钢渣-矿渣-水泥-脱硫石膏四元胶凝体系的水化硬化机理与性能优化研究

doi:10.16552/j.cnki.issn1001-1625.2025.1110

摘要/Abstract

摘要：

为实现大宗工业固废的高附加值资源化利用，本文构建了以钢渣（SS）-矿渣（GBFS）协同为核心，辅以水泥与脱硫石膏（DG）激发的四元胶凝体系。本研究通过系统的配合比设计与压汞法孔隙测试（MIP）、扫描电子显微镜（SEM）等微观表征手段，揭示了该四元胶凝体系在复合激发作用下的协同水化机制，阐明了水化产物钙矾石（AFt）与水化硅酸钙（C-S-H）凝胶交织生成、持续消耗Ca（OH）₂，从而驱动孔隙显著细化与结构致密化。研究确定了各关键组分的最优质量分数：矿渣40%、水泥10%、脱硫石膏8%~12%。水化动力学分析表明，体系呈典型的三段式放热特征，依次对应铝酸盐相反应、水泥主矿物水化及矿渣后期激发。其中石膏提供的硫酸盐与水泥提供的碱度共同激发了矿渣与钢渣的活性，促使水化产物AFt与C-S-H凝胶持续生成并大量消耗Ca（OH）₂。MIP与SEM测试结果进一步证实，四元胶凝体系在28 d龄期时实现了显著的微观结构致密化，有害孔（>50 nm）占比大幅降低，无害凝胶孔（<50 nm）占比从68%增至81%，C-S-H凝胶亦由交错分布发展为连续的蜂窝状结构，与AFt晶体紧密交织形成致密网络。本研究阐明了四元胶凝体系通过协同激发与孔隙细化实现强度发展的机理，为开发高性能低碳建筑材料提供了技术路径。

关键词: 钢渣, 多元胶凝体系, 力学性能, 微观结构, 孔隙结构特征

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

中图分类号:

U454

吴言坤, 陈健, 郝建帅, 房奎圳. 钢渣-矿渣-水泥-脱硫石膏四元胶凝体系的水化硬化机理与性能优化研究[J]. 硅酸盐通报, 2026, 45(6): 2052-2062.

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.

图/表 13

图1 原材料的物化性质测试结果

Fig.1 Physical and chemical property test results of raw materials

表1 原材料的主要化学成分

Table 1 Main chemical composition of raw materials

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

表2 四元胶凝体系的配合比设计

Table 2 Mix proportion design of quaternary cementitious system

No.	Mass fraction/%
No.	GBFS	Cement	DG	SS
1	0	10	12	78
2	10	10	12	68
7	20	10	12	58
4	30	10	12	48
5	40	10	12	38
10	50	10	12	28
11	60	10	12	18
12	10	0	12	78
13	10	5	12	73
14	10	10	12	68
15	10	15	12	63
16	10	20	12	58
17	20	0	12	68
18	20	5	12	63
19	20	10	12	58
20	20	15	12	53
21	20	20	12	48
22	10	10	0	80
23	10	10	4	76
24	10	10	8	72
25	10	10	12	68
26	10	10	16	64
27	10	10	20	60
28	20	10	0	70
29	20	10	4	66
30	20	10	8	62
31	20	10	12	68
32	20	10	16	64
33	20	10	20	50

图2 不同矿渣掺量下硬化浆体的抗压强度

Fig.2 Compressive strength of hardened pastes with different GBFS content

图3 不同水泥掺量下硬化浆体的抗压强度

Fig.3 Compressive strength of hardened pastes with different cement content

图4 不同脱硫石膏掺量下硬化浆体的抗压强度

Fig.4 Compressive strength of hardened pastes with different DG content

图5 四元胶凝体系的水化放热特征

Fig.5 Heat release characteristics during hydration of quaternary cementitious system

图6 硬化浆体的TG-DTG曲线

Fig.6 TG-DTG curves of hardened paste

表3 硬化浆体在不同温度区间的质量损失率

Table 3 Mass loss of hardened paste in different temperature ranges

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

图7 硬化浆体的孔隙结构特征

Fig.7 Pore structure characteristics of hardened paste

表4 硬化浆体中各级孔径占比

Table 4 Proportion of pore size at different levels in hardened paste

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

图8 钢渣-矿渣-水泥-脱硫石膏四元胶凝体系协同作用机制

Fig.8 Schematic diagram of synergistic mechanism in SS-GBFS-cement-DG quaternary cementitious system

图9 7与28 d龄期下硬化浆体的微观结构

Fig.9 Microstructure of hardened paste at curing age of 7 and 28 d

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