Impact of calcium aluminate cement and calcium sulfate on gel C-A-S-H formation during the Portland cement hydration

D. Torrens-Martín; L. Fernández-Carrasco

doi:10.3989/mc.2025.417825

Authors

D. Torrens-Martín ATEM Research Group, Civil and Environmental Engineering Department (DECA), Universitat Politècnica de Catalunya https://orcid.org/0000-0003-1675-5726
L. Fernández-Carrasco ATEM Research Group, Civil and Environmental Engineering Department (DECA), Universitat Politècnica de Catalunya https://orcid.org/0000-0002-2379-3782

DOI:

https://doi.org/10.3989/mc.2025.417825

Keywords:

Portland cement, Calcium aluminate cement, Calcium sulfates, C-A-S-H, FTIR

Abstract

This study examines how calcium aluminate cement (CAC) and calcium sulfate influence the hydration and gel structure of Portland cement (PC). A binary PC/CAC (85/15) mix was compared with ternary systems containing 3% and 5% calcium sulfate under two curing conditions. FTIR and ²⁹Si NMR analyses showed that CAC promotes aluminum incorporation into the C-S-H gel, leading to a more homogeneous C-A-S-H structure. Water curing further enhanced this integration, with increased Q² and reduced Q¹ signals. Calcium sulfate addition mitigated the silicate hydration delay caused by CAC and promoted longer silicate chains and higher Al(IV)/Si ratios. Overall, CAC enhances aluminum incorporation, while calcium sulfate improves silicate polymerization, resulting in a more uniform and well-structured C-A-S-H gel.

Downloads

Download data is not yet available.

References

Shahrin R, Bobko CP. 2017. Characterizing strength and failure of calcium silicate hydrate aggregates in cement paste under micropillar compression. J. Nanomech. Micromech. 7(4):06017002. https://doi.org/10.1061/(ASCE)NM.2153-5477.0000137

Monteiro PJ, Miller SA, Horvath A. 2017. Towards sustainable concrete. Nat. Mater. 16(7):698-699. https://doi.org/10.1038/nmat4930 PMid:28653697

Lothenbach B, Scrivener K, Hooton RD. 2011. Supplementary cementitious materials. Cem. Concr. Res. 41(12):1244-1256. https://doi.org/10.1016/j.cemconres.2010.12.001

Taylor HFW. 1990. Cement Chemistry, Thomas Telford. London.

Merlino S, Bonaccorsi E, Armbruster T. 2001. The real structure of tobermorite 11A: normal and anomalous forms, OD character and polytypic modifications. Eur. J. Mineral. 13(3):577-590. https://doi.org/10.1127/0935-1221/2001/0013-0577

Andersen MD, Jakobsen HJ, Skibsted J. 2003. Incorporation of aluminum in the calcium silicate hydrate (C− S− H) of hydrated Portland cements: A high-field 27Al and 29Si MAS NMR investigation. Inorg. Chem. 42(7):2280-2287. https://doi.org/10.1021/ic020607b PMid:12665361

. Li J, Geng G, Myers R, Yu YS, Shapiro D, Carraro C, Maboudian R, Monteiro PJM. 2019. The chemistry and structure of calcium (alumino) silicate hydrate: a study by XANES, ptychographic imaging, and wide-and small-angle scattering. Cem. Concr. Res. 115:367-378. https://doi.org/10.1016/j.cemconres.2018.09.008

Li J, Geng, G, Zhang W, Yu YS, Shapiro DA, Monteiro PJ. 2018. The hydration of β-and α′ H-dicalcium silicates: an X-ray spectromicroscopic study. ACS Sustain. Chem. Eng. 7(2):2316-2326. https://doi.org/10.1021/acssuschemeng.8b05060

Lothenbach B, Nonat A. 2015. Calcium silicate hydrates: Solid and liquid phase composition. Cem. Concr. Res. 78:57-70. https://doi.org/10.1016/j.cemconres.2015.03.019

Thomas JJ, Jennings HM. 2006. A colloidal interpretation of chemical aging of the C-S-H gel and its effects on the properties of .cement paste. Cem. Concr. Res. 36:30-38. https://doi.org/10.1016/j.cemconres.2004.10.022

Barzgar S, Tarik M, Ludwig C, Lothenbach B. 2021. The effect of equilibration time on Al uptake in CSH. Cem. Concr. Res. 144:106438. https://doi.org/10.1016/j.cemconres.2021.106438

L'Hôpital E, Lothenbach B, Kulik DA, Scrivener K. 2016.Influence of calcium to silica ratio on aluminium uptake in calcium silicate hydrate. Cem. Concr. Res. 85:111-121. https://doi.org/10.1016/j.cemconres.2016.01.014

