Alkali-activated materials (AAMs) are one of green cementitious materials in building materials industry and beneficial to the goals of carbon peaking and carbon neutrality. Compared with ordinary Portland cement (PC) based materials, however, the raw material composition, reaction products and pore solution composition of AAMs are complex and thus their reaction mechanisms and performance evolutions still need to be further clarified. Thermodynamic modelling is an effective method in analyzing AAMs. It can predict the phase assemblage and pore solution composition based on the raw material composition and given reaction conditions, which is of great significance to profoundly investigate the reaction mechanisms and performance evolutions of AAMs. The existing thermodynamic modelling is increasingly applied in AAMs and the related results are achieved. However, the corresponding comprehensive review on the state-of-art in thermodynamic modelling of AAMs is lack. A clear and systematic knowledge of the principles, thermodynamic databases, methods, challenges and gaps remains implicit for thermodynamic modelling of AAMs. In this context, this review summarized recent progress on thermodynamic modelling of AAMs, pointed out the deficiency gaps of current thermodynamic modelling research work and put forward the relevant prospects. This review could provide a theoretical guidance for thermodynamic modelling of AAMs. Chemical reactions in AAMs follow the laws of thermodynamics. There exists two thermodynamic equilibriums in AAMs, i.e., one is between the precursor and aqueous solution and another is between the reaction products and aqueous solution. Thermodynamic modelling can be performed to predict the phase assemblage and pore solution composition of AAMs by assuming the thermodynamic equilobriume. The accuracy and reliability of results by thermodynamic modelling largely depend on the quality of thermodynamic database that consist of solubility products (K_sp), heat capacity (C^Θ_p ), entropy (S^Θ ), Gibbs free energy(Δ_f G_m^Θ ), enthalpy (Δ_f H^Θ ) and molar volume (V ^Θ ) for all solid, liquid and gas phases involved in the system. The thermodynamic database of AAMs is usually established based on the thermodynamic database of PC via introducing the unique reaction products of AAMs. The unique reaction products and their thermodynamic parameters are available for alkali-activated high-Ca and alkali-activated low-Ca systems. Thermodynamic modelling of alkali-activated slag was initially conducted via the thermodynamic database of PC. Although the modelling results can predict the phase composition evolution, it still needs the corresponding experimental measurements to calibrate. with the established CNASH_ss model for describing C-(N-)A-S-H gel, thermodynamic modelling is increasingly used to investigate the phase assemblage evolution of alkali-activated slag cements. Besides the phase evolution, thermodynamic modelling is also applied to predict the phase diagram, providing a theoretical basis for the refined design of chemical properties of alkali-activated slag cement. In recent years, thermodynamic modelling tends to be used to investigate the durability of alkali-activated slag cements under single factor action such as carbonation, chloride attack and sulfate attack, as well as under multi-factors action, i.e., the combined attack by chloride and sulfate salts. Thermodynamic modelling is also applied to predict the phase assemblage evolution of alkali-activated low- and medium-Ca systems. However, it is less applied to those for alkali-activated high-Ca system. This is mainly due to the less developed thermodynamic database for alkali-activated low- and medium-Ca systems. In addition, thermodynamic modelling is also coupled with other simulation techniques to numerically analyze AAMs. For instance, a novel numerical model GeoMicro3D was proposed by coupling thermodynamic modelling and lattice Boltzmann method to simulate the reaction process and microstructure formation of alkali-activated slag cement, clarifing the interaction mechanisms between chemical reaction, multi-ions transport and microstructure formation. However, the numerical studies by coupling thermodynamic modelling and other simulation techniques are still limited for AAMs when compared to those for PC based materials. Summary and prospects Thermodynamic modelling has a robustness in studying the phase evolution and durability performance of AAMs induced by chemical reactions. Firstly, thermodynamic modelling can predict the reaction products assemblage and pore solution composition of AAMs. Secondly, thermodynamic modelling can calculate the phase evolution of AAMs under the action of aggressive media, and then study the deteriation mechanism of AAMs. Finally, thermodynamic modelling can be combined with other numerical simulation techniques to investigate AAMs. At present, however, there are still some issues that need to be further studied as follows: 1) The incomplete thermodynamic database for alkali-activated low-Ca system is an important reason for the limited thermodynamic modelling studies on alkali activated low and medium calcium systems. It is expected that a thermodynamic model describing the N-A-S-H gel can be established by ab-initio calculations and molecular dynamics simulations with the development of atomic- and molecular-scale simulation techniques. 2) It is generally assumed that the amorphous phases in precursors are dissolved synchronously in current thermodynamic modelling of AAMs. However, the heterogeneous distribution of composition and structure of precursor makes this assumption in doubt. The non-uniformity of the dissolution of amorphous phases in precursor is an issue to be further considered in future thermodynamic modelling studies. 3) The phase evolution of AAMs is actually a process coupling thermodynamics and kinetics. However, most of the thermodynamic modelling studies only focus on the phase assemblage in the equilibrium state, ignoring the kinetic issues before reaching the equilibrium. Considering the kinetic parameters (i.e., dissolution rate and reaction rate, etc.) in thermodynamic modelling should be a focus of current and future thermodynamic modelling studies. 4) The phase evolution, microstructure damage and ions transport are three inter-dependent aspects for studying the durability performance of AAMs. However, the current thermodynamic modelling studies mainly focus on the phase evolution under the chemical attacks, while ignoring the interaction between the phase evolution, microstructure damage and ions transport. In future studies, it is necessary to consider the interaction and establish a chemical-damage-transport model to numerically analyze the durability performance of AAMs.

Thermodynamic parameters of chloride and sulfate intercalated hydrotalcites were deduced. The phase evolutions in alkali‑activated slag cement upon only sodium chloride or only magnesium sulfate attack and combined attack of those two salts were investigated via thermodynamic modelling. Friedel's salt was predicted to form under sodium chloride attack， while monosulfate， ettringite， gypsum， magnesium silicate hydrate and sulfate intercalated hydrotalcite were predicted to form upon magnesium sulfate attack. The combined attack of sodium chloride and magnesium sulfate exhibited not only characteristics by single attack of those two salts but also coupling effects which promoted the formation of chloride intercalated hydrotalcite and inhibited the formation of Friedel's salt and magnesium silicate hydrate. An increase of the magnesium sulfate proportion led to lower capacity of chemically binding chloride.