Evaluation on the effects of Cu(II) on the properties of blast furnace slag–cement composites with adding Cu-bearing solid wastes

Abstract

The effect of heavy metals on the properties and hydration of blast furnace slag–cement composites (BFS-CC) remain unclear. In this study, two BFS-CC (denoted as DBFS-CC and WBFS-CC) were prepared by dry and wet grinding of BFS, respectively. The effect of Cu(II) on BFS-CC’s properties and hydration was investigated by adding representative copper contaminants (CuO, CuCl₂, and CuS) to the composites. Adding 1.0wt% CuO and 0.5wt% CuS increased the 3-d compressive strength of DBFS-CC by 14.9% and 5.7%, respectively, but suppressed the 3-d strength of WBFS-CC. This trend reversed at 28-d curing, where adding 1.5wt% CuO, 2.0wt% CuCl₂, and 1.5wt% CuS enhanced the compressive strength of WBFS-CC by 23.4%, 6.2%, and 13.6%, respectively, but adversely affected the strength of DBFS-CC. For 28-d hydration, adding CuCl₂ decreased the hydration degree of DBFS-CC but enhanced that of WBFS-CC. Adding CuO promoted the hydration degree of both composites, while adding CuS exhibited inhibitory effects. DBFS-CC immobilized CuCl₂ better due to a higher hydration degree, while WBFS-CC immobilized CuO and CuS better due to having finer unhydrated BFS particles and a denser matrix. This study not only focuses on the Cu(II) immobilization effect but also reveals the differential effects of Cu(II) species on the hydration process, providing novel insights into heavy metal interactions in BFS-CC systems and their safe disposal.

Keywords

copper contaminants / blast furnace slag–cement composites / mechanical properties / hydration process / immobilization process

References

[1] Goodarzi AR, Movahedrad M. Stabilization/solidification of zinc-contaminated kaolin clay using ground granulated blastfurnace slag and different types of activators. Appl. Geochem.. 2017, 81: 155

[2] Keramatikerman M, Chegenizadeh A, Nikraz H. Effect of GGBFS and lime binders on the engineering properties of clay. Appl. Clay Sci.. 2016, 132–133: 722

[3] Xue GL, Yilmaz E, Wang YD. Progress and prospects of mining with backfill in metal mines in China. Int. J. Miner. Metall. Mater.. 2023, 30(8): 1455

[4] Onopriyenko Z, Shon CS, Zhang DC, Kim JR. Agarwal RK. Compressive strength and expansion characteristics of BOFS-based geopolymer mortar under different curing regimes. Proceedings of the 8th International Conference on Manufacturing, Material and Metallurgical Engineering (ICMMME) 2024. 2025, Cham, Springer: 217

[5] Q. Zhang, B. Liu, Z. Sun, et al., Preparation and hydration process of copper slag-granulated blast furnace slag-cement composites, Constr. Build. Mater., 421(2024), art. No. 135717.

[6] Z.G. Liu and Z.X. Huang, Influence of steel slag–superfine blast furnace slag composite mineral admixture on the properties of mortar and concrete, Adv. Civ. Eng., 2021(2021), art. No. 9983019.

[7] L. Lang, M.Z. Zhu, and S.Y. Pu, Recycling engineering sediment waste as sustainable subgrade material using ground granulated blast-furnace slag, electrolytic manganese residue and cement, Environ. Technol. Innovation, 37(2025), art. No. 103969.

[8] W. Li, W.X. Wang, D.Q. Wu, S.S. Yang, H.S. Fang, and S.Y. Sun, Mechanochemical treatment with red mud added for heavy metals solidification in municipal solid waste incineration fly ash, J. Cleaner Prod., 398(2023), art. No. 136642.

[9] Z. Zhang, C.T. Zhao, Y. Rao, et al., Solidification/stabilization and risk assessment of heavy metals in municipal solid waste incineration fly ash: A review, Sci. Total Environ., 892(2023), art. No. 164451.

[10] B.Y. Tian, Y.C. Cui, J. Zhao, et al., Stepwise recovery of Ni, Cu, Zn, and Cr: A green route to resourceful disposal of electroplating sludge, J. Environ. Chem. Eng., 11(2023), No. 3, art. No. 109767.

