Thermo-Mechano-Chemo Dynamics of Clay’s Reactivity and its Correlation with Limestone Calcined Clay Cement (LC3) Performance
Source abstract
Abstract
This study aimed to enhance calcined clay reactivity via mechanical or chemical treatments. Properties were analyzed using XRF, TGA, and XRD; reactivity was assessed with modified Chappelle and R3-bound water tests. XRD patterns for thermally (Th) and thermo-mechanically (ThM) treated clays were similar. Zeolite formation in thermo-chemically (ThC) treated clay was observed and confirmed by TGA with significant mass loss below 400°C. The reactivity of calcined clay exceeded that of untreated clay, in the order Th > ThM > ThC, as confirmed by tests. Subsequently, LC3 mortar was formulated using these activated clays. Assessments included heat of hydration and compressive strength over 90 days, along with XRD and TGA characterizations. The findings demonstrated that the trends in heat of hydration and compressive strength paralleled those observed in reactivity, with LC3-Th > LC3-ThM > LC3-ThC. Although the cement mortar had higher compressive strength than LC3 at 7 days, LC3 showed greater strength after 28 days. A correlation matrix and heat map were also created to analyze the relationship between reactivity and strength. Normalized values confirmed the findings, showing a strong correlation between the R3-bound water value, heat of hydration, and strength up to 90 days.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Concrete and Cement Materials Research · Soil and Unsaturated Flow · Clay minerals and soil interactions
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Architectural Engineering and Design, Faculty of Civil Engineering, University of Engineering and Technology, Lahore, Pakistan.
Department of Building and Architectural Engineering, Faculty of Engineering and Technology, Bahauddin Zakariya University, Multan, Pakistan.
References (58)
Show source-provided references
1. 1) Abdelaziz, G. E., Shoukry, H., Selim, A. A. and Saif, M. S., (2023). “Recent progress in limestone-calcined clay cement (LC3): A review.” Materials Science Forum, 1089, 165-174.10.4028/p-74p7so ↗
2. 2) Abu, T. O., Adegoke, H. I., Odebunmi, E. O. and Shehzad, M. A., (2024). “Enhancing adsorption capacity of a kaolinite mineral through acid activation and manual blending with a 2:1 clay.” Nigerian Journal of Technological Development, 21(1), 131-151.10.4314/njtd.v21i1.2269 ↗
3. 3) AFNOR, (2012). “Addition for concrete - Metakaolin - Specifications and conformity criteria (NF P18-513).” Paris: French Standardization Association (AFNOR).
4. 4) Ahmad, M. and Rashid, K., (2022). “Novel approach to synthesize clay-based geopolymer brick: Optimizing molding pressure and precursors’ proportioning.” Construction and Building Materials, 322, 126472.10.1016/j.conbuildmat.2022.126472 ↗
5. 5) Ahmed, A. H., Nune, S., Liebscher, M., Köberle, T., Willomitzer, A., Noack, I., Butler, M. and Mechtcherine, V., (2023). “Exploring the role of dilutive effects on microstructural development and hydration kinetics of limestone calcined clay cement (LC3) made of low-grade raw materials.” Journal of Cleaner Production, 428, 139438.10.1016/j.jclepro.2023.139438 ↗
6. 6) Alqahtani, F. K., Rashid, K., Zafar, I., Iqbal Khan, M. and Ababtain, A. A., (2021). “Production of sustainable green mortar by ultrahigh utilization of fly ash: Technical, economic and environmental assessment.” Construction and Building Materials, 281, 122617.10.1016/j.conbuildmat.2021.122617 ↗
7. 7) ASTM, (2008). “Standard test method for compressive strength of hydraulic cement mortars (using 2-in. or 50-mm cube specimens) (ASTM C109/C109M).” West Conshohocken, Pennsylvania: ASTM International.