Irbe L, Beddoe RE, Heinz D. 2019. The role of aluminium in C-A-S-H during sulfate attack on concrete. Cem. Concr. Res. 116: 71-80. https://doi.org/10.1016/j.cemconres.2018.11.012

Sakir S, Raman SN, Safiuddin M, Amrul Kaish ABM, Mutalib AA. 2020. Utilization of by-products and wastes as supplementary cementitious materials in structural mortar for sustainable construction. Sustain. 12(9): 3888. https://doi.org/10.3390/su12093888

Myers RJ, Bernal SA, San Nicolas R, Provis JL. 2013. Generalized structural description of calcium-sodium aluminosilicate hydrate gels: the cross-linked substituted tobermorite model. Langmuir. 29 (17): 5294-5306. https://doi.org/10.1021/la4000473 PMid:23534827

L'Hôpital E, Lothenbach B, Le Saout G, Kulik D, Scrivener K. 2015. Incorporation of aluminium in calcium-silicate hydrates. Cem. Concr. Res. 75: 91-103. https://doi.org/10.1016/j.cemconres.2015.04.007

Richardson IG, Brough AR, Brydson R, Groves GW, Dobson CM. 1993. Location of aluminium in substituted calcium silicate hydrate (C-S-H) gels as determined by 29Si and 27Al NMR and EELS. J. Am. Ceram. Soc. 76:2285-2288. https://doi.org/10.1111/j.1151-2916.1993.tb07765.x

Chen, JJ, Thomas JJ, Taylor HFW, Jennings HM. 2004. Solubility and structure of calcium silicate hydrate. Cem. Concr. .Res. 34(9): 1499-1519. https://doi.org/10.1016/j.cemconres.2004.04.034

Andersen MD, Jakobsen HJ, Skibsted J. 2006. A new aluminium-hydrate species in hydrated Portland cements characterized by 27Al and 29Si MAS NMR spectroscopy. Cem. Concr. Res. 36(1): 3-17. https://doi.org/10.1016/j.cemconres.2005.04.010

Kunhi A, Moutzouri P, Berruyer P, Walder BJ, Siramanont J, Siramanont J, Harris M, Negroni M, Galmarini SC, Parker SC, Scrivener K, Emsley L, Bowen P. 2020. The atomic-level structure of cementitious calcium aluminate silicate hydrate. J. Am. Chem. Soc. 142(25):11060-11071. https://doi.org/10.1021/jacs.0c02988 PMid:32406680

L'Hôpital E, Lothenbach B, Scrivener K, Kulik DA. 2016. Alkali uptake in calcium alumina silicate hydrate (CASH). Cem. Concr. Res. 85:122-136. https://doi.org/10.1016/j.cemconres.2016.03.009

Pardal X, Brunet F, Charpentier T, Pochard I, Nonat A. 2012. 27Al and 29Si solid-state NMR characterization of calcium-aluminosilicate hydrate. Inorg. Chem. 51(3):1827-1836. https://doi.org/10.1021/ic202124x PMid:22277014

Pardal X, Pochard I, Nonat A. 2009. Experimental study of Si-Al substitution in calcium-silicate-hydrate (CSH) prepared under equilibrium conditions. Cem. Concr. Res. 39(8): 637-643. https://doi.org/10.1016/j.cemconres.2009.05.001

Kalousek GL. 1957. Crystal chemistry of hydrous calcium silicates: I, substitution of aluminum in lattice of tobermorite. J. Am. Chem. Soc. 40(3): 74-80. https://doi.org/10.1111/j.1151-2916.1957.tb12579.x

Bonaccorsi E, Merlino S, Kampf AR. 2005. The crystal structure of tobermorite 14 Å (plombierite), a C-S-H phase. J. Am. Chem. Soc. 88(3): 505-512. https://doi.org/10.1111/j.1551-2916.2005.00116.x

Merlino S, Bonaccorsi E, Armbruster T. 1999. Tobermorites: Their real structure and order-disorder (OD) character. Am. Mineral. 84 (10): 1613-1621. https://doi.org/10.2138/am-1999-1015

Torrens-Martí D. 2013. Mezclas ternarias de cemento Portland, cemento de aluminato de calcio y sulfato cálcico: mecanismos de expansión. [PhD thesis]. Universitat Politècnica de Catalunya. Barcelona.

