天然石膏掺量对高铝精炼渣复合胶凝材料水化及性能的影响

doi:10.16552/j.cnki.issn1001-1625.2025.1291

摘要/Abstract

摘要：

高铝精炼渣是粗钢二次精炼过程排放的固体废弃物，其组成、结构及特性与铝酸盐水泥近似，具备作为低等级铝酸盐水泥潜质。本文采用高铝精炼渣和天然石膏配制了复合胶凝材料，研究了天然石膏掺量对高铝精炼渣复合胶凝材料水化及性能的影响。结果表明，天然石膏的掺入可降低复合胶凝材料标准稠度用水量，使含40%~60%（质量分数，下同）天然石膏的复合胶凝材料标准稠度用水量降低至约27.6%。复合胶凝材料凝结硬化相比纯高铝精炼渣更快，含10%~40%天然石膏的复合胶凝材料的初凝时间为18~24 min，终凝时间为64~71 min；进一步提高天然石膏含量，复合胶凝材料凝结时间延长。随着天然石膏掺量增大，复合胶凝材料胶砂抗压强度呈先上升后下降趋势，含50%天然石膏的复合胶凝材料胶砂28 d抗压强度最高，达到29.8 MPa，但低于纯高铝精炼渣胶砂；合适含量的天然石膏可克服高铝精炼渣胶砂抗折强度倒缩问题，含40%和50%天然石膏的复合胶凝材料胶砂抗折强度无倒缩，28 d抗折强度可约达6.0 MPa，高于纯高铝精炼渣胶砂。复合胶凝材料胶砂28 d干燥收缩率随着天然石膏含量增加呈先提高后降低趋势，含10%天然石膏的复合胶凝材料胶砂28 d干燥收缩率最高可达0.073 2%；天然石膏含量30%~60%的复合胶凝材料胶砂干燥收缩率则均低于纯高铝精炼渣胶砂。天然石膏对高铝精炼渣水化影响较大，天然石膏与高铝精炼渣中铝酸钙及其水化产物优先反应生成钙矾石（AFt），减少了亚稳态铝酸钙水化产物含量，使复合胶凝材料水化体系结构更为稳定。

关键词: 高铝精炼渣, 天然石膏, 复合胶凝材料, 水化特性, 水化产物, 干燥收缩

Abstract:

High-alumina ladle slag is a solid waste generated during the secondary refining process of crude steel. Its composition， structure， and properties are similar to those of aluminate cement， suggesting its potential use as a low-grade aluminate cement. In this study， a compound cementitious material was prepared using high-alumina ladle slag and natural gypsum， and the effect of natural gypsum content on its hydration and performances was investigated. The results show that the incorporation of natural gypsum reduces the water requirement for normal consistency of the compound cementitious material. Specifically， for compound cementitious material containing 40% to 60% （mass fraction， same below） natural gypsum， the water requirement for normal consistency decreases to approximately 27.6%. The setting and hardening of the compound cementitious material are accelerated compared to pure high-alumina ladle slag. For compound cementitious material with 10% to 40% natural gypsum， the initial setting time ranges from 18 min to 24 min， and the final setting time from 64 min to 71 min. Further increasing the natural gypsum content prolongs the setting time. As the natural gypsum content increases， the compressive strength of the compound cementitious material mortars increases first and then decreases. The compound cementitious material mortar containing 50% natural gypsum exhibits the highest 28 d compressive strength， reaching 29.8 MPa， although it remains lower than that of the pure high-alumina ladle slag mortar. An appropriate amount of natural gypsum mitigates the flexural strength regression observed in high-alumina ladle slag mortars. The compound cementitious material mortars with 40% and 50% natural gypsum show no flexural strength regression， achieving a 28 d flexural strength of approximately 6.0 MPa， which is higher than that of the pure high-alumina ladle slag mortar. The 28 d drying shrinkage of the compound cementitious material mortars increases first and then decreases with increasing natural gypsum content. The compound cementitious material mortar with 10% natural gypsum exhibits the highest 28 d drying shrinkage rate of 0.073 2%. In contrast， the compound cementitious material mortars with 30% to 60% natural gypsum show lower drying shrinkage than the pure high-alumina ladle slag mortar. Natural gypsum significantly influences the hydration of high-alumina ladle slag. It preferentially reacts with calcium aluminate in the high-alumina ladle slag and its hydration products to form ettringite （AFt）， reducing the content of metastable hydration phases and leading to a more stable hydration structure in the compound cementitious material system.

Key words: high-alumina ladle slag, natural gypsum, compound cementitious material, hydration characteristic, hydration product, drying shrinkage

中图分类号:

TU52

张柳, 龚明, 丁盼, 周飞, 杨奉源, 卢忠远, 李军. 天然石膏掺量对高铝精炼渣复合胶凝材料水化及性能的影响[J]. 硅酸盐通报, 2026, 45(7): 2389-2396.

ZHANG Liu, GONG Ming, DING Pan, ZHOU Fei, YANG Fengyuan, LU Zhongyuan, LI Jun. Effect of Natural Gypsum Content on Hydration and Performances of High-Alumina Ladle Slag Based Compound Cementitious Materials[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(7): 2389-2396.

图/表 11

表1 原材料的主要化学成分

Table 1 Main chemical composition of raw materials

Material	Mass fraction/%
Material	MgO	Al₂O₃	SiO₂	SO₃	CaO	Fe₂O₃	K₂O	Na₂O	Loss
High-alumina ladle slag	0.68	50.35	7.67	0.67	29.19	1.62	0.28	0.09	7.40
Natural gypsum	3.13	1.05	3.74	42.65	41.09	0.38	0.27	0.07	7.28

图1 高铝精炼渣的XRD谱

Fig.1 XRD pattern of high-alumina ladle slag

图2 原材料的粒径分布

Fig.2 Particle size distribution of raw materials

图3 天然石膏的XRD谱

Fig.3 XRD pattern of natural gypsum

表2 复合胶凝材料配合比

Table 2 Mix proportion of compound cementitious materials

Sample No.	Mass fraction/%
Sample No.	High-alumina ladle slag	Natural gypsum
LF0	100	0
LF1	90	10
LF2	80	20
LF3	70	30
LF4	60	40
LF5	50	50
LF6	40	60

表3 复合胶凝材料标准稠度用水量、凝结时间和安定性

Table 3 Water requirement for normal consistency， setting time， and soundness of compound cementitious materials

Sample No.	Water requirement for normal consistency/%	Setting time/min		Soundness
Sample No.	Water requirement for normal consistency/%	Initial	Final	Soundness
LF0	29.8	60	255	Qualified
LF1	29.3	22	67	Qualified
LF2	28.8	24	64	Qualified
LF3	28.2	22	71	Qualified
LF4	27.6	18	67	Qualified
LF5	27.7	29	88	Qualified
LF6	27.6	29	111	Qualified

图4 复合胶凝材料胶砂力学性能

Fig.4 Mechanical properties of compound cementitious material mortars

表4 复合胶凝材料胶砂干燥收缩率

Table 4 Drying shrinkage rate of compound cementitious material mortars

Sample No.	LF0	LF1	LF2	LF3	LF4	LF5	LF6
Drying shrinkage rate/%	0.052 4	0.073 2	0.059 2	0.048 8	0.022 0	0.022 0	0.002 4

图5 高铝精炼渣-天然石膏复合胶凝材料水化热

Fig.5 Heat of hydration of high-alumina ladle slag-natural gypsum compound cementitious materials

图6 水化产物XRD谱

Fig.6 XRD patterns of hydration products

图7 水化产物TG-DTG分析

Fig.7 TG-DTG analysis of hydration products

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