Early Hydration Behavior of Phosphorous Slag Composite Cementitious Materials at Different Curing Temperatures

Abstract

Curing temperature significantly affects the pozzolanic reaction kinetics of phosphorous slag (PS), thereby governing the early-age (7 d) hydration behavior of PS composite binders at 20, 30, and 60 °C. The Krstulovic-Dabic kinetic model was applied to identify three characteristic processes: nucleation and growth (NG), phase boundary interaction (I), and diffusion (D). Control mixtures containing inert quartz powder with comparable particle size distributions were prepared for comparison. Pore characteristics of hardened PS pastes at different temperatures were analyzed via mercury intrusion porosimetry, while hydration products were characterized using X-ray diffraction (XRD) and thermogravimetric analysis (TG-DTG). The experimental results indicate that the retarding effect of PS on early cement hydration outweighs its accelerating effect, attributed to the combined influence of nucleation and dilution, with retardation decreasing as temperature increases. PS exhibits early reactivity and continuously consumes calcium hydroxide through the pozzolanic reaction, as evidenced by stable phase assemblages accompanied by reduced CH content in XRD and TG-DTG analyses. At 20 °C, increasing PS content maintains the NG→I→D mechanism but slows reaction rates across all stages. Elevated temperatures significantly accelerate the NG process, shifting the dominant mechanism from NG toward D. Simultaneously, enhanced PS reactivity contributes to a refined pore structure and improved compressive strength.

Keywords

phosphorous slag / temperatures / hydration kinetics / pore structure / compressive strength

References

[1] Wu T, Ng ST, Chen J. Deciphering the CO₂ Emissions and Emission Intensity of Cement Sector in China Through Decomposition Analysis. J. Clean. Prod., 2022, 352: 131 627 J]

[2] Zhang CY, Yu B, Chen JM, et al. . Green Transition Pathways for Cement Industry in China. Resour. Conserv. Recycl., 2021, 166: 105 355 J]

[3] Bignozzi MC. Sustainable Cements for Green Buildings Construction. Procedia Eng., 2011, 21: 915-921 J]

[4] Madlool NA, Saidur R, Hossain MS, et al. . A Critical Review on Energy Use and Savings in the Cement Industries. Renew. Sustain. Energy Rev., 2011, 15(4): 2 042-2 060 J]

[5] Rehan R, Nehdi M. Carbon Dioxide Emissions and Climate Change: Policy Implications for the Cement Industry. Environ. Sci. Policy, 2005, 8(2): 105-114 J]

[6] Shen W, Liu Y, Yan B, et al. . Cement Industry of China: Driving Force, Environment Impact and Sustainable Development. Renew. Sustain. Energy Rev., 2017, 75: 618-628 J]

[7] Gu X, Wang H, Zhu Z, et al. . Synergistic Effect and Mechanism of Lithium Slag on Mechanical Properties and Microstructure of Steel Slag-cement System. Constr. Build. Mater., 2023, 396: 131 768 J]

[8] Lothenbach B, Scrivener K, Hooton R D. Supplementary Cementitious Materials. Cem. Concr. Res., 2011, 41(12): 1 244-1 256 J]

[9] Mapa D G, Zhu H, Nosouhian F, et al. . Chloride Binding and Diffusion of Slag Blended Concrete Mixtures. Constr. Build. Mater., 2023, 388: 131 584 J]

[10] Parvin F, Luan Y, Habirun AN. Experimental Study on Chloride Binding of Slag-blended Portland Cement with Different Slag Ratios. J. Mater. Civ. Eng., 2024, 36(8): 04 024 220 J]

[11] Zhang Y, Çopuroğlu O. Correlation between Slag Reactivity and Cement Paste Properties: The Influence of Slag Chemistry. J. Mater. Civ. Eng., 2024, 36(3): 04 023 618 J]

[12] Qiang W, Peiyu Y, Jingjing F. Mag. Concr. Res. for a Massive Foundation Slab. Magazine of Concrete Research, 2013, 65(2): 71-81 J]

[13] Wang L, Guo F, Lin Y, et al. . Comparison between the Effects of Phosphorous Slag and Fly Ash on the C-S-H Structure, Long-term Hydration Heat and Volume Deformation of Cement-based Materials. Constr. Build. Mater., 2020, 250: 118 807 J]

[14] Chen R, Chen C. Autoclave Expansion and Compressive Strength of MgO-admixed RCC with Partial Fly Ash Replacement by Phosphorus slag. Crystals, 2025, 15(12): 1 048 J]

