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The exposure of concrete structures to acid attack is a growing concern. This study employs thermodynamic modeling to investigate the changes in phase assemblage of powdered cement pastes subjected to a wide range of sulfuric and acetic acid concentrations. A modeling approach utilizing IPHREEQC implemented through Matlab is presented, and the obtained results are compared with pH measurements and compositions of equilibrated calcium and sulfate solutions. The influence of incorporating 11% silica fume (SF) as a replacement for cement predicted a 70% reduction of Portlandite content in the hardened cement paste. Consequently, the acid attack processes and subsequent pH reduction are affected. The modeling approach demonstrates good agreement with experimental data for acetic acid, across a broad range of acid concentrations, for both Portland cement and a blend with SF, without the need for any fitting parameters. However, significant discrepancies between the model and experiments are observed in the case of sulfuric acid. This discrepancy arises due to the formation of lump pieces of material in the experimental setup at higher acid concentrations. These lumps consist of a thin layer of altered hardened cement paste, primarily composed of sulfate‐rich phases, encapsulating unaltered hardened cement paste. Since the reaction was not homogeneous and the powder did not entirely react, the sulfuric attack experimental setup was not representative for validating the thermodynamic model. [ABSTRACT FROM AUTHOR]

Concrete structures are increasingly becoming exposed to organic acid attack conditions, such as those found in agriculture and food-related industries. This paper aims to experimentally verify the thermodynamic modeling of cement pastes under acetic acid attack. For this, a modeling approach implemented in IPHREEQC via Matlab is described, and results are compared with measured pH and compositions of equilibrated solutions (MP-AES) as well as unreacted/precipitated solids (XRF, XRD and STA) for a wide range of acid concentrations. The 11% replacement of cement by silica fume (SF) led to a 60 or 70% reduction (measured or modeled, respectively) of Portlandite content in the hardened cement paste due to the pozzolanic reaction resulting in higher content of CSH phases, which has effects on the progression of dissolution processes and a resulting pH with increased acid concentrations. Considering that no fitting parameter was used, the model predictions showed good agreement with measured values of pH, dissolved ion concentrations and composition of the remaining (degraded) solids overall. The discrepancies here were more pronounced at very high acid concentrations (equilibrium pH < ~4), i.e., after the full dissolution of hydrate phases due to limitations in the model used to describe Al-, Si- and Fe-gel phases and/or identified experimental challenges in precipitation of calcium and aluminum acetate hydrates. [ABSTRACT FROM AUTHOR]

This study aims to increase the pozzolanic reactivity of metakaolin (MK) in Portland cement (PC) blends by adding additional calcium hydroxide (CH_add) to the initial mixture. Cement paste samples were prepared with PC, MK and water with a water-to-binder ratio of 0.6. Cement replacement ratios were chosen from 5 to 40 wt.% MK. For higher replacement ratios, i.e., 20, 30 and 40 wt.% MK, CH_add was included in the mixture. CH_add-to-MK ratios of 0.1, 0.25 and 0.5 were investigated. Thermogravimetric analysis (TGA) was carried out to study the pozzolanic reactivity after 1, 7, 28 and 56 days of hydration. A modified mass balance approach was used to normalize thermogravimetric data and to calculate the calcium hydroxide (CH) consumption of samples with CH_add. Results showed that, without CH_add, a replacement ratio of 30 wt.% or higher results in the complete consumption of CH after 28 days at the latest. In these samples, the pozzolanic reaction of MK turned out to be restricted by the amount of CH available from the cement hydration. The increased amount of CH in the samples with CH_add resulted in an enhanced pozzolanic reaction of MK as confirmed by CH consumption measurements from TGA. [ABSTRACT FROM AUTHOR]