Journal of Thermal Analysis and Calorimetry

, Volume 124, Issue 3, pp 1691–1703 | Cite as

Hydration kinetics of composite binder containing fly ash at different temperatures

  • Fanghui Han
  • Zengqi Zhang
  • Juanhong Liu
  • Peiyu Yan


Fly ash has been widely used as supplementary cementitious material in concrete industry. Hydration mechanism of composite binder containing fly ash is much more complicated due to the mutual effect of the hydration of cement and the pozzolanic reaction of fly ash. This paper involves the hydration kinetics of composite binder containing up to 65 % of fly ash and comparison of the results with data on composite binder containing slag that are previously published. The hydration heat evolution rate and cumulative hydration heat of composite binder containing fly ash were measured at 298, 318 and 333 K with an isothermal calorimeter. Based on the hydration kinetics model, three hydration processes, namely nucleation and crystal growth (NG), interactions at phase boundaries (I) and diffusion (D) were characterized, the relationship between the hydration rate and hydration degree was discussed at different stages, and kinetics parameters, n, K and E a, were calculated and analyzed. Results show that the hydration heat evolution rate and cumulative hydration heat of composite binder obviously decrease with increasing the replacement ratio of fly ash. Elevated temperatures promote the hydration process, especially for composite binder containing high amount of fly ash. The kinetics model could simulate the hydration process of composite binder containing no more than 65 % of fly ash, whose hydration process sequence is NG → I → D at 298 and 318 K, but it becomes NG → D at 333 K. Fly ash has relatively smaller effect on the overall reaction of composite binder than slag. The reaction rates of composite binder containing fly ash at different stages are higher than those of composite binder containing slag at the same replacement ratio. The value of E a for the overall reaction of composite binder decreases first and then increases with increasing the content of fly ash, and it is lower than that of composite binder containing slag at the same replacement ratio.


Composite binder Fly ash Hydration Kinetics Temperature 



Authors would like to acknowledge the National Natural Science Foundation of China (Grant Nos. U1134008 and 51278277), the Postdoctoral Science Foundation of China (No. 2015M580992) and Fundamental Research Funds for the Central Universities (No. FRF-TP-15-108A1).


