Hydration and Hardening Mechanism and Property Optimization of SS-GBFS-Cement-DG Quaternary Cementitious System

doi:10.16552/j.cnki.issn1001-1625.2025.1110

Abstract

Abstract:

To achieve the high-value resource utilization of bulk industrial solid wastes， this study constructed a quaternary cementitious system centered on the synergy between steel slag （SS） and granulated blast furnace slag （GBFS）， activated by cement and desulfurization gypsum （DG）. The synergistic hydration mechanism of the quaternary cementitious system under composite activation was revealed through systematic mixture proportion design and micro-characterization techniques such as mercury intrusion porosimetry （MIP） and scanning electron microscopy （SEM）. The interwoven formation of hydration products ettringite （AFt） and calcium silicate hydrate （C-S-H） gel continuously consumed Ca（OH）₂， thereby driving significant pore refinement and microstructural densification， was elucidated. The optimal mass fractions for each key component is 40% GBFS， 10% cement， and 8%~12% DG. Hydration kinetics analysis indicates that the system exhibits typical three-stage exothermic characteristics： aluminate phase reaction， silicate hydration of cement， and a pronounced secondary reaction stage attributable to the alkaline-sulfate activation of GBFS. The sulfate from DG and alkalinity from cement jointly activated the GBFS and SS， promoting continuous formation of AFt and C-S-H gel while extensively consuming Ca（OH）₂. MIP and SEM results further demonstrate significant microstructural densification of the quaternary cementitious system at 28 d： the proportion of harmful pores （>50 nm） decreases markedly， while that of harmless gel pores （<50 nm） increases from 68% to 81%. The C-S-H gel develops from an interlaced distribution into a continuous honeycomb-like structure， tightly interwoven with AFt crystals to form a dense network. This research clarifies the underlying strength development mechanism of the quaternary binder system， driven by synergistic activation and pore structure refinement. It offers a theoretical foundation and technical route for the development of high-performance， low-carbon construction materials.

Key words: steel slag, multi-component cementitious system, mechanical property, microstructure, pore structure characteristic

CLC Number:

U454

WU Yankun, CHEN Jian, HAO Jianshuai, FANG Kuizhen. Hydration and Hardening Mechanism and Property Optimization of SS-GBFS-Cement-DG Quaternary Cementitious System[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(6): 2052-2062.

