Impact of Alkali Salts on the Hydration of Ordinary Portland Cement and Limestone–Calcined Clay Cement
Publication: Journal of Materials in Civil Engineering
Volume 33, Issue 9
Abstract
Soluble alkalis play a vital role during early age hydration and strength development in cement. This study investigates the influence of alkali addition on the hydration, phase assemblage, and strength development in ordinary portland cement (OPC) and limestone–calcined clay cement () produced with 50% clinker replacement. The alkalinity (% ) of OPC and was increased using four different alkali salts: NaOH, , KOH, and . An acceleration of the early age hydration and an increase in the early age compressive strength development was observed with increasing alkalinity in OPC and systems. The characteristic features of the calorimetry curves were seen to be significantly influenced by the presence of alkalis. The presence of additional sulfate ions was seen to modify the phase assemblage, with additional ettringite forming in these systems. However, increasing the alkalinity was also seen to reduce the later age clinker hydration and strength development.
Get full access to this article
View all available purchase options and get full access to this article.
Data Availability Statement
Some or all data, models, or code that support the findings of this study are available from the corresponding author upon reasonable request.
Acknowledgments
The financial support of the Swiss Agency for Development and Cooperation is gratefully acknowledged.
References
Antoni, M., J. Rossen, F. Martirena, and K. Scrivener. 2012. “Cement substitution by a combination of metakaolin and limestone.” Cem. Concr. Res. 42 (12): 1579–1589. https://doi.org/10.1016/j.cemconres.2012.09.006.
Avet, F., E. Boehm-Courjault, and K. Scrivener. 2019. “Investigation of C─ A─ S─ H composition, morphology and density in limestone calcined clay cement ().” Cem. Concr. Res. 115 (Jan): 70–79. https://doi.org/10.1016/j.cemconres.2018.10.011.
Avet, F., and K. L. Scrivener. 2018. “Investigation of the calcined kaolinite content on the hydration of limestone calcined clay cement ()” Cem. Concr. Res. 107 (May): 124–135. https://doi.org/10.1016/j.cemconres.2018.02.016.
Avet, H. 2017. “Investigation of the grade of calcined clays used as clinker substitute in limestone calcined clay cement ().” Thesis, School of Engineering, Swiss Federal Institute of Technology Lausanne.
Barnes, P., and J. Bensted. 2002. Structure and performance of cements. 2nd ed. London: Spon Press.
Chappex, T., and K. Scrivener. 2012. “Alkali fixation of C─ S─ H in blended cement pastes and its relation to alkali silica reaction.” Cem. Concr. Res. 42 (8): 1049–1054. https://doi.org/10.1016/j.cemconres.2012.03.010.
Chen, W., and H. J. H. Brouwers. 2010. “Alkali binding in hydrated portland cement paste.” Cem. Concr. Res. 40 (5): 716–722. https://doi.org/10.1016/j.cemconres.2009.12.007.
Chen, W., and H. J. H. Brouwers. 2011. “A method for predicting the alkali concentrations in pore solution of hydrated slag cement paste.” J. Mater. Sci. 46 (10): 3622–3631. https://doi.org/10.1007/s10853-011-5278-1.
Clark, B. A., and P. W. Brown. 1999. “Formation of ettringite from monosubstituted calcium sulfoaluminate hydrate and gypsum.” J. Am. Ceram. Soc. 82 (10): 2900–2905. https://doi.org/10.1111/j.1151-2916.1999.tb02174.x.
Cyr, M., M. Trinh, B. Husson, and G. Casaux-Ginestet. 2014. “Effect of cement type on metakaolin efficiency.” Cem. Concr. Res. 64 (Oct): 63–72. https://doi.org/10.1016/j.cemconres.2014.06.007.
Diamond, S. 1981. “Effects of two Danish flyashes on alkali contents of pore solutions of cement-flyash pastes.” Cem. Concr. Res. 11 (3): 383–394. https://doi.org/10.1016/0008-8846(81)90110-1.