  1. 1.
    Baert G, Hoste S, De Schutter G, De Belie N. Reactivity of fly ash in cement paste study by means of thermogravimetry and isothermal calorimetry. J Therm Anal Calorim. 2008;94:485–92.CrossRefGoogle Scholar
  2. 2.
    Han FH, Liu RG, Wang DM, Yan PY. Characteristics of the hydration heat evolution of composite binder at different temperature. Thermochim Acta. 2014;586:52–7.CrossRefGoogle Scholar
  3. 3.
    Kumar M, Singh SK, Singh NP. Heat evolution during the hydration of Portland cement in the presence of fly ash, calcium hydroxide and super plasticizer. Thermochim Acta. 2012;548:27–32.CrossRefGoogle Scholar
  4. 4.
    Narmluk M, Nawa T. Effect of fly ash on the kinetics of Portland cement hydration at different curing temperatures. Cem Concr Res. 2011;41:579–89.CrossRefGoogle Scholar
  5. 5.
    Deschner F, Lothenbach B, Winnefeld F, Neubauer J. Effect of temperature on the hydration of Portland cement blended with siliceous fly ash. Cem Concr Res. 2013;52:169–81.CrossRefGoogle Scholar
  6. 6.
    Deschner F, Winnefeld F, Lothenbach B, Seufert S, et al. Hydration of Portland cement with high replacement by siliceous fly ash. Cem Concr Res. 2012;42:1389–400.CrossRefGoogle Scholar
  7. 7.
    Bentz DP. Powder additions to mitigate retardation in high-volume fly ash mixtures. ACI Mater J. 2010;107:508–14.Google Scholar
  8. 8.
    Lothenbach B, Scrivener K, Hooton RD. Supplementary cementitious materials. Cem Concr Res. 2011;41:1244–56.CrossRefGoogle Scholar
  9. 9.
    Papadakis VG. Effect of fly ash on Portland cement systems part I. Low-calcium fly ash. Cem Concr Res. 1999;29:1727–36.CrossRefGoogle Scholar
  10. 10.
    Dittrich S, Neubauer J, Goetz-Neunhoeffer F. The influence of fly ash on the hydration of OPC within the first 44 h–a quantitative in situ XRD and heat flow calorimetry study. Cem Concr Res. 2014;56:129–38.CrossRefGoogle Scholar
  11. 11.
    Nocuń-Wczelik W. Heat evolution in hydrated cementitious systems admixtured with fly ash. J Therm Anal Calorim. 2001;65:613–9.CrossRefGoogle Scholar
  12. 12.
    Langan BW, Weng K, Ward MA. Effect of silica fume and fly ash on heat of hydration of Portland cement. Cem Concr Res. 2002;32:1045–51.CrossRefGoogle Scholar
  13. 13.
    Thomas JJ, Biernacki JJ, Bullard JW, Bishnoi S, et al. Modeling and simulation of cement hydration kinetics and microstructure development. Cem Concr Res. 2011;41:1257–78.CrossRefGoogle Scholar
  14. 14.
    Wang XY. Properties prediction of fly ash blended concrete using hydration model. Sci China Technol Sci. 2013;56:2317–25.CrossRefGoogle Scholar
  15. 15.
    Wang XY. Modeling the hydration of concrete incorporating fly ash or slag. Cem Concr Res. 2010;40:984–96.CrossRefGoogle Scholar
  16. 16.
    Thomas JJ. A new approach to modeling the nucleation and growth kinetics of tricalcium silicate hydration. J Am Ceram Soc. 2007;90:3282–8.CrossRefGoogle Scholar
  17. 17.
    Scherer GW, Zhang J, Thomas JJ. Nucleation and growth models for hydration of cement. Cem Concr Res. 2012;42:982–93.CrossRefGoogle Scholar
  18. 18.
    Scherer GW. Models of confined growth. Cem Concr Res. 2012;42:1252–60.CrossRefGoogle Scholar
  19. 19.
    Krstulovic R, Dabic P. A conceptual model of the cement hydration process. Cem Concr Res. 2000;30:693–8.CrossRefGoogle Scholar
  20. 20.
    Dabic P, Krstulovic R, Rušic D. A new approach in mathematical modeling of cement hydration development. Cem Concr Res. 2000;30:1017–21.CrossRefGoogle Scholar
  21. 21.
    Merzouki T, Bouasker M, EI Houda Khalifa N, Mounanga P. Contribution to the modeling of hydration and chemical shrinkage of slag-blended cement at early age. Constr Build Mater. 2013;44:368–80.CrossRefGoogle Scholar
  22. 22.
    Han FH, Zhang ZQ, Wang DM, Yan PY. Hydration kinetics of composite binder containing slag at different temperatures. J Therm Anal Calorim. 2015;121:815–27.CrossRefGoogle Scholar
  23. 23.
    Gruyaert E, Robeyst N, De Belie N. Study of the hydration of Portland cement blended with blast-furnace slag by calorimetry and thermogravimetry. J Therm Anal Calorim. 2010;102:941–51.CrossRefGoogle Scholar
  24. 24.
    Lam L, Wong YL, Poon CS. Degree of hydration and gel/space ratio of high volume fly ash/cement systems. Cem Concr Res. 2000;30:747–56.CrossRefGoogle Scholar