[11] J.J. Sun, T.F. Zhang, L.Y. Dong, H. Zhu, P.L. Shen, and D.W. Liu, Eco-friendly recovery of copper from copper slag via magnetic separation followed by flotation: Experimental and mechanistic insights, J. Environ. Chem. Eng., 13(2025), No. 2, art. No. 115746.

[12] T. Kundu, S. Senapati, S.K. Das, S.I. Angadi, and S.S. Rath, A comprehensive review on the recovery of copper values from copper slag, Powder Technol., 426(2023), art. No. 118693.

[13] Chi XP, Liu HY, Xia J, et al. . Breaking the Fe₃O₄-wrapped copper microstructure to enhance copper–slag separation. Int. J. Miner. Metall. Mater.. 2024, 31(10): 2312

[14] Roy S, Datta A, Rehani S. Flotation of copper sulphide from copper smelter slag using multiple collectors and their mixtures. Int. J. Miner. Process.. 2015, 143: 43

[15] T.C. Phiri, P. Singh, and A.N. Nikoloski, The potential for copper slag waste as a resource for a circular economy: A review–Part I, Miner. Eng., 180(2022), art. No. 107474.

[16] Uzun Kart E, Yazğan Z, Gümüşsoy A. Investigation of iron selectivity behaviour of copper smelter slag flotation tailing with hematitization baking and base metals leaching methods. Physicochem. Probl. Miner. Process.. 2021, 57: 164

[17] M. Jamalimoghadam, A.H. Vakili, I. Keskin, A. Totonchi, and H. Bahmyari, Solidification and utilization of municipal solid waste incineration ashes: Advancements in alkali-activated materials and stabilization techniques, a review, J. Environ. Manage., 367(2024), art. No. 122014.

[18] Y. Xue and X.M. Liu, Detoxification, solidification and recycling of municipal solid waste incineration fly ash: A review, Chem. Eng. J., 420(2021), art. No. 130349.

[19] R. Karyappa, P.J. Ong, J. Bu, L.G. Tao, Q. Zhu, and C. Wang, Recent advances in immobilization of heavy metals from municipal solid waste incineration fly ash, Fuel, 381(2025), Part A, art. No. 133216.

[20] H.M. Wang, X.M. Liu, and Z.Q. Zhang, Approaches for electroplating sludge treatment and disposal technology: Reduction, pretreatment and reuse, J. Environ. Manage., 349(2024), art. No. 119535.

[21] J. Wang, R.Y. Zhou, J.X. Yu, et al., Sequential recovery of Cu(II), Cr(III), and Zn(II) from electroplating sludge leaching solution by an on-line biosorption method with dosage controlling, J. Cleaner Prod., 337(2022), art. No. 130427.

[22] Tiberg C, Sjöstedt C, Karlfeldt Fedje K. Speciation of Cu and Zn in bottom ash from solid waste incineration studied by XAS, XRD, and geochemical modelling. Waste Manage.. 2021, 119: 389

[23] S. Keber, T. Schirmer, T. Elwert, and D. Goldmann, Characterization of fine fractions from the processing of municipal solid waste incinerator bottom ashes for the potential recovery of valuable metals, Minerals, 10(2020), No. 10, art. No. 838.

[24] H. Zhang, D.Y. Lan, F. Lü, L.M. Shao, and P.J. He, Inhibition of chlorobenzenes formation by calcium oxide during solid waste incineration, J. Hazard. Mater., 400(2020), art. No. 123321.

[25] Liu YX, Lv MZ, Wu XY, et al. . Recovery of copper from electroplating sludge using integrated bipolar membrane electrodialysis and electrodeposition. J. Colloid Interface Sci.. 2023, 642: 29

[26] Q. Zhang, B. Liu, S.Y. Wang, et al., Effect of wet milling activation on mechanical properties and hydration process of cement composites with blast furnace slag, Constr. Build. Mater., 427(2024), art. No. 136298.

[27] He XY, Ma MY, Su Y, et al. . The effect of ultrahigh volume ultrafine blast furnace slag on the properties of cement pastes. Constr. Build. Mater.. 2018, 189: 438

[28] J.Q. Wei, B. Gencturk, A. Jain, and M. Hanifehzadeh, Mitigating alkali-silica reaction induced concrete degradation through cement substitution by metakaolin and bentonite, Appl. Clay Sci., 182(2019), art. No. 105257.

