Thermal analysis of raw meals doped with Li, Cu and S for burning of Portland cement clinker
DOI:
https://doi.org/10.14311/AP.2026.66.0089Keywords:
clinker, TG/DTA, XRD, phase composition, lithium, copper, sulphurAbstract
The intensification of clinker production is one of the strategies for reducing energy consumption and CO2 emissions associated with cement manufacturing. This study explores the use of various mineralisers and fluxes, specifically lithium, copper, and sulphur, added to the raw meal for clinker burning. These components can originate from both traditional and alternative fuels and raw materials. The influence of these elements on clinker melt formation, phase composition, and microstructure was investigated in the laboratory. Raw meals prepared from common cement materials were doped with chemically pure compounds Li2CO3, CuO, and (NH4)2SO4 in graded amounts. The thermal processes of the raw meals were monitored using differential thermal analysis coupled with a thermogravimetric analysis. The phase composition and microstructure of the resulting clinkers were analysed using X-ray powder diffraction and light microscopy. All dopants were found to lower the melt formation temperature, with lithium having the most significant effect. The dopants also caused changes in the phase composition and microstructure of the clinker, particularly affecting the size and shape of the alite crystals and the volume of the belite unit cell.
Downloads
References
C. J. Engelsen. Effect of mineralizers in cement production. Tech. Rep. SBF BK A07021, SINTEF Building and Infrastructure, 2007. [2025-01-30]. https://www.sintef.no/globalassets/sintefbyggforsk/coin/sintef-reports/sbf-bka07021_effect-of-mineralizers-in-cementproduction.pdf
V. V. Timašev, A. P. Osokin. Fiziko-khimitcheskie osnovy formirovaniya struktury i svoystv klinkera [In Russian; Physico-chemical basics of the structure formation and properties of clinker]. Cement 9:4–6, 1982.
A. P. Osokin, E. N. Potapova. Alitbildung in Oxid-Salz-Schmelzen. Struktur und Eigenschaften der flüssigen Klinkerphase [In German; Alite formation in oxide-salt melts. Structure and properties of the liquid clinker phase]. Silikattechnik 40(1):4–6, 1989.
I. Maki, K. Goto. Factors influencing the phase constitution of alite in Portland cement clinker. Cement and Concrete Research 12(3):301–308, 1982. https://doi.org/10.1016/0008-8846(82)90078-3
T. Staněk, P. Sulovský. The influence of the alite polymorphism on the strength of the Portland cement. Cement and Concrete Research 32(7):1169–1175, 2002. https://doi.org/10.1016/S0008-8846(02)00756-1
X. Li, H. Huang, J. Xu, et al. Statistical research on phase formation and modification of alite polymorphs in cement clinker with SO3 and MgO. Construction and Building Materials 37:548–555, 1985. https://doi.org/10.1016/j.conbuildmat.2012.07.099
J. Strunge, D. Knöfel, I. Dreizler. Einfluss der Alkalien und des Schwefels auf die Zementeigenschaften [In German; Influence of alkalis and sulfur on cement properties]. Zement-Kalk-Gips 38(3):150–158, 1985.
T. Staněk. The influence of SO3 and MgO on kinetics of alite formation. Procedia Engineering 151:26–33, 2016. https://doi.org/10.1016/j.proeng.2016.07.353
O. Sheshukov, M. Mikheenkov. Peculiarities of Portland cement clinker synthesis in the presence of a significant amount of SO3 in a raw mix. In H. M. Saleh (ed.), Cement Industry – Optimization, Characterization and Sustainable Application. IntechOpen, 2021. https://doi.org/10.5772/intechopen.94915
J. I. Bhatty. Role of minor elements in cement manufacture and use. Research and Development Bulletin p. RD109T, 1995.
I. P. Saraswat, V. K. Mathur, S. C. Ahluwalia. Thermal studies of the CaCO3: Sio2 (2:1) system containing lithium as dopant. Termochimal Acta 97:313–320, 1986. https://doi.org/10.1016/0040-6031(86)87033-2
V. K. Mathur, R. S. Gupta, S. C. Ahluwalia. Lithium as intensifier in the formation of dicalcium silicate phase. In Proceedings of the 9th International Congress on the Chemistry of Cement, vol. 2, pp. 406–412. 1992.