8. 8) Avet, F. and Scrivener, K., (2020). “Simple and reliable quantification of kaolinite in clay using an oven and a balance.” In: S. Bishnoi, Ed. Proc. 3rd International Conference on Calcined Clays for Sustainable Concrete, New Delhi 15-17 October 2019. Singapore: Springer Singapore, 147-156.10.1007/978-981-15-2806-4_17 ↗
9. 9) Avet, F., Li, X., Ben Haha, M., Bernal, S. A., Bishnoi, S., Cizer, Ö., Cyr, M., Dolenec, S., Durdzinski, P., Haufe, J., Hooton, D., Juenger, M. C. G., Kamali-Bernard, S., Londono-Zuluaga, D., Marsh, A. T. M., Marroccoli, M., Mrak, M., Parashar, A., Patapy, C., Pedersen, M., Provis, J. L., Sabio, S., Schulze, S., Snellings, R., Telesca, A., Thomas, M., Vargas, F., Vollpracht, A., Walkley, B., Winnefeld, F., Ye, G., Zhang, S. and Scrivener, K., (2022). “Report of RILEM TC 267-TRM, Phase 2: Optimization and testing of the robustness of the R3 reactivity tests for supplementary cementitious materials.” Materials and Structures, 55, 92.10.1617/s11527-022-01928-6 ↗
10. 10) Avet, F., Snellings, R., Alujas Diaz, A., Ben Haha, M. and Scrivener, K., (2016). “Development of a new rapid, relevant and reliable (R3) test method to evaluate the pozzolanic reactivity of calcined kaolinitic clays.” Cement and Concrete Research, 85, 1-11.10.1016/j.cemconres.2016.02.015 ↗
11. 11) Azubuike, T. C., Nnabo, P. N., Osonwa, N. O., Odoala, C. E., Nwabineli, E. O. and Koreyo, V. D., (2024). “Mineralogical, geochemical and physical properties assessment of clay deposits in Umuoke Obowo Southeastern Nigeria for industrial applications.” World Journal of Advanced Research and Reviews, 21(3), 533-545.10.30574/wjarr.2024.21.3.0699 ↗
12. 12) Baki, V. A., Ke, X., Heath, A., Calabria-Holley, J. and Terzi, C., (2023). “Improving the pozzolanic reactivity of clay, marl and obsidian through mechanochemical or thermal activation.” Materials and Structures, 57, 9.10.1617/s11527-023-02280-z ↗
13. 13) Balaz, P., Achimovicova, M., Balaz, M., Billik, P., Cherkezova-Zheleva, Z., Criado, J. M., Delogu, F., Dutkova, E., Gaffet, E., Gotor, F. J., Kumar, R., Mitov, I., Rojac, T., Senna, M., Streletskii, A. and Wieczorek-Ciurowa, K., (2013). “Hallmarks of mechanochemistry: From nanoparticles to technology.” Chemical Society Reviews, 42(18), 7571-7637.10.1039/c3cs35468g ↗
14. 14) Bergaya, F. and Lagaly, G., (2013). “General introduction: Clays, clay minerals, and clay science.” In: F. Bergaya, B. K. G. Theng and G. Lagaly, Eds. Handbook of Clay Science. Amsterdam, The Netherlands: Elsevier Science, 1-18.10.1016/B978-0-08-098258-8.00001-8 ↗
15. 15) Blouch, N., Rashid, K. and Ju, M., (2023a). “Exploring low-grade clay minerals diving into limestone calcined clay cement (LC3): Characterization − Hydration − Performance.” Journal of Cleaner Production, 426, 139065.10.1016/j.jclepro.2023.139065 ↗
16. 16) Blouch, N., Rashid, K., Zafar, I., Ltifi, M. and Ju, M., (2023b). “Prioritization of low-grade kaolinite and mixed clays for performance evaluation of limestone calcined clay cement (LC3): Multi-criteria assessment.” Applied Clay Science, 243, 107080.10.1016/j.clay.2023.107080 ↗
17. 17) Borno, I. B., Nair, N. and Ashraf, W., (2024). “Alkali thermal fusion: A prospective route to enhance the reactivity of low-grade clay and utilize as supplementary cementitious material (SCM).” Cement and Concrete Composites, 147, 105417.10.1016/j.cemconcomp.2023.105417 ↗