  25. 25.
    Papadakis VG. Effect of fly ash on Portland cement systems part II: high-calcium fly ash. Cem Concr Res. 2000;30:1647–54.CrossRefGoogle Scholar
  26. 26.
    Sakai E, Miyahara S, Ohsawa S, Lee SH, Daimon M. Hydration of fly ash cement. Cem Concr Res. 2005;35:1135–40.CrossRefGoogle Scholar
  27. 27.
    Pane I, Hansen W. Investigation of blended cement hydration by isothermal calorimetry and thermal analysis. Cem Concr Res. 2005;35:1155–64.CrossRefGoogle Scholar
  28. 28.
    Wang A, Zhang C, Sun W. Fly ash effects II. The active effect of fly ash. Cem Concr Res. 2004;34:2057–60.CrossRefGoogle Scholar
  29. 29.
    Tydlitát V, Matas T, Cerný R. Effect of w/c and temperature on the early-stage hydration heat development in Portland-limestone cement. Constr Build Mater. 2014;50:140–7.CrossRefGoogle Scholar
  30. 30.
    Christian JW. The theory of transformations in metals and alloys, part 1. 3rd ed. Oxford: Pergamon Press; 2002.Google Scholar
  31. 31.
    Fajun W, Grutzeck MW, Roy DM. The retarding effects of fly ash upon the hydration of cement pastes: the first 24 hours. Cem Concr Res. 1985;15:174–84.CrossRefGoogle Scholar
  32. 32.
    Jun-yuan H, Scheetz BE, Roy DM. Hydration of fly ash-portland cements. Cem Concr Res. 1984;14:505–12.CrossRefGoogle Scholar
  33. 33.
    Han FH, Liu RG, Yan PY. Effect of fresh water leaching on the microstructure of hardened composite binder pastes. Constr Build Mater. 2014;68:630–6.CrossRefGoogle Scholar
  34. 34.
    Roy DM, Idorn GM. Hydration, structure, and properties of blast furnace slag cements, mortars and concrete. ACI J. 1982;79:444–57.Google Scholar
  35. 35.
    Taylor R, Richardson IG, Brydson RMD. Composition and microstructure of 20-year-old ordinary Portland cement-ground granulated blast-furnace slag blends containing 0 to 100 % slag. Cem Concr Res. 2010;40:971–83.CrossRefGoogle Scholar
  36. 36.
    Lothenbach B, Winnefeld F, Alder C, Wieland E, Lunk P. Effect of temperature on the pore solution, microstructure and hydration products of Portland cement pastes. Cem Concr Res. 2007;37:483–91.CrossRefGoogle Scholar
  37. 37.
    Famy C, Scrivener KL, Atkinson A, Brough AR. Effects of an early or a late heat treatment on the microstructure and composition of inner C–S–H products of Portland cement mortars. Cem Concr Res. 2002;32:269–78.CrossRefGoogle Scholar
  38. 38.
    Escalante-García J, Sharp J. Effect of temperature on the hydration of the main clinker phases in Portland cements: part II blended cements. Cem Concr Res. 1988;28:1259–74.CrossRefGoogle Scholar
  39. 39.
    Hannesson G, Kuder K, Shogren R, Lehman D. The influence of high volume of fly ash and slag on the compressive strength of self-consolidating concrete. Constr Build Mater. 2012;30:161–8.CrossRefGoogle Scholar
  40. 40.
    Broda M, Wirquin E, Duthoit B. Conception of an isothermal calorimeter for concrete-determination of the apparent activation energy. Mater Struct. 2002;35:389–94.Google Scholar
  41. 41.
    Poppe AM, De Shutter G. Cement hydration in the presence of higher filler contents. Cem Concr Res. 2005;35:2290–9.CrossRefGoogle Scholar
  42. 42.
    Ravikumar D, Neithalath N. Reaction kinetics in sodium silicate powder and liquid activated slag binders evaluated using isothermal calorimetry. Thermochim Acta. 2012;546:32–43.CrossRefGoogle Scholar
  43. 43.
    ASTM International. ASTM C1074-11 standard practice for estimating concrete strength by the maturity method. West Conshohocken: ASTM International; 2011.Google Scholar
  44. 44.
    Sang-Hun H, Jin-Keun K, Yon-Dong P. Prediction of compressive strength of fly ash concrete by new apparent activation energy function. Cem Concr Res. 2003;33:965–71.CrossRefGoogle Scholar
  45. 45.
    Bentz DP. Activation energies of high-volume fly ash ternary blends: hydration and setting. Cem Concr Compos. 2014;53:214–23.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2016

Authors and Affiliations

  1. 1.College of Civil and Environmental EngineeringUniversity of Science and Technology BeijingBeijingChina
  2. 2.Key Laboratory of Civil Engineering Safety and Durability of China Education Ministry, Department of Civil EngineeringTsinghua UniversityBeijingChina

Personalised recommendations