钙矾石主导的泛碱抑制新机制

doi:10.16552/j.cnki.issn1001-1625.2025.0772

摘要/Abstract

摘要：

水泥基装饰材料的泛碱问题影响其色泽稳定性，传统方法存在效率低、损害强度等局限。本研究首次提出并验证了一个新假设：通过外源Ca²⁺调控，可将钙矾石（AFt）从泛碱促进相转变为高效抑碱相。以硫铝酸盐水泥（SAC）为基体，外掺CaCl₂作为钙源，利用XRD、SEM、TG-DSC、MIP等多尺度表征手段，系统研究了AFt的抑碱机制。结果表明：10%（质量分数）CaCl₂掺量的SAC试样光密度值（OD）相较于未掺CaCl₂试样降低39.2%，证明外掺CaCl₂可显著降低泛碱程度。核心机制在于：1）AFt晶体结构（3CaO·Al₂O₃·3CaSO₄·32H₂O）固定游离Ca²⁺，减少可迁移离子源；2）AFt晶体能束缚大量结晶水，降低离子迁移载体；3）大量AFt交错生长形成致密骨架，总孔隙率低至2.78%，阻断离子迁移通道。三者协同实现“固定离子源、束缚迁移载体、阻断迁移通道”抑碱效应。本研究揭示了AFt的主动抑碱新功能，为设计长效抗泛碱水泥基装饰材料提供了新思路。

关键词: 氯化钙, 硝酸钙, 硫铝酸盐水泥, 钙矾石, 泛碱抑制, 离子固定, 通道阻断

Abstract:

Efflorescence poses a critical challenge to the stability of cement-based decorative materials. Traditional methods have limitations such as low efficiency and strength damage. This study proposed and verified a new hypothesis： through the regulation of exogenous Ca²⁺， ettringite （AFt） can be transformed from an efflorescence promoting phase to an efficient efflorescence inhibition phase. Using sulphoaluminate cement （SAC） as the matrix and adding CaCl₂ as calcium sources， the efflorescence inhibition mechanism of AFt was systematically studied by multi-scale characterization methods such as XRD， SEM， TG-DSC and MIP. The results show that the optical density （OD） value of the SAC sample with 10% CaCl₂ （mass fraction） admixture is reduced by 39.2% compared to the sample without CaCl₂， indicating that it can significantly reduce the degree of efflorescence. The core mechanism lies in： 1） AFt crystal structure （3CaO·Al₂O₃·3CaSO₄·32H₂O） fixes free Ca²⁺， reducing the source of migratory ions. 2） AFt crystals can bind a large amount of crystalline water， reducing the carrier of ion migration. 3） A large amount of AFt interlaced growth forms a dense skeletonon， total porosity as low as 2.78%， blocking the ion migration channels. The three work together to achieve the "fixed ion source， bound migration carrier， and blocking migration channel" alkali inhibition effect. This study reveals the new function of AFt in active alkali inhibition and provides a new idea for the design of long-lasting anti-alkali efflorescence cement-based decorative materials.

Key words: CaCl₂, Ca（NO₃）₂, sulphoaluminate cement, ettringite, efflorescence inhibition, ion immobilization, channel blocking

中图分类号:

TU528

李朗, 张玉玮, 高育慧, 刘悦, 程艳, 郑卫国. 钙矾石主导的泛碱抑制新机制[J]. 硅酸盐通报, 2026, 45(2): 482-489.

LI Lang, ZHANG Yuwei, GAO Yuhui, LIU Yue, CHENG Yan, ZHENG Weiguo. A New Mechanism for Inhibiting Alkali Efflorescence Dominated by Ettringite[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(2): 482-489.

图/表 12

表1 不同CaCl2掺量的SAC净浆配方

Table 1 Formulations of SAC cement paste with different CaCl2 dosages

Sample No.	Mass ratio
Sample No.	SAC	Water	Iron black	CaCl₂	Optical density
1#	1	0.33	0.17	0	39.72
2#	1	0.33	0.17	0.10	24.17
3#	1	0.33	0.17	0.20	17.75
4#	1	0.33	0	0	—
5#	1	0.33	0	0.05	—
6#	1	0.33	0	0.10	—
7#	1	0.33	0	0.20	—

表2 不同CaCl2掺量的SAC砂浆配方

Table 2 Formulations of SAC mortar with different CaCl2 dosages

Sample No.	Mass ratio				Compressive strength/MPa
Sample No.	SAC	Water	Sand	CaCl₂	1 d	3 d	28 d
8#	1	0.5	3	0.10	42.3	49.4	57.6
9#	1	0.5	3	0	32.6	41.5	65.1

表3 对比试验配方

Table 3 Formulation of comparative test

Sample No.	Mass ratio
Sample No.	SAC	Water	Iron black	Ca（NO₃）₂	NaCl	Optical density
10#	1	0.27	0	0	0	—
11#	1	0.27	0	0.2	0	—
12#	1	0.27	0.2	0.2	0	20.45
13#	1	0.27	0	0	0.2	—
14#	1	0.27	0.2	0	0.2	36.39

图1 SAC的XRD谱

Fig.1 XRD pattern of SAC

图2 不同CaCl2掺量下SAC净浆试样的泛碱程度

Fig.2 Efflorescence degree of SAC paste samples with different CaCl2 dosages

图3 不同CaCl2掺量下SAC净浆试样的XRD谱

Fig.3 XRD patterns of SAC paste with different CaCl2 dosages

表4 不同CaCl2掺杂量下SAC的Rietveld精修定量相分析结果

Table 4 Results of Rietveld refinement quantitative phase analysis of SAC with different CaCl2 dosages

Sample No.	Mass fraction/%							Refined reliable factor R_wp/%
Sample No.	AFt	CaSO₄	β-C₂S	SiO₂	CaCO₃	C₃S	Ca₄Al₂O₆CO₃·11H₂O	Refined reliable factor R_wp/%
5#	1.4	17.4	26.7	28.3	22.4	3.8	—	7.7
6#	10.5	21.0	8.4	26.8	27.7	1.8	3.8	9.4
7#	13.2	15.5	16.6	25.2	20.6	4.9	4.0	5.5

图4 SAC净浆试样水化产物的SEM照片

Fig.4 SEM images of hydration products of SAC paste samples

图5 掺10%CaCl2 SAC净浆试样的TG-DSC曲线

Fig.5 TG-DSC curves of SAC paste with 10% CaCl2

图6 掺Ca（NO3）2和NaCl SAC净浆试样的泛碱程度

Fig.6 Efflorescence degree of SAC paste samples withCa（NO3）2 and NaCl dosages

图7 掺0%和10% CaCl2 SAC净浆试样的孔隙结构参数

Fig.7 Pore structure parameters of SAC paste samples with 0% and 10% CaCl2

图8 掺10% Ca（NO3）2 SAC净浆试件的孔隙分布参数

Fig.8 Pore distribution parameters of SAC paste sample with 10% Ca（NO3）2

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