Title:
Preferential Adsorption of PCEs on OPC in Calcined Clay Blended Cements
Author(s):
Jiaxin Chen, Johann Plank
Publication:
Symposium Paper
Volume:
369
Issue:
Appears on pages(s):
49-64
Keywords:
ordinary Portland cement (OPC); supplementary cementitious materials (SCMs); calcined clay (CC); polycarboxylate (PCE) superplasticizer; workability; competitive adsorption; surface occupancy, zeta potential
DOI:
10.14359/51750721
Date:
5/1/2026
Abstract:
Calcined clay (CC) blended cements frequently exhibit poor workability, indicated by high water demand and increased dosage requirement for polycarboxylate (PCE) superplasticizers.
Generally, the dispersing performance of PCEs is correlated to their amount adsorbed onto the binder. To elucidate whether PCEs show preferential adsorption on OPC or CC, substrate-selective adsorption of PCEs was studied on an OPC/CC = 70:30 (wt./wt.) blend holding a calcined common clay from Germany. As PCE superplasticizer, a ready-mix type HPEG (methallyl ether) PCE was used. A novel filtration method combined with total organic carbon (TOC) analysis was employed to quantify the adsorbed amount of HPEG PCE on each individual component in the OPC/CC composite.
It was found that OPC and CC show considerably different affinities to PCEs. First, by weight of the binder the adsorbed amount of PCE on OPC is almost twice than that on CC at saturation point. However, when looking at PCE adsorption per surface area of a binder, then the PCE by far adsorbs mainly on cement (> 90%), and only very little on CC. The study confirms that significant preferential/selective adsorption of PCE superplasticizers in OPC/CC blends occurs, which explains the decreased performance of PCEs in CC blended cements versus OPC.
Related References:
1. B. Lothenbach, K. Scrivener, R. Hooton, Supplementary cementitious materials, Cement and concrete research, 41 (2011) 1244-1256.
2. R. Snellings, P. Suraneni, J. Skibsted, Future and emerging supplementary cementitious materials, Cement and concrete research, 171 (2023) 107199.
3. I.H. Shah, S.A. Miller, D. Jiang, R.J. Myers, Cement substitution with secondary materials can reduce annual global CO2 emissions by up to 1.3 gigatons, Nature Communications, 13 (2022) 5758.
4. K. Scrivener, F. Martirena, S. Bishnoi, S. Maity, Calcined clay limestone cements (LC3), Cement and concrete research, 114 (2018) 49-56.
5. M.C. Juenger, R. Snellings, S.A. Bernal, Supplementary cementitious materials: New sources, characterization, and performance insights, Cement and Concrete Research, 122 (2019) 257-273.
6. T. Hanein, K.-C. Thienel, F. Zunino, A.T.M. Marsh, M. Maier, B. Wang, M. Canut, M.C.G. Juenger, M. Ben Haha, F. Avet, A. Parashar, L.A. Al-Jaberi, R.S. Almenares-Reyes, A. Alujas-Diaz, K.L. Scrivener, S.A. Bernal, J.L. Provis, T. Sui, S. Bishnoi, F. Martirena-Hernández, Clay calcination technology: state-of-the-art review by the RILEM TC 282-CCL, Materials and Structures, 55 (2021) 3.
7. S. Barbhuiya, J. Nepal, B.B. Das, Properties, compatibility, environmental benefits and future directions of limestone calcined clay cement (LC3) concrete: A review, Journal of Building Engineering, 79 (2023) 107794.
8. H. Maraghechi, F. Avet, H. Wong, H. Kamyab, K. Scrivener, Performance of Limestone Calcined Clay Cement (LC 3) with various kaolinite contents with respect to chloride transport, Materials and structures, 51 (2018) 1-17.
9. R.-S. Lin, S. Oh, W. Du, X.-Y. Wang, Strengthening the performance of limestone-calcined clay cement (LC3) using nano silica, Construction and Building Materials, 340 (2022) 127723.
10. L. Lei, M. Palacios, J. Plank, A.A. Jeknavorian, Interaction between polycarboxylate superplasticizers and non-calcined clays and calcined clays: A review, Cement and Concrete Research, 154 (2022) 106717.
11. S. Ferreiro, D. Herfort, J.S. Damtoft, Effect of raw clay type, fineness, water-to-cement ratio and fly ash addition on workability and strength performance of calcined clay – Limestone Portland cements, Cement and Concrete Research, 101 (2017) 1-12.