[15] Juenger MCG, Siddique R. Recent Advances in Understanding the Role of Supplementary Cementitious Materials in Concrete. Cem. Concr. Res., 2015, 78: 71-80 J]

[16] Anbia M, Ahmadian F, Rezaie M. Preparation of Titanium Dioxide Nanostructure from Ilmenite Through Sulfate-leaching Process and Solvent Extraction by D2EHPA. J. Iran. Chem. Soc., 2018, 15(11): 2 533-2 540 J]

[17] Hassankhani-Majd Z, Anbia M. Recovery of Valuable Materials from Phosphorus Slag Using Nitric Acid Leaching Followed by Precipitation Method. Resour. Conserv. Recycl., 2021, 169: 105 547 J]

[18] Yang R, Yu R, Shui Z, et al. . Low Carbon Design of an Ultra-high Performance Concrete (UHPC) Incorporating Phosphorous Slag. J. Clean. Prod., 2019, 240: 118 157 J]

[19] Jia R, Wang Q, Luo T. Understanding the Workability of Alkali-activated Phosphorus Slag Pastes: Effects of Alkali Dose and Silicate Modulus on Early-age Hydration Reactions. Cem. Concr. Compos., 2022, 133: 104 649 J]

[20] Chen Q, Ding W, Sun H, et al. . Mineral Carbonation of Yellow Phosphorus Slag and Characterization of Carbonated Product. Energy, 2019, 188: 116 102 J]

[21] Li X, Zhang Q, Mao S, et al. . Study on the Preparation and Fracture Behavior of Red Mud-yellow Phosphorus Slag-based Concrete. Adv. Mater. Sci. Eng, 2019, 2019: 1-15[J]

[22] Wang D, Wang Q. Clarifying and Quantifying the Immobilization Capacity of Cement Pastes on Heavy Metals. Cem. Concr. Res., 2022, 161: 106 945 J]

[23] Hu J. Comparison between the Effects of Superfine Steel Slag and Superfine Phosphorus Slag on the Long-term Performances and Durability of Concrete. J. Therm. Anal. Calorim., 2017, 128(3): 1 251-1 263 J]

[24] Peng Y, Zhang J, Liu J, et al. . Properties and Microstructure of Reactive Powder Concrete Having a High Content of Phosphorous Slag Powder and Silica Fume. Constr. Build. Mater., 2015, 101: 482-487 J]

[25] Wang Q, Huang Z, Wang D. Influence of High-volume Electric Furnace Nickel Slag and Phosphorous Slag on the Properties of Massive Concrete. J. Therm. Anal. Calorim., 2018, 131(2): 873-885 J]

[26] Allahverdi A, Mahinroosta M. Mechanical Activation of Chemically Activated High Phosphorous Slag Content Cement. Powder Technol., 2013, 245: 182-188 J]

[27] Chen X, Zeng L, Fang K. Anti-crack Performance of Phosphorus Slag Concrete. Wuhan Univ. J. Nat. Sci., 2009, 14(1): 80-86 J]

[28] Dongxu L, Jinlin S, Lin C, et al. . The Influence of Fast-setting/Early-strength Agent on High Phosphorous Slag Content Cement. Cem. Concr. Res., 2001, 31(1): 19-24 J]

[29] Dong-xu L, Lin C, Zhong-zi X, et al. . A Blended Cement Containing Blast Furnace Slag and Phosphorous Slag. J. Wuhan Univ. Technol.- Mater. Sci. Ed., 2002, 17(2): 62-65 J]

[30] Allahverdi A, Pilehvar S, Mahinroosta M. Influence of Curing Conditions on the Mechanical and Physical Properties of Chemically-activated Phosphorous Slag Cement. Powder Technol., 2016, 288: 132-139 J]

[31] Li D, Shen J, Mao L, et al. . The Influence of Admixtures on the Properties of Phosphorous Slag Cement. Cem. Concr. Res., 2000, 30(7): 1 169-1 173 J]

[32] Gao P, Lu X, Yang C, et al. . Microstructure and Pore Structure of Concrete Mixed with Superfine Phosphorous Slag and Superplasticizer. Constr. Build. Mater., 2008, 22(5): 837-840 J]

[33] Smith I W M. The Temperature-dependence of Elementary Reaction Rates: Beyond Arrhenius. Chem. Soc. Rev., 2008, 37(4): 812-826 J]

[34] Lothenbach B, Winnefeld F, Alder C, et al. . Effect of Temperature on the Pore Solution, Microstructure and Hydration Products of Portland Cement Pastes. Cem. Concr. Res., 2007, 37(4): 483-491 J]

