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热力学模拟是研究碱激发材料化学反应的有效方法，对于深入研究和探明碱激发材料物相演变规律与耐久性能具有重要意义。本文从热力学模拟的基本原理出发，介绍了碱激发材料的热力学数据库以及热力学模拟方法，分析和总结了热力学模拟在碱激发材料反应机理、侵蚀性介质作用下物相演变规律、耐久性能和原材料组成设计等研究中的应用进展，指出了现阶段碱激发材料领域热力学模拟研究存在的不足并提出了展望，为基于热力学模拟的碱激发材料研究提供理论指导。
Abstract：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 (Ksp),heat capacity (Cp~Θ),entropy (S~Θ),Gibbs free energy(?f mG~Θ),enthalpy (?_fH~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 Geo Micro3D 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.
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基本信息:
DOI：10.14062/j.issn.0454-5648.20230323
中图分类号:TU52
引用信息:
[1]左义兵,廖宜顺,杨英姿,等.基于热力学模拟的碱激发材料物相演变与耐久性能研究进展[J].硅酸盐学报,2024,52(02):725-736.DOI:10.14062/j.issn.0454-5648.20230323.
基金信息:
湖北省自然科学基金(2022CFB048); 国家环境保护矿冶资源利用与污染控制重点实验室(HB202103)
2023-05-12
2023
2024-01-05
2024-01-02
2024
1
2023-12-04
2023-12-04
2023-12-04