矿物掺合料对低热水泥水化动力学的影响

doi:10.16552/j.cnki.issn1001-1625.2026.0226

摘要/Abstract

摘要：

为揭示矿物掺合料对低热水泥水化动力学的影响规律，采用等温量热法测定了20%（质量分数，下同）、30%、40%掺量下单掺粉煤灰、单掺矿渣粉，以及粉煤灰-矿渣粉复掺的三种胶凝体系的水化放热速率和放热量。结合Krstulovic-Dabic水化动力学模型，定量分析了各水化阶段动力学参数的变化规律，并通过力学性能测试进行验证。结果表明，矿物掺合料的掺入降低了低热水泥的水化热和胶砂强度。Krstulovic-Dabic模型拟合显示，粉煤灰和矿渣粉对水化动力学的影响呈不同规律，单掺粉煤灰及粉煤灰-矿渣粉复掺时，扩散控制阶段速率常数 $K 3'$ 随掺量增加而降低，而单掺矿渣粉时该常数随掺量增加而升高。在矿物掺合料总掺量恒定的条件下，粉煤灰-矿渣粉复掺体系在各水化阶段的水化速率常数及转变水化程度均介于单掺粉煤灰与单掺矿渣粉体系之间，体现了二者在低热水泥中的协同作用。力学性能测试从宏观上验证了粉煤灰与矿渣粉复掺对强度发展的协同优化效应。综合考虑强度发展和水化温升控制，粉煤灰与矿渣粉复掺是实现低热水泥性能优化的平衡策略。

关键词: 低热水泥, 粉煤灰, 矿渣粉, 水化动力学模型, 水化反应速率, 力学性能

Abstract:

To reveal the influence of mineral admixtures on the hydration kinetics of low-heat Portland cement， the isothermal calorimetry was employed to measure the hydration heat evolution rate and cumulative heat of three cementitious systems with fly ash （FA）， ground granulated blast furnace slag （SL）， and their blend at mass replacement levels of 20%， 30%， and 40%， respectively. The Krstulovic-Dabic hydration kinetic model was used to quantitatively analyze the variations of kinetic parameters at different hydration stages， and the results were verified by mechanical property tests. The results show that the incorporation of mineral admixtures reduces the hydration heat and strength of low-heat Portland cement. The fitting results of the Krstulovic-Dabic model indicate that FA and SL exhibit different effects on the hydration kinetics. Specifically， the rate constant $K 3'$ in the diffusion-controlled stage decreases with increasing dosage when FA is added alone or when FA and SL are blended， but increases with increasing dosage when SL is added alone. Under a constant total dosage of mineral admixtures， the hydration rate constants and the degree of hydration at the transition points of the FA-SL blended system are intermediate between those of the single FA system and the single SL system， demonstrating a synergistic effect between the two admixtures in low-heat Portland cement. Mechanical property tests macroscopically verify the synergistic optimization effect of FA and SL blending on strength development. Considering both strength development and hydration temperature rise control， the combined use of FA and SL is a balanced strategy to optimize the performance of low-heat Portland cement.

Key words: low-heat Portland cement, fly ash, ground granulated blast furnace slag, hydration kinetic model, hydration reaction rate, mechanical property

中图分类号:

TQ172

周骏康, 李北星, 田继坤, 田沈华. 矿物掺合料对低热水泥水化动力学的影响[J]. 硅酸盐通报, 2026, 45(8): 2770-2781.

ZHOU Junkang, LI Beixing, TIAN Jikun, TIAN Shenhua. Effect of Mineral Admixtures on Hydration Kinetics of Low-Heat Portland Cement[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(8): 2770-2781.