Diamond, S., and S. Ong. 1994. “Effects of added alkali hydroxides in mix water on long-term SO42- concentrations in pore solution.” Cem. Concr. Compos. 16 (3): 219–226. https://doi.org/10.1016/0958-9465(94)90019-1.
Feng, P., C. Miao, and J. W. Bullard. 2016. “Factors influencing the stability of AFm and AFt in the Ca─ Al─ S─ O─ H system at 25°C.” J. Am. Ceram. Soc. 99 (3): 1031–1041. https://doi.org/10.1111/jace.13971.
Fraay, A. L. A., J. M. Bijen, and Y. M. de Haan. 1989. “The reaction of fly ash in concrete a critical examination.” Cem. Concr. Res. 19 (2): 235–246. https://doi.org/10.1016/0008-8846(89)90088-4.
Frølich, L., L. Wadsö, and P. Sandberg. 2016. “Using isothermal calorimetry to predict one day mortar strengths.” Cem. Concr. Res. 88 (Oct): 108–113. https://doi.org/10.1016/j.cemconres.2016.06.009.
Gobbo, L., L. Sant’Agostino, and L. Garcez. 2004. “C3A polymorphs related to industrial clinker alkalies content.” Cem. Concr. Res. 34 (4): 657–664. https://doi.org/10.1016/j.cemconres.2003.10.020.
Hanpongpun, W., and K. Scrivener. 2018. “The effect of alkali on the properties of limestone calcined clay cement (LC3).” In Calcined clays for sustainable concrete, edited by F. Martirena, A. Favier, and K. Scrivener, 200–204. Dordrecht, Netherlands: Springer.
Ipavec, A., R. Gabrovšek, T. Vuk, V. Kaučič, J. MačEk, and A. Meden. 2011. “Carboaluminate phases formation during the hydration of calcite-containing portland cement.” J. Am. Ceram. Soc. 94 (4): 1238–1242. https://doi.org/10.1111/j.1551-2916.2010.04201.x.
Jawed, I., and J. Skalny. 1977. “Alkalies in cement: A review I. Forms of alkalies and their effect on clinker formation.” Cem. Concr. Res. 7 (6): 719–729. https://doi.org/10.1016/0008-8846(77)90056-4.
Jawed, I., and J. Skalny. 1978. “Alkalies in cement: A review. II. Effects of alkalies on hydration and performance of portland cement.” Cem. Concr. Res. 8 (1): 37–51. https://doi.org/10.1016/0008-8846(78)90056-X.
Joseph, S., R. Snellings, and Ö. Cizer. 2019. “Activation of portland cement blended with high volume of fly ash using Na2SO4.” Cem. Concr. Compos. 104 (Nov): 103417. https://doi.org/10.1016/j.cemconcomp.2019.103417.
Juilland, P., E. Gallucci, R. Flatt, and K. Scrivener. 2010. “Dissolution theory applied to the induction period in alite hydration.” Cem. Concr. Res. 40 (6): 831–844. https://doi.org/10.1016/j.cemconres.2010.01.012.
Krishnan, S. 2019. “Hydration and microstructure development in limestone calcined clay cement.” Thesis, Dept. of Civil Engineering, Indian Institute of Technology Delhi.
Krishnan, S., and S. Bishnoi. 2018. “Understanding the hydration of dolomite in cementitious systems with reactive aluminosilicates such as calcined clay.” Cem. Concr. Res. 108 (Jun): 116–128. https://doi.org/10.1016/j.cemconres.2018.03.010.
Krishnan, S., A. C. Emmanuel, and S. Bishnoi. 2019a. “Hydration and phase assemblage of ternary cements with calcined clay and limestone.” Constr. Build. Mater. 222 (Oct): 64–72. https://doi.org/10.1016/j.conbuildmat.2019.06.123.