[35] Zhang Z, Zhang B, Yan P. Hydration and Microstructures of Concrete Containing Raw or Densified Silica Fume at Different Curing Temperatures. Constr. Build. Mater., 2016, 121: 483-490 J]

[36] Boubekeur T, Ezziane K, Kadri EH. Estimation of Mortars Compressive Strength at Different Curing Temperature by the Maturity Method. Constr. Build. Mater., 2014, 71: 299-307 J]

[37] Bentz DP. Activation Energies of High-Volume Fly Ash Ternary Blends: Hydration and Setting. Cem. Concr. Compos., 2014, 53: 214-223 J]

[38] Castellano CC, Bonavetti VL, Donza HA, et al. . The Effect of W/B and Temperature on the Hydration and Strength of Blastfurnace Slag Cements. Constr. Build. Mater., 2016, 111: 679-688 J]

[39] Juilland P, Kumar A, Gallucci E, et al. . Effect of Mixing on the Early Hydration of Alite and Opc Systems. Cem. Concr. Res., 2012, 42(9): 1 175-1 188 J]

[40] He J, Long G, Ma C, et al. . Effect of Triethanolamine on Hydration Kinetics of Cement-Fly Ash System at Elevated Curing Temperature. ACS Sustain. Chem. Eng., 2020, 8(27): 10 053-10 064 J]

[41] Dabiĉ P, Krstuloviĉ R, Rušiĉ D. A New Approach in Mathematical Modelling of Cement Hydration Development. Cem. Concr. Res., 2000, 30(7): 1 017-1 021 J]

[42] Krstulović R, Dabić P. A Conceptual Model of the Cement Hydration Process. Cem. Concr. Res., 2000, 30(5): 693-698 J]

[43] Long Z, Long G, Tang Z, et al. . Analysis of Hydration Kinetics in High Early-Strength Cementitious System with Calcium Sulphoaluminate Cement and Csh Seeds. Constr. Build. Mater., 2024, 448: 138 222 J]

[44] Zhan P, Wang J, Zhao H, et al. . Impact of Synthetic C-S-H Seeds on Early Hydration and Pore Structure Evolution of Cement Pastes: A Study by 1H Low-Field Nmr and Path Analysis. Cem. Concr. Res., 2024, 175: 107 376 J]

[45] Zhang R, Long Z, Long G, et al. . Investigating Concrete Performance: Compressive Strength and Pore-Structure Evolution in Simulated Permafrost Conditions of the Qinghai-Tibet Plateau Zone. J. Mater. Civ. Eng., 2024, 36(5): 4 024 063 J]

[46] Long J, Yang K, Wang S, et al. . New Insights into the Contribution of Quartz Powder Byproduct from Manufactured Sand to the Performance of Cementitious Materials. J. Therm. Anal. Calorim., 2023, 148(10): 4 105-4 117 J]

[47] Chen X, Fang K, Yang H, et al. . Hydration Kinetics of Phosphorus Slag-Cement Paste[J]. J. Wuhan Univ. Technol.-Mater. Sci. Ed., 2011, 26(1): 142-146

[48] Zheng Z, He X, Tan H, et al. . Ultrafine Granulated Blast-Furnace Slag/Phosphorus Slag Blends Activated by Sodium Carbonate at Ambient Temperature. J. Wuhan Univ. Technol.-Mater. Sci. Ed., 2025, 40(5): 1 463-1 476 J]

[49] Hu X, Xu L, Li M, et al. . Effect of Temperature and Superplasticizer on Hydration of C₃S and Carbonation Products of C-S-H. Constr. Build. Mater., 2024, 444: 137 864 J]

[50] Yu S, He J, Sang G, et al. . Study on Hydration Process of Alkali-Activated Slag Cement Activated by Weakly Alkaline Components. Constr. Build. Mater., 2024, 413: 134 716 J]

[51] Han F, Zhang H, Pu S, et al. . Hydration Heat And Kinetics of Composite Binder Containing Blast Furnace Ferronickel Slag at Different Temperatures. Thermochim. Acta., 2021, 702: 178 985 J]

[52] Zhang Z, Wang Q, Yang J. Hydration Mechanisms of Composite Binders Containing Phosphorus Slag at Different Temperatures. Constr. Build. Mater., 2017, 147: 720-732 J]

RIGHTS & PERMISSIONS

Wuhan University of Technology and Springer-Verlag GmbH Germany, Part of Springer Nature