活化工艺对高岭土基低碳水泥性能的影响

doi:10.16552/j.cnki.issn1001-1625.2025.1116

摘要/Abstract

摘要：

本文利用活化高岭土、石灰石粉和少量水泥熟料制备低碳水泥，系统研究了机械化学法活化和热活化两种工艺对高岭土微观结构、低碳水泥性能及其水化产物组成与结构的影响规律。结果表明，经活化处理后，高岭土转变为无定形态。机械化学法活化对高岭土活性的提升效果优于热活化。当掺入质量分数为40%的机械化学法活化高岭土和质量分数20%的石灰石粉，并外掺质量分数5%的氢氧化钙时，所制备的低碳水泥3和28 d抗压强度分别为14.8和39.4 MPa，主要水化产物是水化硅酸钙（C-S-H）凝胶、钙矾石（AFt）和水化硫铝酸钙（AFm）。外掺氢氧化钙可进一步激发高岭土的火山灰反应，促进更多水化产物的生成，优化浆体的孔隙结构并提升力学性能。本研究探索了基于活化高岭土制备低碳水泥的技术路径，在60%熟料质量替代率下实现良好的性能发展，为低碳水泥的开发提供了有效路径。

关键词: 高岭土, 低碳水泥, 机械化学法活化, 热活化, 水化机理

Abstract:

This study utilized activated kaolin， limestone powder， and a small amount of cement clinker to prepare low-carbon cement. The effects of two activation methods， mechanochemical activation and thermal activation on the microstructure of kaolin， the properties of the low-carbon cement， and the composition and structure of its hydration products were systematically examined. The results indicate that kaolin transforms into an amorphous state after activation treatment. Mechanochemical activation is more effective in enhancing the reactivity of kaolin than thermal activation. When 40% （mass fraction） mechanochemically activated kaolin and 20% （mass fraction） limestone powder are incorporated， together with an external addition of 5% by mass of calcium hydroxide， the prepared low-carbon cement achieves compressive strengths of 14.8 MPa at 3 d and 39.4 MPa at 28 d. The main hydration products are calcium silicate hydrate （C-S-H） gel， ettringite （AFt）， and calcium sulfoaluminate hydrate （AFm）. Furthermore， the external addition of calcium hydroxide enhances the pozzolanic reaction of kaolin， increases the formation of hydration products， and improves pore structure of the paste and enhances its mechanical properties. This study explores a technical pathway for producing low-carbon cement with activated kaolin， achieving favorable performance development at a 60% clinker replacement rate by mass， thereby providing an effective approach for the development of low-carbon cement.

Key words: kaolin, low-carbon cement, mechanochemical activation, thermal activation, hydration mechanism

中图分类号:

TU525

廖云天, 彭文洁, 李博, 陈伟, 郑旭航. 活化工艺对高岭土基低碳水泥性能的影响[J]. 硅酸盐通报, 2026, 45(6): 1979-1987.

LIAO Yuntian, PENG Wenjie, LI Bo, CHEN Wei, ZHENG Xuhang. Effect of Activation Process on Properties of Kaolin-Based Low-Carbon Cement[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(6): 1979-1987.

图/表 14

图1 高岭土的XRD谱

Fig.1 XRD pattern of kaolin

表1 高岭土和水泥熟料的化学成分

Table 1 Chemical composition of kaolin and cement clinker

Material	Mass fraction/%
Material	CaO	Al₂O₃	MgO	SiO₂	P₂O₅	K₂O	SO₃	LOI	Other
Cement clinker	61.40	6.00	1.38	21.06	0.19	0.81	2.79	2.02	4.35
Kaolin	1.22	30.16	0.57	54.09	0.06	2.08	0.09	7.16	4.57

图2 原料高岭土与活化高岭土的粒度分布

Fig.2 Particle size distribution of raw kaolin and activated kaolin

表2 原料高岭土与活化高岭土粒度与比表面积分布

Table 2 Particle size and specific surface area distribution of raw kaolin and activated kaolin

Sample	D₅₀/μm	Specific surface area/（m²·g^-1）
Kaolin	5.302	1.130
CK	6.100	0.984
MK	1.897	3.160

图3 活化后高岭土的XRD谱与无定形含量

Fig.3 XRD patterns and amorphous content of activated kaolin

表3 低碳水泥浆体的配合比

Table 3 Mix proportion of low carbon cement paste

Sample	Mix proportion /（kg·m^-3）								W/B
Sample	Cement clinker	CK	MK	Limestone	Gypsum	Ca（OH）₂	Water	PCE	W/B
CAL-MK	35	0	40	20	5	5	40	0.7	0.4
CAL-MK-CH	35	0	40	20	5	0	40	0.7	0.4
CAL-CK	35	40	0	20	5	0	40	0.4	0.4
CAL-CK-CH	35	40	0	20	5	5	40	0.4	0.4

表4 活化高岭土对低碳水泥凝结时间和标准稠度用水量的影响

Table 4 Effect of activated kaolin on setting time and standard consistency of low carbon cement

Sample	Initial setting time/min	Final setting time/min	Standard consistency/%
CAL-CK	168	206	28.2
CAL-CK-CH	160	187	30.1
CAL-MK	194	236	35.6
CAL-MK-CH	184	223	38.4

图4 活化高岭土对低碳水泥抗压强度的影响

Fig.4 Effect of activated kaolin on compressive strength of low carbon cement

图5 28 d时样品的核磁共振弛豫分析

Fig.5 NMR relaxation analysis of samples at 28 d

表5 样品的孔隙率计算结果

Table 5 Porosity calculation results of samples

Sample	CAL-MK	CAL-MK-CH	CAL-CK	CAL-CK-CH
Porosity/%	18.22	13.98	21.66	16.31

图6 3、28 d龄期下低碳水泥水化产物的XRD谱

Fig.6 XRD patterns of hydration products of low carbon cement at 3 and 28 d

图7 低碳水泥水化产物各龄期的TG-DTG曲线

Fig.7 TG-DTG curves of hydration products of low carbon cement at different ages

图8 热重分析计算3、7和28 d时样品中CH的含量

Fig.8 CH content in samples determined by thermogravimetric analysis at 3， 7， and 28 d

图9 28 d龄期下水化产物的27Al和 29Si MAS NMR谱

Fig.9 27Al and 29Si MAS NMR spectra of hydration products at 28 d

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