T. Staněk, I. Khongová, A. Zezulová, et al. Method of intensifying cement clinker production. In Proceedings of the 16th International Congress on the Chemistry of Cement 2023 – ICCC2023, vol. 1, pp. 62–65. Thailand Concrete Association, 2023.
G. Kakali, G. Parissakis, D. Bouras, et al. A study on the burnability and the phase formation of PC clinker containing Cu oxide. Cement and Concrete Research 26(10):1473–1478, 1996. https://doi.org/10.1016/0008-8846(96)00143-3
X.-W. Ma, H.-X. Chen, P.-M. Wang. Effect of CuO on the formation of clinker minerals and the hydration properties. Cement and Concrete Research 40(12):1681–1687, 2010. https://doi.org/10.1016/j.cemconres.2010.08.009
K. G. Kolovos, S. Tsivilis, G. Kakali. SEM examination of clinkers containing foreign elements. Cement and Concrete Composites 27(2):163–167, 2005. https://doi.org/10.1016/j.cemconcomp.2004.02.003
S. Ma, X. Shen, X. Gong, B. Zhong. Influence of CuO on the formation and coexistence of 3CaO·SiO2 and 3CaO·3Al2O3·CaSO4 minerals. Cement and Concrete Research 36(9):1784–1787, 2006. https://doi.org/10.1016/j.cemconres.2006.05.030
A. Ghosh, T. K. Bhattacharya, B. Mukherjee, S. K. Das. The effect of CuO addition sintering of lime. Ceramics International 27(2):201–204, 2001. https://doi.org/10.1016/S0272-8842(00)00064-X
N. Gineys, G. Aouad, F. Sorrentino, D. Damidot. Incorporation of trace elements in Portland cement clinker: Thresholds limits for Cu, Ni, S or Zn. Cement and Concrete Research 41(11):1177–1184, 2011. https://doi.org/10.1016/j.cemconres.2011.07.006
M. Boháč, D. Kubátová, M. K. Kotlánová, et al. The role of Li2O, MgO and CuO on SO3 activated clinkers. Cement and Concrete Research 152:106672, 2022. https://doi.org/10.1016/j.cemconres.2021.106672
Q. Deng, M. Zhao, M. Rao, F. Wang. Effect of CuO-doping on the hydration mechanism and the chloride-binding capacity of C4AF and high ferrite Portland clinker. Construction and Building Materials 252:119119, 2020. https://doi.org/10.1016/j.conbuildmat.2020.119119
S. Chromý. Anfärben des freiem CaO und Silikate in anschliffen von Portlandklinker [In German; Etching of free CaO and silicates in polished sections of Portland clinker]. Zement-Kalk-Gips 27:79–84, 1974.
R. Kondo, S. Choi. Mechanism and kinetics of Portland cement formation for and example of the solid-state reaction in the presence of a liquid phase. In Proceedings of the 5th International Congress on the Chemistry of Cement 1968 – ICCC1968, vol. 1, pp. 163–171. 1968.
T. Staněk, P. Sulovský. Dicalcium silicate doped with sulfur. Advances in Cement Research 24(4):233–238, 2012. https://doi.org/10.1680/adcr.11.00021
X. Li, G. Kang, S. Dou, et al. Preparation and properties of sulfur-modified alite calcium sulfoaluminate cement. Materials 17(24):6258, 2024. https://doi.org/10.3390/ma17246258
Y. Tao, W. Zhang, N. Li, et al. Fundamental principles that govern the copper doping behavior in complex clinker system. Journal of the American Ceramic Society 101(6):2527–2536, 2018. https://doi.org/10.1111/jace.15393
Y. Da, T. He, C. Shi, et al. Revealing the co-doping effects of fluorine and copper on the formation and hydration of cement clinker. Construction and Building Materials 335:127516, 2022. https://doi.org/10.1016/j.conbuildmat.2022.127516
T. Staněk, A. Rybová, A. Zezulová, M. Boháč. Formation of clinker containing lithium. Materials Science Forum 955:50–55, 2019. https://doi.org/10.4028/www.scientific.net/MSF.955.50
Downloads
Published
Issue
Section
License
Copyright (c) 2026 Theodor Staněk, Dalibor Všianský, Michaela Krejčí Kotlánová, Martin Boháč, Zdeněk Krejza, Eva Bartoníčková
This work is licensed under a Creative Commons Attribution 4.0 International License.