[29] Shao QY, Zheng KR, Zhou XJ, Zhou J, Zeng XH. Enhancement of nano-alumina on long-term strength of Portland cement and the relation to its influences on compositional and microstructural aspects. Cem. Concr. Compos.. 2019, 98: 39

[30] M.H. Liu, Y.D. Zhao, Z.Y. Yu, and Z.G. Cao, Binding of Cu(II) and Zn(II) in Portland cement immobilization systems: Effect of C–A–S–H composition, Cem. Concr. Compos., 131(2022), art. No. 104602.

[31] Maiti S, Malik J, Prasad B, Minocha AK. Solidification/stabilisation of Pb (II) and Cu (II) containing wastewater in cement matrix. Environ. Technol.. 2023, 44(19): 2876

[32] T. Gutsalenko, A. Bourdot, V. Montouillout, et al., Impact of trace metals Zn, Cu, Cd and Ni on the reactivity of OPC and GGBS-based hydraulic binders at early age for sediment stabilization, Constr. Build. Mater., 346(2022), art. No. 128406.

[33] Zhang Q, Liu B, Xiao K, Ekberg C, Zhang SG. Preparation and hydration of industrial solid waste–cement blends: A review. Int. J. Miner. Metall. Mater.. 2022, 29(12): 2106

[34] Abdel Gawwad HA, Abd El-Aleem S, Ouda AS. Preparation and characterization of one-part non-Portland cement. Ceram. Int.. 2016, 42(1): 220

[35] Mijarsh MJA, Megat Johari MA, Ahmad ZA. Effect of delay time and Na₂SiO₃ concentrations on compressive strength development of geopolymer mortar synthesized from TPOFA. Constr. Build. Mater.. 2015, 86: 64

[36] Gao X, Yu QL, Brouwers HJH. Properties of alkali activated slag–fly ash blends with limestone addition. Cem. Concr. Compos.. 2015, 59: 119

[37] Sakulich AR, Anderson E, Schauer CL, Barsoum MW. Influence of Si: Al ratio on the microstructural and mechanical properties of a fine-limestone aggregate alkali-activated slag concrete. Mater. Struct.. 2010, 43(7): 1025

[38] Kim MS, Jun YB, Lee CH, Oh JE. Use of CaO as an activator for producing a price-competitive non-cement structural binder using ground granulated blast furnace slag. Cem. Concr. Res.. 2013, 54: 208

[39] 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): 1251

[40] Chen QY, Hills CD, Tyrer M, Slipper I, Shen HG, Brough A. Characterisation of products of tricalcium silicate hydration in the presence of heavy metals. J. Hazard. Mater.. 2007, 147(3): 817

[41] Guo B, Liu B, Yang J, Zhang SG. The mechanisms of heavy metal immobilization by cementitious material treatments and thermal treatments: A review. J. Environ. Manage.. 2017, 193: 410

[42] X.W. Gu, H.Y. Wang, Z.G. Zhu, J.P. Liu, X.C. Xu, and Q. Wang, Synergistic effect and mechanism of lithium slag on mechanical properties and microstructure of steel slag–cement system, Constr. Build. Mater., 396(2023), art. No. 131768.

[43] Gineys N, Aouad G, Damidot D. Managing trace elements in Portland cement–Part I: Interactions between cement paste and heavy metals added during mixing as soluble salts. Cem. Concr. Compos.. 2010, 32(8): 563

[44] J.H. Ma, Q. Wang, H.Z. Jiao, et al., Solidification/stabilization and leaching behavior of heavy metals in low-binder cemented tailings backfill, Case Stud. Constr. Mater., 21(2024), art. No. e03934.

[45] H.M. Wang, Y.J. Ding, Y.B. Ren, Y.X. Zhou, and Y.X. Shi, Comparison of phosphogypsum–steel slag-based cement and Portland cement for stabilization of heavy metals in oil-based drillings cuttings, Sci. Total Environ., 946(2024), art. No. 174082.

RIGHTS & PERMISSIONS

University of Science and Technology Beijing