Krishnan, S., A. C. Emmanuel, V. Shah, A. Parashar, G. Mishra, S. Maity, and S. Bishnoi. 2019b. “Industrial production of limestone calcined clay cement: Experience and insights.” Green Mater. 7 (1): 15–27. https://doi.org/10.1680/jgrma.18.00003.
Krishnan, S., S. K. Kanaujia, S. Mithia, and S. Bishnoi. 2018. “Hydration kinetics and mechanisms of carbonates from stone wastes in ternary blends with calcined clay.” Constr. Build. Mater. 164 (Mar): 265–274. https://doi.org/10.1016/j.conbuildmat.2017.12.240.
Kulik, D. A. 2011. “Improving the structural consistency of C─ S─ H solid solution thermodynamic models.” Cem. Concr. Res 41 (5): 477–495. https://doi.org/10.1016/j.cemconres.2011.01.012.
Kulik, D. A., T. Wagner, S. V. Dmytrieva, G. Kosakowski, F. F. Hingerl, K. V. Chudnenko, and U. R. Berner. 2013. “GEM-Selektor geochemical modeling package: Revised algorithm and GEMS3K numerical kernel for coupled simulation codes.” Comput. Geosci. 17 (1): 1–24. https://doi.org/10.1007/s10596-012-9310-6.
Lagier, F., and K. E. Kurtis. 2007. “Influence of portland cement composition on early age reactions with metakaolin.” Cem. Concr. Res. 37 (10): 1411–1417. https://doi.org/10.1016/j.cemconres.2007.07.002.
Leming, M., and B. Nguyen. 2000. “Limits on alkali content in cement—Results from a field study.” Cem. Concr. Aggregates 22 (1): 41–47. https://doi.org/10.1520/CCA10462J.
L’Hôpital, E., B. Lothenbach, K. Scrivener, and D. A. Kulik. 2016. “Alkali uptake in calcium alumina silicate hydrate (C─ A─ S─ H).” Cem. Concr. Res. 85 (Jul): 122–136. https://doi.org/10.1016/j.cemconres.2016.03.009.
Li, G., P. Le Bescop, and M. Moranville-Regourd. 1997. “Synthesis of the U phase ().” Cem. Concr. Res. 27 (1): 7–13. https://doi.org/10.1016/S0008-8846(96)00194-9.
Lothenbach, B., K. Scrivener, and R. D. Hooton. 2011. “Supplementary cementitious materials.” Cem. Concr. Res. 41 (12): 1244–1256. https://doi.org/10.1016/j.cemconres.2010.12.001.
Ma, Y., and J. Qian. 2018. “Influence of alkali sulfates in clinker on the hydration and hardening of portland cement.” Constr. Build. Mater. 180 (Aug): 351–363. https://doi.org/10.1016/j.conbuildmat.2018.05.196.
Machner, A., M. Zajac, M. Ben Haha, K. O. Kjellsen, M. R. Geiker, and K. De Weerdt. 2018. “Limitations of the hydrotalcite formation in portland composite cement pastes containing dolomite and metakaolin.” Cem. Concr. Res. 105 (Jan): 1–17. https://doi.org/10.1016/j.cemconres.2017.11.007.
Macphee, D. E., K. Luke, F. P. Glasser, and E. E. Lachowski. 1989. “Solubility and aging of calcium silicate hydrates in alkaline solutions at 25°C.” J. Am. Ceram. Soc. 72 (4): 646–654. https://doi.org/10.1111/j.1151-2916.1989.tb06189.x.
Matschei, T., B. Lothenbach, and F. P. Glasser. 2007a. “The role of calcium carbonate in cement hydration.” Cem. Concr. Res. 37 (4): 551–558. https://doi.org/10.1016/j.cemconres.2006.10.013.