18. 18) Brigatti, M. F., Galan, E. and Theng, B., (2013). “Structure and mineralogy of clay minerals.” Developments in Clay Science, 1, 19-86.10.1016/S1572-4352(05)01002-0 ↗
19. 19) Canbek, O., Xu, Q., Mei, Y., Washburn, N. R. and Kurtis, K. E., (2022). “Predicting the rheology of limestone calcined clay cements (LC3): Linking composition and hydration kinetics to yield stress through machine learning.” Cement and Concrete Research, 160, 106925.10.1016/j.cemconres.2022.106925 ↗
20. 20) Cardinaud, G., Rozière, E., Martinage, O., Loukili, A., Barnes-Davin, L., Paris, M. and Deneele, D., (2021). “Calcined clay – limestone cements: Hydration processes with high and low-grade kaolinite clays.” Construction and Building Materials, 277, 122271.10.1016/j.conbuildmat.2021.122271 ↗
21. 21) Chen, J., Jia, J., Zhu, M. and Zhang, L., (2023). “Advances of alkanolamine in hydration of Portland cement.” Materials Today Communications, 37, 107129.10.1016/j.mtcomm.2023.107129 ↗
22. 22) Chen, Y., Romero Rodriguez, C., Li, Z., Chen, B., Çopuroğlu, O. and Schlangen, E., (2020). “Effect of different grade levels of calcined clays on fresh and hardened properties of ternary-blended cementitious materials for 3D printing.” Cement and Concrete Composites, 114, 103708.10.1016/j.cemconcomp.2020.103708 ↗
23. 23) Cundy, C. S. and Cox, P. A., (2005). “The hydrothermal synthesis of zeolites: Precursors, intermediates and reaction mechanism.” Microporous and Mesoporous Materials, 82(1-2), 1-78.10.1016/j.micromeso.2005.02.016 ↗
24. 24) da Silva, M. R. C., Andrade Neto, J. d. S., Walkley, B. and Kirchheim, A. P., (2024). “Exploring sulfate optimization techniques in limestone calcined clay cements (LC3): Limitations and insights.” Cement and Concrete Research, 175, 107375.10.1016/j.cemconres.2023.107375 ↗
25. 25) Dhandapani, Y., Sakthivel, T., Santhanam, M., Gettu, R. and Pillai, R. G., (2018). “Mechanical properties and durability performance of concretes with limestone calcined clay cement (LC3).” Cement and Concrete Research, 107, 136-151.10.1016/j.cemconres.2018.02.005 ↗
26. 26) Dixit, A., Du, H., Dang, J. and Pang, S. D., (2021). “Quaternary blended limestone-calcined clay cement concrete incorporating fly ash.” Cement and Concrete Composites, 123, 104174.10.1016/j.cemconcomp.2021.104174 ↗
27. 27) Ferraz, E., (2015). “Pozzolanic activity of metakaolins by the French standard of the modified Chapelle test: A direct methology.” Acta Geodynamica et Geomaterialia, 12(3), 289-298.10.13168/AGG.2015.0026 ↗
28. 28) Franco Zunino, K. S., (2024). “Reactivity of kaolinitic clays calcined in the 650°C - 1050°C temperature range: Towards a robust assessment of overcalcination.” Cement and Concrete Composites, 146, 105380.10.1016/j.cemconcomp.2023.105380 ↗
29. 29) Hay, R. and Celik, K., (2023). “Performance enhancement and characterization of limestone calcined clay cement (LC3) produced with low-reactivity kaolinitic clay.” Construction and Building Materials, 392, 131831.10.1016/j.conbuildmat.2023.131831 ↗
30. 30) Hazarika, A., Huang, L. and Babaahmadi, A., (2024). “Characterisation, activation, and reactivity of heterogenous natural clays.” Materials and Structures, 57, 68.10.1617/s11527-024-02335-9 ↗
31. 31) Islam, M. S. and Mohr, B. J., (2023). “Effect of treated clinoptilolite zeolite on alkali-silica reaction.” Materials Today: Proceedings (accepted for publication).10.1016/j.matpr.2023.04.029 ↗
32. 32) Johnson, E. B. G. and Arshad, S. E., (2014). “Hydrothermally synthesized zeolites based on kaolinite: A review.” Applied Clay Science, 97-98, 215-221.10.1016/j.clay.2014.06.005 ↗
