites is to soak the samples or change the humidity at 70 ºC and higher temperature. However, the dynamic wetting and drying cycling treatment has a more accelerating effect on the alkali hydrolysis of fiber's amorphous components evidenced by the highest crystallinity indices, minimum content of holocellulose, and lowest tensile strength. Based on the understanding of degradation mechanisms, two approaches are proposed to mitigate the degradation of sisal fiber in the cement matrix.

In order to relieve the aggressive environment of hydrated cement, cement substitution by a combination of metakaolin and nanoclay, and a combination of rice husk ash and limestone are studied. Both metakaolin and nanoclay significantly optimize the cement hydration, while the combination of these two supplementary cementitious materials validates their complementary and synergistic effect at different stages of aging. The presented approaches effectively reduce the calcium hydroxide content and the alkalinity of the pore solution, thereby mitigating the fiber degradation and improving both the initial mechanical properties and durability of the fiber-cement composites. The role of rice husk ash in cement modification is mainly as the active cementitious supplementary material. In order to improve the degradation resistance of sisal fiber itself, two novel, simple, and economical pretreatments of the fibers (thermal and sodium carbonate treatment) are investigated. Both thermal treatment and Na2CO3 treatment effectively improve the durability of sisal fiber-reinforced concrete.

The thermal treatment achieves improvement of cellulose's crystallization, which ensures the initial strength and improved durability of sisal fiber. A layer consisting of calcium carbonate sediments, which protects the internals of a fiber from the strong alkali pore solution, is formed and filled in pits and cavities on the Na2CO3 treated sisal fiber's surface.