Figures/Tables 13

References 28

[1]	陈　明，赵大鹏，张敬祥，等. 同步注浆材料中盾构渣土的再利用及性能试验［J］. 现代隧道技术， 2025， 62（4）： 248-258.
	CHEN M， ZHAO D P， ZHANG J X， et al. The reuse and performance testing of shield tunnel mucks in synchronous grouting materials［J］. Modern Tunnelling Technology， 2025， 62（4）： 248-258 （in Chinese）.
[2]	HAO J S， LIN Z J， WANG Q， et al. Utilization of tunnel waste slurry and steel slag for preparation of backfill grouting materials： properties and hydration behavior［J］. Cleaner Materials， 2025， 18： 100341. DOI URL
[3]	赫明胜，秦庆金，高　慧，等. 减水剂对镁渣-粉煤灰基流态固化土流变性及强度的影响［J］. 硅酸盐通报， 2025， 44（7）： 2710-2719. DOI
	HE M S， QIN Q J， GAO H， et al. Effects of water-reducing agents on rheological property and strength of magnesium slag-fly ash-based flowable solidified soil［J］. Bulletin of the Chinese Ceramic Society， 2025， 44（7）： 2710-2719 （in Chinese）. DOI
[4]	FANG K Z， LIN Z， WANG Q， et al. Magnesium slag-fly ash-cement binders for flowable solidified soil： hydration behavior， rheological control and strength performance［J］. Journal of Building Engineering， 2025， 112： 113987. DOI URL
[5]	HAO J S， ZHOU Z H， ZHANG L F. Optimisation and mechanism of steel slag-cement based grouting for water ingress control［J］. Case Studies in Construction Materials， 2025， 23： e05211.
[6]	ZHAO J H， YAN P Y， WANG D M. Research on mineral characteristics of converter steel slag and its comprehensive utilization of internal and external recycle［J］. Journal of Cleaner Production， 2017， 156： 50-61. DOI URL
[7]	郝建帅，周子涵，陈忠辉，等. 钢渣在矿山充填胶凝材料中的水化硬化性能研究现状分析［J］. 矿业科学学报， 2024， 9（4）： 573-585.
	HAO J S， ZHOU Z H， CHEN Z H， et al. Review of hydration and hardening properties of steel slag in mine filling cementitious materials［J］. Journal of Mining Science and Technology， 2024， 9（4）： 573-585 （in Chinese）.
[8]	ZHUANG S Y， WANG Q. Inhibition mechanisms of steel slag on the early-age hydration of cement［J］. Cement and Concrete Research， 2021， 140： 106283. DOI URL
[9]	NUNES V A， BORGES P H R. Recent advances in the reuse of steel slags and future perspectives as binder and aggregate for alkali-activated materials［J］. Construction and Building Materials， 2021， 281： 122605. DOI URL
[10]	DU H H， XU D， LI X， et al. Application of molten iron desulfurization slag to replace steel slag as an alkaline component in solid waste-based cementitious materials［J］. Journal of Cleaner Production， 2022， 377： 134353. DOI URL
[11]	霍彬彬，张亚梅，王栋民，等. 甲酸干法化学改性钢渣粉及其浆体性能研究［J］. 矿业科学学报， 2022， 7（5）： 522-528.
	HUO B B， ZHANG Y M， WANG D M， et al. Investigating the performance of dry chemically modified steel slag powder and pastes by formic acid［J］. Journal of Mining Science and Technology， 2022， 7（5）： 522-528 （in Chinese）.
[12]	HUO B B， LI B L， HUANG S Y， et al. Hydration and soundness properties of phosphoric acid modified steel slag powder［J］. Construction and Building Materials， 2020， 254： 119319. DOI URL
[13]	LIU Y， ZHANG Z Q， HOU G H， et al. Preparation of sustainable and green cement-based composite binders with high-volume steel slag powder and ultrafine blast furnace slag powder［J］. Journal of Cleaner Production， 2021， 289： 125133. DOI URL
[14]	WANG J， LIU X M， ZHANG Z Q， et al. Synergistic utilization， critical mechanisms， and environmental suitability of bauxite residue （red mud） based multi-solid wastes cementitious materials and special concrete［J］. Journal of Environmental Management， 2024， 361： 121255. DOI URL
[15]	HAO J S， ZHOU Z H， CHEN Z H， et al. Mechanical performance and damage mechanisms of steel slag-cement pasted backfill under high-temperature cured and cyclic static loading for deep-mining applications［J］. Journal of Materials Research and Technology， 2025， 35： 5698-5716. DOI URL
[16]	ZHANG M G， LI K Q， NI W， et al. Preparation of mine backfilling from steel slag-based non-clinker combined with ultra-fine tailing［J］. Construction and Building Materials， 2022， 320： 126248. DOI URL
[17]	HAO X S， LIU X M， ZHANG Z Q， et al. In-depth insight into the cementitious synergistic effect of steel slag and red mud on the properties of composite cementitious materials［J］. Journal of Building Engineering， 2022， 52： 104449. DOI URL
[18]	YANG Z X， XIONG X L， CHEN S H， et al. Effect of fineness on the hydration and microstructure of cementitious materials with high-volume steel slag and blast furnace slag［J］. Journal of Building Engineering， 2023， 72： 106682. DOI URL
[19]	刘满超. 矿山充填胶凝材料的研究及应用［D］. 石家庄：河北科技大学， 2018.
	LIU M C. Research and application of backfilling cementing material for mine industry［D］. Shijiazhuang： Hebei University of Science and Technology， 2018 （in Chinese）.
[20]	阎爱云，倪　文，黄晓燕，等. 膏体充填用矿渣：钢渣基胶结剂协同固化Pb²⁺ ［J］. 工程科学学报， 2016， 38（7）： 899-905.
	YAN A Y， NI W， HUANG X Y， et al. Solidification/stabilization of Pb²⁺ within a blast furnace slag-steel slag based cementing agent for paste backfilling［J］. Chinese Journal of Engineering， 2016， 38（7）： 899-905 （in Chinese）.
[21]	WANG X， NI W， LI J J， et al. Carbonation of steel slag and gypsum for building materials and associated reaction mechanisms［J］. Cement and Concrete Research， 2019， 125： 105893. DOI URL
[22]	HAO J S， ZHOU Z H， CHEN Z H， et al. Synergistic mechanisms of steel slag， granulated blast furnace slag， and desulfurization gypsum in high-content steel slag-based cementitious backfill materials［J］. International Journal of Mining Science and Technology， 2025， 35（6）： 1005-1018. DOI URL
[23]	JOSEPH S， SKIBSTED J， CIZER Ö. A quantitative study of the C₃A hydration［J］. Cement and Concrete Research， 2019， 115： 145-159. DOI URL
[24]	WANG Q， YAN P Y， HAN S. The influence of steel slag on the hydration of cement during the hydration process of complex binder［J］. Science China Technological Sciences， 2011， 54（2）： 388-394. DOI URL
[25]	庄诗雨. 钢渣延缓水泥早期水化的机理及应用［D］. 北京：清华大学， 2022.
	ZHUANG S Y. Mechanism and application of steel slag delaying early hydration of cement［D］. Beijing： Tsinghua University， 2022 （in Chinese）.
[26]	YAO G， LIU Q， WANG J X， et al. Effect of mechanical grinding on pozzolanic activity and hydration properties of siliceous gold ore tailings［J］. Journal of Cleaner Production， 2019， 217： 12-21. DOI URL
[27]	ZHAO J H， WANG D M， YAN P Y. Design and experimental study of a ternary blended cement containing high volume steel slag and blast-furnace slag based on Fuller distribution model［J］. Construction and Building Materials， 2017， 140： 248-256. DOI URL
[28]	HAO J S， ZHOU Z H， CHEN Z H， et al. Utilization of high-volume steel slag in sustainable low carbon cementitious composites for mine backfill： synergistic mechanisms and environmental benefits［J］. Process Safety and Environmental Protection， 2025， 202： 107689. DOI URL