33. 33) Joseph, S., Skibsted, J. and Cizer, Ö., (2019). “A quantitative study of the C3A hydration.” Cement and Concrete Research, 115, 145-159.10.1016/j.cemconres.2018.10.017 ↗
34. 34) Juenger, M. C. G., Snellings, R. and Bernal, S. A., (2019). “Supplementary cementitious materials: New sources, characterization, and performance insights.” Cement and Concrete Research, 122, 257-273.10.1016/j.cemconres.2019.05.008 ↗
35. 35) Kása, E., Szabados, M., Baán, K., Kónya, Z., Kukovecz, Á., Kutus, B., Pálinkó, I. and Sipos, P., (2021). “The dissolution kinetics of raw and mechanochemically treated kaolinites in industrial spent liquor – The effect of the physico-chemical properties of the solids.” Applied Clay Science, 203, 105994.10.1016/j.clay.2021.105994 ↗
36. 36) Khalifa, A. Z., Cizer, Ö., Pontikes, Y., Heath, A., Patureau, P., Bernal, S. A. and Marsh, A. T. M., (2020). “Advances in alkali-activation of clay minerals.” Cement and Concrete Research, 132, 106050.10.1016/j.cemconres.2020.106050 ↗
37. 37) Khan, K., Johari, M. A. M., Amin, M. N. and Iqbal, M., (2024). “Evaluation of the mechanical properties, microstructure, and environmental impact of mortar incorporating metakaolin, micro and nano-silica.” Case Studies in Construction Materials, 20, e02699.10.1016/j.cscm.2023.e02699 ↗
38. 38) Krishnan, S., (2019). “Hydration and microstructure development in limestone calcined clay cement.” Thesis (PhD). Indian Institute of Technology.
39. 39) Kumar, S., Panda, A. K. and Singh, R. K., (2013). “Preparation and characterization of acid and alkaline treated kaolin clay.” Bulletin of Chemical Reaction Engineering & Catalysis, 8(1), 61-69.10.9767/bcrec.8.1.4530.61-69 ↗
40. 40) Londono-Zuluaga, D., Gholizadeh-Vayghan, A., Winnefeld, F., Avet, F., Ben Haha, M., Bernal, S. A., Cizer, Ö., Cyr, M., Dolenec, S., Durdzinski, P., Haufe, J., Hooton, D., Kamali-Bernard, S., Li, X., Marsh, A. T. M., Marroccoli, M., Mrak, M., Muy, Y., Patapy, C., Pedersen, M., Sabio, S., Schulze, S., Snellings, R., Telesca, A., Vollpracht, A., Ye, G., Zhang, S. and Scrivener, K. L., (2022). “Report of RILEM TC 267-TRM phase 3: Validation of the R3 reactivity test across a wide range of materials.” Materials and Structures, 55(5), 142.10.1617/s11527-022-01947-3 ↗
41. 41) Luan, C., Wang, J. and Zhou, Z., (2023). “Synergic effect of triethanolamine and C-S-H seeding on early hydration of the limestone calcined clay cement in UHPC.” Construction and Building Materials, 400, 132675.10.1016/j.conbuildmat.2023.132675 ↗
42. 42) Maghfirah, A., Ilmi, M. M., Fajar, A. T. N. and Kadja, G. T. M., (2020). “A review on the green synthesis of hierarchically porous zeolite.” Materials Today Chemistry, 17, 100348.10.1016/j.mtchem.2020.100348 ↗
43. 43) Makó, É. and Őze, C., (2022). “The effects of silica fume and diatomaceous earth on the mechanochemical activation and pozzolanic activity of kaolin.” Applied Clay Science, 228, 106636.10.1016/j.clay.2022.106636 ↗
44. 44) Mañosa, J., Alvarez-Coscojuela, A., Marco-Gibert, J., Maldonado-Alameda, A. and Chimenos, J. M., (2024). “Enhancing reactivity in muscovitic clays: Mechanical activation as a sustainable alternative to thermal activation for cement production.” Applied Clay Science, 250, 107266.10.1016/j.clay.2024.107266 ↗