Torrens-Martín D, Fernández-Carrasco L. 2013. Effect of sulfate content on cement mixtures. Constr. Build. Mater. 48: 144-150. https://doi.org/10.1016/j.conbuildmat.2013.05.106

Torrens-Martín D, Fernández-Carrasco L, Blanco-Varela MT. 2013. Conduction calorimetric studies of ternary binders based on Portland cement, calcium aluminate cement and calcium sulphate. J. Therm. Anal. Calorim. 114: 799-807. https://doi.org/10.1007/s10973-013-3003-9

Torrens-Martín D, Winnefeld F, Fernández-Carrasco L. 2021. Thermodynamic model for ternary OPC/CAC/Calcium Sulfate binders. Constr. Build. Mater. 302: 124120. https://doi.org/10.1016/j.conbuildmat.2021.124120

Palomo A, Krivenko P, García-Lodeiro I, Kavalerova E, Maltseva O, Fernández-Jiménez A. (2014). A review on alkaline activation: new analytical perspectives. Mater. Construcc. 64 (135): e022. https://doi.org/10.3989/mc.2014.00314

Robayo-Salazar R, Mejía de Gutiérrez R, Puertas F. 2019. Alkali-activated binary concrete based on a natural pozzolan: physical, mechanical and microstructural characterization. Mater. Construcc. 69 (335): e191. https://doi.org/10.3989/mc.2019.06618

Zhang J, Scherer GW. 2011. Comparison of methods for arresting hydration of cement. Cem. Concr. Res. 41(10):1024 1036. https://doi.org/10.1016/j.cemconres.2011.06.003

Guirado F, Galí S. 2006. Quantitative Rietveld analysis of CAC clinker phases using synchrotron radiation. Cem. Concr. Res. 36 (11): 2021-2032. https://doi.org/10.1016/j.cemconres.2006.05.019

Griffiths PR, Pariente GL. 1986. Introduction to spectral deconvolution. Anal. Chem. 5 (8): 209-215. https://doi.org/10.1016/0165-9936(86)80015-2

Fernández-Carrasco L, Torrens-Martín D, Morales LM, Martínez-Ramírez S. 2012. Infrared spectroscopy in the analysis of building and construction materials. InTech. 357-372. https://doi.org/10.5772/36186

Yu P, Kirkpatrick RJ, Poe B, McMillan PF, Cong X. 1999. Structure of calcium silicate hydrate (C-S-H): Near-, Mid-, and Farinfrared spectroscopy. J. Am. Chem. Soc. 82 (3): 742-748. https://doi.org/10.1111/j.1151-2916.1999.tb01826.x

Bonaccorsi E, Merlino S, Taylor HFW. 2004. The crystal structure of jennite, Ca9Si6O18(OH)6·8H2O. Cem. Concr. Res. 34 (9): 1481-1488. https://doi.org/10.1016/j.cemconres.2003.12.033

Kirkpatrick RJ, Yarger JL, McMillan PF, Ping Y, Cong X. 1997. Raman spectroscopy of CSH, tobermorite, and jennite. Adv. Cem. Based Mater. 5 (3-4): 93-99. https://doi.org/10.1016/S1065-7355(97)00001-1

Masse S, Zanni H, Lecourtier J, Roussel JC, Rivereau A. 1993. 29Si solid state NMR study of tricalcium silicate and cement hydration at high temperature. Cem. Concr. Res. 23 (5): 1169-1177. https://doi.org/10.1016/0008-8846(93)90177-B

García-Lodeiro I, Fernández-Jiménez A, Sobrados I, Sanz J, Palomo A. 2012. C-S-H Gels: Interpretation of 29Si MAS-NMR Spectra. J. Am. Chem. Soc. 95 (4): 1440-1446. https://doi.org/10.1111/j.1551-2916.2012.05091.x

Sáez del Bosque IF, Martínez-Ramírez S, Blanco-Varela MT. (2015). Calorimetric study of the early stages of the nanosilica - tricalcium silicate hydration. Effect of temperature. Mater. Construcc. 65 (320): e070. https://doi.org/10.3989/mc.2015.06814

Kapeluszna E, Kotwica Ł, Różycka A, Gołek Ł. 2017. Incorporation of Al in CASH gels with various Ca/Si and Al/Si ratio: Microstructural and structural characteristics with DTA/TG, XRD, FTIR and TEM analysis. Constr. Build. Mater. 155: 643-653. https://doi.org/10.1016/j.conbuildmat.2017.08.091

Adamczyk A, Długoń E. 2012. The FTIR studies of gels and thin films of Al2O3-TiO2 and Al2O3-TiO2-SiO2 systems. Spectrochim. Acta A Mol. Biomol. Spectrosc. 89:11-17. https://doi.org/10.1016/j.saa.2011.12.018 PMid:22240231

Gu P, Beaudoin JJ. 1997. A conduction calorimetric study of early hydration of ordinary Portland cement/high alumina cement pastes. J. Mater. Sci. 32: 3875-3881. https://doi.org/10.1023/A:1018600412638

