Abstract

Calcium silicate cement (CSC) can be a promising cementitious binder for its
reduced CO2 footprint in comparison with ordinary Portland cement, while its
detailed chemical information remains undisclosed. Herein, we present thermodynamic
calculation results that illustrate the effect of reaction and carbonation degrees
on the reaction products of CSC that undergoes the hardening process at an elevated
atmospheric CO2 concentration. The obtained simulation results are discussed in
relation to stability of phases. It is revealed that C-S-H can be a stable and
strength-giving phase when the carbonation degree is less than one-third of the
reaction degree. Amorphous aluminosilicate and calcite become the main binding
phases at higher carbonation degrees when C-S-H is depleted.

The hydrated cement matrix undergoes a mass loss account from 13% to 15% at ∼450 °C
due to dehyroxylation of portlandite, while the CSC paste experiences mass loss of
∼3% after exposure to a similar temperature.

Although previous studies have revealed the main reaction products of CSC and its
general durability aspects, detailed information regarding its phase assemblages
remains undisclosed. The carbonation degrees of CSC are reported in prior works,
while their relationship with reaction degrees and the resultant products are not
yet available. Against this backdrop, thermodynamic calculations were conducted to
investigate the effect of reaction and carbonation degrees on the obtained
products, thereby providing some theoretical basis which can be used to obtain
better understanding of CSC. In addition, simulation of a binary binder system with
the addition of PC was perfomed to examine if it can facilitate as a self-
supporting binder before CSC is hardened by carbonation.

2. Methods

In this study, the Gibbs free energy minimization software GEM-Selektor

v.3.7 [16] was used as thermodynamic modeling software with a CEMDATA 18
database [17]. Thermodynamic calculations predict the phase assemblage of
the hydration products based on the composition of the binder and its hydration
time. It uses thermodynamic databases in which chemical interactions in all
physical states (solid, liquid, gaseous) are considered simultaneously. The
database contains thermodynamic properties of all the solid, aqueous and gaseous
species which were obtained from multiple experimental results and that can form in
the system. The codes in the modelling software make use of the database to compute
the equilibrium phase assemblages under the given conditions [18].

The GEM-Selektor software was selected because the required thermodynamic database
(CEMDATA 18) is available for use with this software, and numerous studies have
been conducted using this software, which have provided reliable results that match
the experimental outputs [19], [20], [21], [22], [23]. Other modeling tools such as
PHREEQC, can be used as well.

The Extended Debye-Hueckel equation was selected for the aqueous electrolyte model
with a common ion size parameter of 3.67 Å and a short range interaction parameter
of 0.123 kg/mol for the KOH background electrolyte. The Extended Debye-Hueckel
equation and the specific parameters are used to obtain the activity coefficients,
as the ionic strength requirements of the equation are expected to match those of
the pore solution in the system. Since the pore solution in hydrated Portland
cement and other cementitious materials is typically dominated with KOH, the
background electrolyte was assumed to be dominated by KOH and parameters that fit
the selection of KOH background were chosen [24], [25].

Based on the previous studies [17], [22], [26], CSHQ model was selected among the
several C-S-H solid solution models in CEMDATA 18 for the simulation as it is
believed to better represent the C-S-H formation in binders with
low aluminium content such as PC and CSC.

The presence of charged electrolytes in a system has an impact on the reactivity of

the ions, and activity coefficients account for this impact. The activity
coefficients of aqueous species can be calculated with the Extended Debye-Hueckel
equation [24], [27] as follows.