Quantum Chemical Modeling of the Effects of Hydrated Lime (Calcium Hydroxide) as a Filler in Bituminous Materials

Abstract

Hydrated lime is widely used as a mineral filler to improve several properties of bituminous materials such as reducing the susceptibility of the composite to moisture-induced damage. Although experimental evidence supports the efficacy of using hydrated lime as a mineral filler, the molecular scale mechanism of reactivity of hydrated lime within the bitumen to reduce moisture damage is not understood. This is important when considering the durability of structural applications of bituminous materials such as asphalt concrete pavements subjected to both environmental and loading extremes. In this study, the interaction between hydrated lime and the key molecular building blocks of bitumen is modeled using density functional theory and compared against analogues of other common fillers such as calcite and quartz. Free energies of dissociation (ΔG dissoc) are calculated, and the nature of the bonds is characterized with contour maps of the Laplacian of the electron density. Hydrated lime is capable of reacting with specific functional groups in bitumen moieties and developing strong, water-resistant complexes. Among the functional groups investigated, carboxylic acids are the preferential reaction sites between hydrated lime and the bitumen moieties. Values as high as ΔG dissoc = +49.42 kcal/mol are reported for hydrated lime with water as the surrounding solvent. In contrast, analogues of calcite (ΔG dissoc = +15.84 kcal/mol) and quartz (ΔG dissoc = +4.76 kcal/mol) are unable to chemically react as strongly as hydrated lime in the presence of water. Contour maps of the Laplacian of the electron density indicate that the bonds between hydrated lime and model asphalt moieties are of an ionic nature. The atomistic modeling results correlate with thermodynamic calculations derived from experimental constants and are consistent with infrared spectrometric data.

Assessing the Effects of Different Fillers and Moisture on Asphalt Mixtures’ Mechanical Properties and Performance

“…On the other hand, Al-Tameemi and Grajales et al, [10,11] found that slaked lime can react with some specific functional groups in the asphalt and form a strong waterproofing compound that significantly improves the water stability of the asphalt mixture. Likewise, Hu et al, [12][13][14][15] successfully used waste brake pads as fillers to modify the asphalt mixture and found satisfactory results with respect to enhancing both the moisture tolerance and high-temperature stability performance of the asphalt mixture.…”