Nakamoto K. 2008. Infrared and Raman Spectra of Inorganic and Coordination Compounds: Theory and applications in inorganic chemistry. Wiley. New York. https://doi.org/10.1002/9780470405840

Andersen MD, Jakobsen HJ, Skibsted J. 2004. Characterization of white Portland cement hydration and the CSH structure in the presence of sodium aluminate by 27Al and 29Si MAS NMR spectroscopy. Cem. Concr. Res. 34 (5): 857-868. https://doi.org/10.1016/j.cemconres.2003.10.009

Zunino F, Scrivener K. 2022. The influence of sulfate addition on hydration kinetics and CSH morphology of C3S and C3S/C3A systems. Cem. Concr. Res. 160: 106930. https://doi.org/10.1016/j.cemconres.2022.106930

Quennoz A, Scrivener K. 2013. Interactions between alite and C3A-gypsum hydrations in model cements. Cem. Concr. Res. 44: 46-54. https://doi.org/10.1016/j.cemconres.2012.10.018

Bergold ST, Goetz-Neunhoeffer F, Neubauer J. 2017. Interaction of silicate and aluminate reaction in a synthetic cement system: Implications for the process of alite hydration. Cem. Concr. Res. 93: 32-44. https://doi.org/10.1016/j.cemconres.2016.12.006

Yang SY, Yan Y, Lothenbach B, Skibsted J. 2021. Incorporation of sodium and aluminum in cementitious calcium alumino-silicatehydrate C-(A)-SH phases studied by 23Na, 27Al, and 29Si MAS NMR spectroscopy. J. Phys. Chem. C. 125 (51): 27975-27995. https://doi.org/10.1021/acs.jpcc.1c08419

Torres-Carrasco M, Palomo JG, Puertas F. 2014. Sodium silicate solutions from dissolution of glasswastes. Statistical analysis. Mater. Construcc. 64 (314): e014. https://doi.org/10.3989/mc.2014.05213

Neto FM, Snellings R, Skibsted J. 2024. Aqueous carbonation of aged blended Portland cement pastes: Impact of the Al/Si ratio on the structure of the alumina-silica gel. Cem. Concr. Res.177: 107428. https://doi.org/10.1016/j.cemconres.2024.107428

Richardson IG, Brough AR, Groves GW, Dobson CM. 1994. The characterization of hardened alkali-activated blast furnace slag pastes and the nature of the calcium silicate hydrate (CSH) phase. Cem. Concr. Res. 24 (5): 813-829. https://doi.org/10.1016/0008-8846(94)90002-7

Richardson IG. 2014. Model structures for C-(A)-S-H(I). Acta Cryst. B. 70 (6): 903-923. https://doi.org/10.1107/S2052520614021982 PMid:25449614 PMCid:PMC4468512

Goñi S, Guerrero A, Puertas F, Hernández MS, Palacios M, Dolado JS, Zhu W, Howind T. 2011. Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C3S, β-C2S and their blends. Mater. Construcc. 61 (302): 169-183. https://doi.org/10.3989/mc.2011.00511

Skibsted J, Hjorth J, Jakobsen HJ. 1990. Correlation between 29Si NMR chemical shifts and mean Si O bond lengths for calcium silicates. Chem. Phys. Lett. 172 (3-4): 279-283. https://doi.org/10.1016/0009-2614(90)85403-Y

Lü Z, Tan H, Liu X, Chen P, Wang Y, Liang W. 2023. Effect of hydrated calcium aluminate cement on the chloride immobilization of Portland cement paste. J. Wuhan Univ. Technol. Mater. Sci. 38 (6): 1360-1371. https://doi.org/10.1007/s11595-023-2830-1

Fan W, Zhuge Y, Ma X, Chow CW, Gorjian N, Oh JA, Duan W. 2020. Durability of fibre-reinforced calcium aluminate cement (CAC)-ground granulated blast furnace slag (GGBFS) blended mortar after sulfuric acid attack. Materials, 13 (17): 3822. https://doi.org/10.3390/ma13173822 PMid:32872478 PMCid:PMC7503559

Pöllmann H. 2012. Calcium aluminate cements-raw materials, differences, hydration and properties. Rev. Mineral. Geochem. 74 (1): 1-82. https://doi.org/10.2138/rmg.2012.74.1

Neto JDSA, Angeles G, Kirchheim AP. 2021. Effects of sulfates on the hydration of Portland cement-A review. Constr. Build. Mater. 279: 122428. https://doi.org/10.1016/j.conbuildmat.2021.122428

Alonso MM, Rodríguez A, Puertas F. 2018. Viability of the use of construction and demolition waste aggregates in alkali-activated mortars. Mater. Construcc. 68 (331): e164. https://doi.org/10.3989/mc.2018.07417