长江科学院院报2026，Vol.43Issue(1)：164-172,9.DOI:10.11988/ckyyb.20241161
基于热力学计算的低热水泥-粉煤灰放热特性与水化机制
Long-term Exothermic Characteristics and Hydration Mechanism of Low-heat Portland Cement Mixed with Fly Ash Based on Thermodynamic Calculation
摘要
Abstract
[Objective]This study aims to reveal the exothermic properties and hydration mechanism of low-heat Portland cement(LHC)(hereafter referred to as low-heat cement)mixed with fly ash,the composition of pore so-lution during hydration,and the evolution mechanism of hydration products.[Methods]Long-term exothermic tests were conducted on the cementitious materials,and a quantitative relationship between heat release and hydra-tion progress was established,from which the hydration state was obtained.Based on the theory of Gibbs free energy minimization using GEMS software,thermodynamic calculations were performed to construct a cement hydration model,whose validity was verified through comparative analysis between simulated and measured Ca(OH)2 con-tents in neat paste.[Results](1)The exotherm from low-heat cement hydration was mainly concentrated within 28 days.Fly ash significantly reduced the hydration heat of low-heat cement:a 20％-50％replacement ratio resul-ting in a reduction of 14.6％-32.7％in total exotherm after 720 days of hydration.Predictive models for exotherm and degree of hydration of the cementitious system were established.At hydration stabilization,the degree of hydra-tion of low-heat cement reached 86.0％,and the reaction degree of fly ash was 53.3％.(2)The Ca(OH)2 content calculated by the cement hydration model showed small deviation from measured values,indicating that the devel-oped model adequately characterized the hydration process of low-heat cement.The cement was dominated by dical-cium silicate(C2S).Compared with ordinary and medium-heat Portland cements,it produced more calcium silicate hydrate(C-S-H)gel and less Ca(OH)2,which explained its higher later-age strength.(3)Different types of C-S-H were found to exhibit distinct saturation indices,ranked from highest to lowest as C1.5S0.67 H2.5,C0.83S0.67H1.83,C1.33SH2.17,and C0.67SH1.5(the last being unstable).All types showed linear positive correlations with the saturation index of Ca(OH)2,as well as with OH-and silicon ion concentrations,and a negative correlation with calcium ion concentration,with the relevant relationships established.(4)After fly ash incorporation(0-25％),the ettringite(AFt)content in the cementitious system gradually decreased to zero,while the monosulfate(AFm)content con-tinuously increased.(5)At low fly ash dosages(0-20％),Si phases in fly ash first reacted with Ca(OH)2 to form C-S-H with a higher Ca/Si ratio,increasing the average from 1.61 to 1.63.At higher dosages(20％-50％),C-S-H content decreased by 16.5％,and both Ca/Si ratio and pH declined markedly,primarily due to exhaustion of CH,reduced Ca phase,and increased Si and Al phases.At very high dosages(65％-80％),severe deficiency of Ca phase along with excess Si,Al,and Fe phases and lower pH caused extensive dissolution of C-S-H and a reduc-tion in its Ca/Si ratio.(6)A relationship among pH,solution composition,and product saturation indices was es-tablished.At pH=12.86,the saturation indices of the above products were highly similar.When pH≤12.86,sig-nificant changes in the stable states of the products occurred.[Conclusion]Incorporation of fly ash further reduces the exotherm of low-heat cement,and heat release is significantly positively correlated with hydration progress.At low dosages,both the content and properties of C-S-H gel are improved,which benefits macroscopic mechanical performance and durability.pH 12.86 appears to be the pH inflection point for the stable state of hydration prod-ucts,which should be considered when designing low-heat cement concrete with high fly ash dosages.关键词
低热硅酸盐水泥/热力学计算/水化机制/放热性能/水化硅酸钙Key words
low-heat Portland cement/thermodynamic calculation/hydration mechanism/exothermic perform-ance/calcium silicate hydrate分类
建筑与水利引用本文复制引用
崔进杨,李曙光,李文伟,杨华美,张铎,张开来..基于热力学计算的低热水泥-粉煤灰放热特性与水化机制[J].长江科学院院报,2026,43(1):164-172,9.基金项目
国家自然科学基金长江联合基金重点项目(U2040222) （U2040222）
湖北省自然科学基金三峡联合基金培育项目(2023AFD196) （2023AFD196）
河南省引江济淮科研服务项目(HNYJJH/JS/FWKY-2021005) （HNYJJH/JS/FWKY-2021005）
中国长江三峡集团有限公司自主科研项目(NBZZ202400043) （NBZZ202400043）