Matschei, T., B. Lothenbach, and F. P. Glasser. 2007b. “Thermodynamic properties of portland cement hydrates in the system .” Cem. Concr. Res. 37 (10): 1379–1410. https://doi.org/10.1016/j.cemconres.2007.06.002.
Mota, B., T. Matschei, and K. Scrivener. 2015. “The influence of sodium salts and gypsum on alite hydration.” Cem. Concr. Res. 75 (Sep): 53–65. https://doi.org/10.1016/j.cemconres.2015.04.015.
Mota, B., T. Matschei, and K. Scrivener. 2018. “Impact of NaOH and Na2SO4 on the kinetics and microstructural development of white cement hydration.” Cem. Concr. Res. 108 (Feb): 172–185. https://doi.org/10.1016/j.cemconres.2018.03.017.
Mota, B., T. Matschei, and K. Scrivener. 2019. “Impact of sodium gluconate on white cement-slag systems with .” Cem. Concr. Res. 122 (April): 59–71. https://doi.org/10.1016/j.cemconres.2019.04.008.
Odler, I., and R. Wonnemann. 1983a. “Effect of alkalies on portland cement hydration. I. Alkali oxides incorporated into the crystalline lattice of clinker minerals.” Cem. Concr. Res. 13 (4): 477–482. https://doi.org/10.1016/0008-8846(83)90005-4.
Odler, I., and R. Wonnemann. 1983b. “Effect of alkalies on portland cement hydration II. Alkalies present in form of sulphates.” Cem. Concr. Res. 13 (6): 771–777. https://doi.org/10.1016/0008-8846(83)90078-9.
Palou, M., E. Kuzielová, M. Žemlička, R. Novotný, and J. Másilko. 2017. “The effect of metakaolin upon the formation of ettringite in metakaolin–lime–gypsum ternary systems.” J. Therm. Anal. Calorim. 72 (4): 646–654. https://doi.org/10.1007/s10973-017-6885-0.
Puerta-Falla, G., M. Balonis, G. Le Saout, N. Neithalath, and G. Sant. 2015. “The influence of metakaolin on limestone reactivity in cementitious materials.” In Calcined clays for sustainable concrete, edited by K. Scrivener, and A. Favier, 11–19. Dordrecht, Netherlands: Springer.
Quennoz, A., and K. L. Scrivener. 2013. “Interactions between alite and C3A-gypsum hydrations in model cements.”Cem. Concr. Res. 44 (Feb): 46–54. https://doi.org/10.1016/j.cemconres.2012.10.018.
Reardon, E. J., and R. Fagan. 2000. “The calcite/portlandite phase boundary: Enhanced calcite solubility at high pH.” Appl. Geochem. 15 (3): 327–335. https://doi.org/10.1016/S0883-2927(99)00061-X.
Sánchez-Herrero, M. J., A. Fernández-Jiménez, and A. Palomo. 2017. “C3S and hydration in the presence of Na2CO3 and Na2SO4.” J. Am. Ceram. Soc. 100 (7): 3188–3198. https://doi.org/10.1111/jace.14855.
Sánchez-Herrero, M. J., A. Fernández-Jiménez, Á. Palomo, and L. Klein. 2016. “Alkaline hydration of and .” J. Am. Ceram. Soc. 99 (2): 604–611. https://doi.org/10.1111/jace.13985.
Scrivener, K., F. Avet, H. Maraghechi, F. Zunino, J. Ston, W. Hanpongpun, and A. Favier. 2019. “Impacting factors and properties of limestone calcined clay cements ().” Green Mater. 7 (1): 3–14. https://doi.org/10.1680/jgrma.18.00029.
Scrivener, K., F. Martirena, S. Bishnoi, and S. Maity. 2018. Calcined clay limestone cements ().” Cem. Concr. Res. 114 (Dec): 49–56. https://doi.org/10.1016/j.cemconres.2017.08.017.