图/表 14

表1 胶凝材料的主要化学成分

Table 1 Main chemical composition of cementitious materials

Material	Mass fraction/%
Material	CaO	SiO₂	Fe₂O₃	Al₂O₃	MgO	TiO₂	SO₃	K₂O	Na₂O	LOI
PLH	60.7	22.8	5.0	3.5	3.7	0.2	1.9	0.6	0.1	0.6
FA	8.4	48.8	6.1	24.3	1.4	1.0	1.2	1.9	1.1	3.4
SL	50.3	27.3	2.2	9.9	4.3	0.5	2.8	0.7	0.2	0.2

图1 低热水泥的XRD谱

Fig.1 XRD pattern of low-heat Portland Cement

表2 低热水泥的主要矿物组成

Table 2 Main mineral composition of low-heat Portland cement

Mineral composition	C₃S	C₂S	C₃A	C₄AF
Percentage/%	37.7^B（39.8^R）	36.9^B（43.0^R）	0.8^B（1.2^R）	15.2^B（16.0^R）

图2 胶凝材料的粒径分布曲线

Fig.2 Particle size distribution curves of cementitious materials

表3 试验配合比

Table 3 Mix proportions of test samples

Sample	Mass fraction/%			Water-to-binder ratio
Sample	PLH	FA	SL	Water-to-binder ratio
PLH100	100	0	0	0.4
FA20	80	20	0	0.4
FA30	70	30	0	0.4
FA40	60	40	0	0.4
SL20	80	0	20	0.4
SL30	70	0	30	0.4
SL40	60	0	40	0.4
FA10SL10	80	10	10	0.4
FA15SL15	70	15	15	0.4
FA20SL20	60	20	20	0.4

图3 单掺FA胶凝体系的水化放热速率和放热量

Fig.3 Hydration heat release rate and heat release of cementitious system with single FA addition

图4 单掺SL胶凝体系的水化放热速率和放热量

Fig.4 Hydration heat release rate and heat release of cementitious system with single SL addition

图5 复掺FA-SL胶凝体系的水化放热速率和放热量

Fig.5 Hydration heat release rate and heat release of cementitious system with combined FA and SL addition

表4 复合胶凝体系7 d水化放热量

Table 4 Hydration heat release at 7 d for composite cementitious system

Sample	Q₇/（J·g^-1）	Sample	Q₇/（J·g^-1）
PLH100	211.9	SL30	177.3
FA20	179.3	SL40	160.9
FA30	160.2	FA10SL10	191.1
FA40	131.1	FA15SL15	173.2
SL20	193.2	FA20SL20	156.5

表5 复合胶凝体系的总水化放热量

Table 5 Total hydration heat release of composite cementitious system

Sample	Q_max/（J·g^-1）	Sample	Q_max/（J·g^-1）
PLH100	249.7	SL30	208.3
FA20	215.0	SL40	187.5
FA30	194.3	FA10SL10	223.8
FA40	161.8	FA15SL15	204.9
SL20	228.4	FA20SL20	188.4

图6 基于Krstulovic-Dabic模型的复合胶凝体系水化反应速率曲线

Fig.6 Hydration reaction rate curves of various composite cementitious systems based on Krstulovic-Dabic model

表6 复合胶凝体系的水化动力学参数

Table 6 Hydration kinetic parameters of composite cementitious systems

Sample	n	K₁′	K₂′	K₃′
PLH100	2.715 85	0.042 25	0.010 48	0.001 19
FA20	2.809 48	0.043 52	0.010 12	0.001 06
FA30	2.814 21	0.044 09	0.009 42	0.000 95
FA40	2.273 11	0.036 45	0.008 13	0.000 76
SL20	2.805 99	0.044 23	0.010 03	0.001 11
SL30	2.670 34	0.045 60	0.010 23	0.001 15
SL40	2.390 43	0.049 02	0.010 08	0.001 21
FA10SL10	2.544 54	0.044 86	0.010 03	0.001 03
FA15SL15	2.605 14	0.044 47	0.009 85	0.000 99
FA20SL20	2.836 46	0.044 93	0.009 24	0.000 90

表7 复合胶凝体系水化阶段转变时的水化程度

Table 7 Hydration degree during transition of hydration stages in composite cementitious systems

Sample	α₁	α₂	α₂-α₁
PLH100	0.127	0.162	0.035
FA20	0.124	0.157	0.033
FA30	0.104	0.142	0.038
FA40	0.090	0.137	0.047
SL20	0.113	0.155	0.042
SL30	0.109	0.160	0.051
SL40	0.100	0.169	0.069
FA10SL10	0.114	0.146	0.032
FA15SL15	0.108	0.143	0.035
FA20SL20	0.097	0.138	0.041

图7 低热水泥复合胶凝体系胶砂抗压强度

Fig.7 Compressive strength of mortar in low-heat cement composite cementitious system

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