12. R. Sposito, N. Beuntner, K.-C. Thienel, Characteristics of components in calcined clays and their influence on the efficiency of superplasticizers, Cement and Concrete Composites, 110 (2020) 103594.
13. I. Bhandari, R. Kumar, A. Sofi, N.S. Nighot, A systematic study on sustainable low carbon cement–Superplasticizer interaction: Fresh, mechanical, microstructural and durability characteristics, Heliyon, 9 (2023).
14. M. Niu, G. Li, Q. Li, G. Zhang, Influence of naphthalene sulphonated and polycarboxylate acid-based superplasticizer on the mechanical properties and hydration behavior of ternary binder: A comparative study, Construction and Building Materials, 312 (2021) 125374.
15. R. Li, L. Lei, J. Plank, Impact of metakaolin content and fineness on the behavior of calcined clay blended cements admixed with HPEG PCE superplasticizer, Cement and Concrete Composites, 133 (2022) 104654.
16. R. Li, L. Lei, J. Plank, Influence of PCE superplasticizers on the fresh properties of low carbon cements containing calcined clays: A comparative study of calcined clays from three different sources, Cement and Concrete Composites, 139 (2023) 105072.
17. M. Schmid, J. Plank, Interaction of individual meta clays with polycarboxylate (PCE) superplasticizers in cement investigated via dispersion, zeta potential and sorption measurements, Applied Clay Science, 207 (2021) 106092.
18. M. Schmid, J. Plank, Dispersing performance of different kinds of polycarboxylate (PCE) superplasticizers in cement blended with a calcined clay, Construction and Building Materials, 258 (2020) 119576.
19. J. Chen, J. Plank, Alkali-activated calcined clay blended cement: Effect of NaOH activator on performance of HPEG PCEs and on early strength, Cement and Concrete Research, 183 (2024) 107588.
20. R. Li, L. Lei, T. Sui, J. Plank, Effectiveness of PCE superplasticizers in calcined clay blended cements, Cement and Concrete Research, 141 (2021) 106334.
21. R.J. Flatt, I. Schober, E. Raphael, C. Plassard, E. Lesniewska, Conformation of adsorbed comb copolymer dispersants, Langmuir, 25 (2009) 845-855.
22. G. Gelardi, R.J. Flatt, 11 - Working mechanisms of water reducers and superplasticizers, in: P.-C. Aïtcin, R.J. Flatt (Eds.) Science and Technology of Concrete Admixtures, Woodhead Publishing2016, pp. 257-278.
23. K. Yoshioka, E.-i. Tazawa, K. Kawai, T. Enohata, Adsorption characteristics of superplasticizers on cement component minerals, Cement and Concrete Research, 32 (2002) 1507-1513.
24. J. Plank, B. Sachsenhauser, J. De Reese, Experimental determination of the thermodynamic parameters affecting the adsorption behaviour and dispersion effectiveness of PCE superplasticizers, Cement and Concrete Research, 40 (2010) 699-709.
25. A. Lange, J. Plank, Contribution of non-adsorbing polymers to cement dispersion, Cement and Concrete Research, 79 (2016) 131-136.
26. J. Plank, B. Sachsenhauser, Experimental determination of the effective anionic charge density of polycarboxylate superplasticizers in cement pore solution, Cement and Concrete Research, 39 (2009) 1-5.
27. K. Yamada, S. Ogawa, S. Hanehara, Controlling of the adsorption and dispersing force of polycarboxylate-type superplasticizer by sulfate ion concentration in aqueous phase, Cement and Concrete Research, 31 (2001) 375-383.
28. J. Plank, N.R. Lummer, F. Dugonjić‐Bilić, Competitive adsorption between an AMPS®‐based fluid loss polymer and Welan gum biopolymer in oil well cement, Journal of Applied Polymer Science, 116 (2010) 2913-2919.
29. H. Bessaies-Bey, R. Baumann, M. Schmitz, M. Radler, N. Roussel, Organic admixtures and cement particles: Competitive adsorption and its macroscopic rheological consequences, Cement and Concrete Research, 80 (2016) 1-9.
30. J. Plank, C. Winter, Competitive adsorption between superplasticizer and retarder molecules on mineral binder surface, Cement and Concrete Research, 38 (2008) 599-605.
31. H. Bessaies-Bey, N. Massoussi, S. Mulik, R. Baumann, M. Schmitz, M. Radler, G. Gelardi, R.J. Flatt, N. Roussel, Polycarboxylate ester adsorption on cement grains: Influence of polydispersity, Cement and Concrete Research, 143 (2021) 106383.