45. 45) Mañosa, J., Calvo de la Rosa, J., Silvello, A., Maldonado-Alameda, A. and Chimenos, J. M., (2023). “Kaolinite structural modifications induced by mechanical activation.” Applied Clay Science, 238, 106918.10.1016/j.clay.2023.106918 ↗
46. 46) Mitrović, A. and Zdujić, M., (2014). “Preparation of pozzolanic addition by mechanical treatment of kaolin clay.” International Journal of Mineral Processing, 132, 59-66.10.1016/j.minpro.2014.09.004 ↗
47. 47) Nair, N., Mohammed Haneefa, K., Santhanam, M. and Gettu, R., (2020). “A study on fresh properties of limestone calcined clay blended cementitious systems.” Construction and Building Materials, 254, 119326.10.1016/j.conbuildmat.2020.119326 ↗
48. 48) Ptáček, P., Frajkorová, F., Šoukal, F. and Opravil, T., (2014). “Kinetics and mechanism of three stages of thermal transformation of kaolinite to metakaolinite.” Powder Technology, 264, 439-445.10.1016/j.powtec.2014.05.047 ↗
49. 49) Py, L., Neto, J. A., Longhi, M. and Kirchheim, A., (2024). “Evaluation of ultrafine calcined clays on LC3 cements on the sulfate requirement, water demand and strength development.” Materials and Structures, 57(1), 13.10.1617/s11527-023-02288-5 ↗
50. 50) Qinfei, L., Han, W., Pengkun, H., Heng, C., Yang, W. and Xin, C. J. C. S., (2019). “The microstructure and mechanical properties of cementitious materials comprised of limestone, calcined clay and clinker.” Ceramics – Silikaty, 63, 356-364.10.13168/cs.2019.0031 ↗
51. 51) Ram, K., Flegar, M., Serdar, M. and Scrivener, K., (2022). “Influence of low-to medium-kaolinite clay on the durability of limestone calcined clay cement (LC3) concrete.” Journal of Materials, 16(1), 374.10.3390/ma16010374 ↗
52. 52) Scrivener, K., Martirena, F., Bishnoi, S. and Maity, S., (2018). “Calcined clay limestone cements (LC3).” Cement and Concrete Research, 114, 49-56.10.1016/j.cemconres.2017.08.017 ↗
53. 53) Sharma, M., Bishnoi, S., Martirena, F. and Scrivener, K., (2021). “Limestone calcined clay cement and concrete: A state-of-the-art review.” Cement and Concrete Research, 149, 106564.10.1016/j.cemconres.2021.106564 ↗
54. 54) Slaný, M., Kuzielová, E., Žemlička, M., Matejdes, M., Struhárová, A. and Palou, M. T., (2023). “Metabentonite and metakaolin-based geopolymers/zeolites: Relation between kind of clay, calcination temperature and concentration of alkaline activator.” Journal of Thermal Analysis and Calorimetry, 148(20), 10531-10547.10.1007/s10973-023-12267-1 ↗
55. 55) Tole, I., Habermehl-Cwirzen, K. and Cwirzen, A., (2019). “Mechanochemical activation of natural clay minerals: an alternative to produce sustainable cementitious binders – Review.” Mineralogy and Petrology, 113(4), 449-462.10.1007/s00710-019-00666-y ↗
56. 56) Wang, T., Medepalli, S., Zheng, Y., Zhang, W., Ishida, T., Bishnoi, S., Hou, D. and Shi, Z., (2024). “Retardation effect of the pozzolanic reaction of low-calcium supplementary cementitious materials on clinker hydration at later age: Effects of pore solution, foreign ions, and pH.” Cement and Concrete Research, 177, 107416.10.1016/j.cemconres.2023.107416 ↗
57. 57) Weng, L. and Sagoe-Crentsil, K., (2007). “Dissolution processes, hydrolysis and condensation reactions during geopolymer synthesis, Part I: Low Si/Al ratio systems.” Journal of Materials Science, 42(9), 2997-3006.10.1007/s10853-006-0820-2 ↗
58. 58) Zunino Sommariva, F. A., (2020). “Limestone calcined clay cements (LC3): Raw material processing, sulfate balance and hydration kinetics.” Thesis (PhD). Swiss Federal Institute of Technology Lausanne (EPFL).