Raw material	Mass fraction/%
Raw material	CaO	Fe₂O₃	SiO₂	Al₂O₃	MgO	MnO	SO₃	P₂O₅	TiO₂	Na₂O
SS	43.45	27.17	12.47	4.38	4.09	3.73	1.45	1.16	0.96	0.31
GBFS	54.17	0.58	22.86	10.40	6.15	0.62	1.81	0.58	1.72	0.43
DG	54.36	0.41	1.76	0.59	0.72	0.01	41.19	0.12	0.04	0.40
Cement	65.79	4.64	16.77	6.80	1.69	0.09	2.71	0.13	0.72	0.22

Raw material	Mass fraction/%
Raw material	CaO	Fe₂O₃	SiO₂	Al₂O₃	MgO	MnO	SO₃	P₂O₅	TiO₂	Na₂O
SS	43.45	27.17	12.47	4.38	4.09	3.73	1.45	1.16	0.96	0.31
GBFS	54.17	0.58	22.86	10.40	6.15	0.62	1.81	0.58	1.72	0.43
DG	54.36	0.41	1.76	0.59	0.72	0.01	41.19	0.12	0.04	0.40
Cement	65.79	4.64	16.77	6.80	1.69	0.09	2.71	0.13	0.72	0.22

Curing age/d	Mass loss/%
Curing age/d	50~260 ℃	415~530 ℃	590~760 ℃	50~1 000 ℃
28	12.7	0.4	3.8	23.0
7	9.8	0.6	2.6	18.5

Curing age/d	Mass loss/%
Curing age/d	50~260 ℃	415~530 ℃	590~760 ℃	50~1 000 ℃
28	12.7	0.4	3.8	23.0
7	9.8	0.6	2.6	18.5

Curing age/d	Volume fraction/%
Curing age/d	<4.5 nm	4.5~<50 nm	50~100 nm	>100 nm
7	5	63	17	15
28	6	75	8	11