Scrivener, K. L., and P. L. Pratt. 1984. “Microstructural studies of the hydration of C3A and C4AF independently and in cement paste.” Proc. Br. Ceram. Soc. 35 (1): 201–219.
Skibsted, J., and M. D. Andersen. 2013. “The effect of alkali ions on the incorporation of aluminum in the calcium silicate hydrate (C─ S─ H) phase resulting from portland cement hydration studied by 29Si MAS NMR.” J. Am. Ceram. Soc. 96 (2): 651–656. https://doi.org/10.1111/jace.12024.
Smillie, S., E. Moulin, and F. P. Glasser. 1993. “Freshness of cement: Conditions for syngenite formation.” Adv. Cem. Res. 5 (19): 93–96. https://doi.org/10.1680/adcr.1993.5.19.93.
Taylor, H. F. W. 1987. “A method for predicting alkali ion concentrations in cement pore solutions.” Adv. Cem. Res. 1 (1): 5–17. https://doi.org/10.1680/adcr.1987.1.1.5.
Taylor, H. F. W. 1997. Cement chemistry. London: Thomas Telford.
Wagner, T., D. A. Kulik, F. F. Hingerl, and S. V. Dmytrievava. 2012. “Gem-selektor geochemical modeling package: TSolMod library and data interface for multicomponent phase models.” Can. Min. 50 (5): 1173–1195. https://doi.org/10.3749/canmin.50.5.1173.
Ye, H., and A. Radlińska. 2017. “Effect of alkalis on cementitious materials: Understanding the relationship between composition, structure, and volume change mechanism.” J. Adv. Concr. Technol. 15 (4): 165–177. https://doi.org/10.3151/jact.15.165.
Zajac, M., J. Skocek, B. Lothenbach, and B. H. Mohsen. 2020. “Late hydration kinetics: Indications from thermodynamic analysis of pore solution data.” Cem. Concr. Res. 129 (Mar): 105975. https://doi.org/10.1016/j.cemconres.2020.105975.
Information & Authors
Information
Published In
Journal of Materials in Civil Engineering
Volume 33 • Issue 9 • September 2021
Copyright
© 2021 American Society of Civil Engineers.
History
Received: Oct 18, 2020
Accepted: Jan 25, 2021
Published online: Jun 25, 2021
Published in print: Sep 1, 2021
Discussion open until: Nov 25, 2021
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.
Cited by
- Cheng Yu, Zhen Li, Jiaping Liu, Degradation of limestone calcined clay cement (LC3) mortars under sulfate attack, Low-carbon Materials and Green Construction, 10.1007/s44242-022-00003-1, 1, 1, (2023).
- Nancy Beuntner, Karl-Christian Thienel, Pozzolanic efficiency of calcined clays in blended cements with a focus on early hydration, Advances in Cement Research, 10.1680/jadcr.21.00034, 34, 8, (341-355), (2022).
- Yi-Sheng Wang, Sung-Ho Tae, Run-Sheng Lin, Xiao-Yong Wang, Effects of Na2CO3 on engineering properties of cement–limestone powder–slag ternary blends, Journal of Building Engineering, 10.1016/j.jobe.2022.104937, 57, (104937), (2022).
- Yan Xia, Minghao Liu, Yading Zhao, Xiaobing Ma, Microstructure of Portland cement blended with high dosage of sewage sludge ash activated by Na2SO4, Journal of Cleaner Production, 10.1016/j.jclepro.2022.131568, 351, (131568), (2022).
- Yi-Sheng Wang, Xiao-Yong Wang, Effects of sodium carbonate on self-healing properties of cement–slag–limestone powder ternary cementitious material, Case Studies in Construction Materials, 10.1016/j.cscm.2022.e01585, 17, (e01585), (2022).
- Ruoying Li, Hailong Ye, Influence of Alkalis on Natural Carbonation of Limestone Calcined Clay Cement Pastes, Sustainability, 10.3390/su132212833, 13, 22, (12833), (2021).