32. D. Atarashi, E. Sakai, R. Obinata, M. Daimon, Interactions between superplasticizers and clay minerals, Cem. Sci. Concr. Technol., 58 (2004) 387-392.
33. E. Sakai, D. Atarashi, M. Daimon, Interaction between superplasticizers and clay minerals: special publication 1/6-CANMET conference on superplasticizers and other chemical admixtures/China, 2006, Р.
34. C. Schröfl, M. Gruber, J. Plank, Preferential adsorption of polycarboxylate superplasticizers on cement and silica fume in ultra-high performance concrete (UHPC), Cement and Concrete Research, 42 (2012) 1401-1408.
35. D. Kosenko, A. Wetzel, B. Middendorf, Fluorescence microscopic investigation of PCE superplasticizer adsorption in calcined clay blended cement, Journal of Microscopy, 294 (2024) 215-224.
36. J. Chen, J. Plank, Do PCEs adsorb preferentially on OPC or calcined clay?, submitted to Cement and Concrete Research in July 2025, under review.
37. U. Pott, C. Crasselt, N. Fobbe, M. Haist, M. Heinemann, S. Hellmann, D. Ivanov, C. Jakob, D. Jansen, L. Lei, Characterization data of reference materials used for phase II of the priority program DFG SPP 2005 “Opus Fluidum Futurum–Rheology of reactive, multiscale, multiphase construction materials”, Data in brief, 47 (2023) 108902.
38. M.T.R. Laguna, R. Medrano, M.P. Plana, M.P. Tarazona, Polymer characterization by size-exclusion chromatography with multiple detection, Journal of Chromatography A, 919 (2001) 13-19.
39. A. Habbaba, J. Plank, Surface chemistry of ground granulated blast furnace slag in cement pore solution and its impact on the effectiveness of polycarboxylate superplasticizers, Journal of the American Ceramic Society, 95 (2012) 768-775.
40. DIN EN 1015-3:2007-5, Methods of Test for Mortar for Masonry -Part 3: Determination of Consistence of Fresh Mortar, DIN, Berlin/Germany, 2007.
41. D. Staude, J. Plank, Phase analysis and hydration behavior of fine and coarse particle fractions contained in a commercial Portland cement, Journal of Sustainable Cement-Based Materials, 12 (2023) 415-426.
42. B.B. Sabir, S. Wild, J. Bai, Metakaolin and calcined clays as pozzolans for concrete: a review, Cement and Concrete Composites, 23 (2001) 441-454.
43. C. Giraudeau, J.B. D'Espinose De Lacaillerie, Z. Souguir, A. Nonat, R.J. Flatt, Surface and intercalation chemistry of polycarboxylate copolymers in cementitious systems, Journal of the American Ceramic Society, 92 (2009) 2471-2488.
44. Y. Zhang, X. Kong, Correlations of the dispersing capability of NSF and PCE types of superplasticizer and their impacts on cement hydration with the adsorption in fresh cement pastes, Cement and concrete research, 69 (2015) 1-9.
45. S. Dhers, A. Müller, R. Guggenberger, D. Freimut, K. Weldert, B. Sachsenhauser, V. Yermakou, N. Mikanovic, P. Schwesig, On the relationship between superplasticizer demand and specific surface area of calcined clays in LC3 systems, Construction and Building Materials, 411 (2024) 134467.
46. R. Sposito, M. Maier, N. Beuntner, K.-C. Thienel, Physical and mineralogical properties of calcined common clays as SCM and their impact on flow resistance and demand for superplasticizer, Cement and Concrete Research, 154 (2022) 106743.
47. J. Chen, J. Plank, Calcined clays for climate neutral (“net zero”) cements: shear-dependent rheological behavior and application performance, Cement and Concrete Composites, 162 (2025) 106145.
48. R. Sposito, M. Maier, N. Beuntner, K.-C. Thienel, Evaluation of zeta potential of calcined clays and time-dependent flowability of blended cements with customized polycarboxylate-based superplasticizers, Construction and Building Materials, 308 (2021) 125061.
49. M. Maier, R. Sposito, N. Beuntner, K.-C. Thienel, Particle characteristics of calcined clays and limestone and their impact on early hydration and sulfate demand of blended cement, Cement and Concrete Research, 154 (2022) 106736.