一步法制备单碳铝酸钙在不同环境下的稳定性

doi:10.16552/j.cnki.issn1001-1625.2025.1237

摘要/Abstract

摘要：

本文采用一步法工艺制备单碳铝酸钙，通过在80、90及100 ℃下使钙源、铝源与碳酸盐直接反应合成材料。利用X射线衍射、扫描电子显微镜及热重分析等手段，系统研究了单碳铝酸钙在不同酸碱度、温度条件及氯盐、硫酸盐及其混合溶液中的稳定性。结果表明，该材料在碱性环境（pH≥11）中展现出优异的化学稳定性，初始热分解温度为130 ℃，在450 ℃时完全分解为CaO和Al（OH）₃。在氯盐环境中，单碳铝酸钙极易固化环境中的游离Cl^-并反应生成弗里德尔盐，其固化速率与环境中的Cl^-浓度呈正相关性。在90 ℃下制备的单碳铝酸钙具有最高的Cl^-反应活性。在硫酸盐溶液中，单碳铝酸钙极易与 $S O 4 2 -$ 反应生成钙矾石。在CaCl₂-Na₂SO₄混合盐溶液中， $S O 4 2 -$ 相比于Cl^-具有更高的反应优先级，低浓度（0.2 mol/L）时，主要生成物为钙矾石与碳酸钙；高浓度（0.5、1.0 mol/L）时，生成物主要向二水石膏相转化。本研究为一步法制备单碳铝酸钙作为钢筋阻锈剂在实际工程中的应用可行性提供了新的思路和数据支持，证实其稳定性与制备温度、环境离子类型及浓度密切相关。

关键词: 一步法, 单碳铝酸钙, 酸碱稳定性, 氯离子阻锈, 阻锈剂

Abstract:

This study used a one-step method to prepare calcium carboaluminate （MC）， which involved the direct reaction of calcium sources， aluminum sources， and carbonate sources at temperatures of 80， 90， and 100 ℃. The stability of the prepared MC in solutions with different pH levels， temperatures， and concenrations of chloride salt， sulfate， and its mixed salt environments was investigated using X-ray diffraction， scanning electron microscopy， and thermogravimetric analysis. The results indicate that MC prepared via the one-step method exhibits excellent chemical stability in alkaline environments （pH≥11）. The initial decomposition temperature of MC is 130 ℃， and it completely decomposes into CaO and Al（OH）₃ at 450 ℃. In chloride solutions， MC readily immobilizes free Cl^- to form Friedel’s salt. The immobilization efficiency shows a positive correlation with the Cl^- concentration， and MC prepared at 90 ℃ demonstrates the highest Cl^- reactivity. In sulfate solutions， MC easily reacts with $S O 4 2 -$ to form ettringite. In CaCl₂-Na₂SO₄ mixed salt solution， $S O 4 2 -$ has a higher reaction priority than Cl^-. At a low concentration （0.2 mol/L） of the mixed salt solution， the main products are ettringite and calcium carbonate， while at high concentrations （0.5 and 1.0 mol/L）， the products shift predominantly toward calcium sulfate dihydrate phases. This study provides new insights and experimental support for the feasibility of using one-step MC as a corrosion inhibitor for steel reinforcement in practical engineering， confirming that its stability is closely related to the synthesis temperature， as well as the type and concentration of environmental ions.

Key words: one-step method, calcium carboaluminate, acid-alkali stability, chloride ion corrosion inhibition, corrosion inhibitor

中图分类号:

TU375

王英翔, 丁天慧, 冀志江, 解帅, 吴子豪, 马超, 余海燕. 一步法制备单碳铝酸钙在不同环境下的稳定性[J]. 硅酸盐通报, 2026, 45(6): 1968-1978.

WANG Yingxiang, DING Tianhui, JI Zhijiang, XIE Shuai, WU Zihao, MA Chao, YU Haiyan. Stability of Calcium Carboaluminate Prepared by One-Step Method Under Various Environmental Conditions[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(6): 1968-1978.

图/表 10

图1 一步法制备单碳铝酸钙的XRD谱

Fig.1 XRD patterns of MC prepared by one-step method

表1 溶液规格与浸泡时间

Table 1 Solution specification and soaking time

CaCl₂ concentration/（mol·L^-1）	Na₂SO₄ concentration/（mol·L^-1）	Solid-to-liquid ratio	Soaking time/d
0.2	—	1∶50	7
0.2	—	1∶50	14
0.2	—	1∶50	28
0.2	—	1∶50	56
0.5	—	1∶50	7
0.5	—	1∶50	14
0.5	—	1∶50	28
0.5	—	1∶50	56
1.0	—	1∶50	7
1.0	—	1∶50	14
1.0	—	1∶50	28
1.0	—	1∶50	56
—	0.2	1∶50	3
—	0.2	1∶50	7
—	0.2	1∶50	14
—	0.2	1∶50	28
—	0.5	1∶50	3
—	0.5	1∶50	7
—	0.5	1∶50	14
—	0.5	1∶50	28
—	1.0	1∶50	3
—	1.0	1∶50	7
—	1.0	1∶50	14
—	1.0	1∶50	28
0.1	0.1	1∶50	3
0.1	0.1	1∶50	28
0.1	0.1	1∶50	56
0.25	0.25	1∶50	3
0.25	0.25	1∶50	28
0.25	0.25	1∶50	56
0.5	0.5	1∶50	3
0.5	0.5	1∶50	28
0.5	0.5	1∶50	56

表2 单碳铝酸钙在不同初始pH值溶液中浸泡不同时间后的上清液pH值

Table 2 Supernatant pH value of MC soaked in solutions with different initial pH values for varying durations

Initial pH value		3.0	5.0	7.0	8.0	9.0	10.0	11.0	12.0
Supernatant pH value	3 d	11.0	12.0	13.0	12.5	13.0	12.0	12.0	12.0
	7 d	10.5	11.0	11.5	12.0	12.5	12.5	12.0	12.0
	14 d	10.5	11.0	10.5	11.5	12.0	12.5	12.5	12.0

图2 单碳铝酸钙在不同初始pH值溶液中浸泡不同时间后的XRD谱

Fig.2 XRD patterns of MC soaked in solutions with different initial pH values for varying durations

图3 不同温度处理后单碳铝酸钙的XRD谱和TG-DTG曲线

Fig.3 XRD patterns and TG-DTG curve of MC after treatment at different temperatures

图4 不同温度处理后的单碳铝酸钙的SEM照片

Fig.4 SEM images of MC after treatment at different temperatures

图5 单碳铝酸钙在不同浓度CaCl2溶液中浸泡不同时间的XRD谱

Fig.5 XRD patterns of MC soaked in CaCl2 solutions with different concentrations for varying durations

图6 单碳铝酸钙在不同浓度Na2SO4溶液中浸泡不同时间的XRD谱

Fig.6 XRD patterns of MC soaked in Na2SO4 solutions with different concentrations for varying durations

图7 90 ℃下制备的单碳铝酸钙在不同浓度Na2SO4溶液中浸泡3 d后的SEM照片

Fig.7 SEM images of MC prepared at 90 ℃ after soaked in Na2SO4 solutions with different concentrations for 3 d

图8 单碳铝酸钙在不同浓度CaCl2-Na2SO4混合盐溶液中浸泡不同时间的XRD谱

Fig.8 XRD patterns of MC soaked in CaCl2-Na2SO4 mixed salt solutions with different concentrations for varying durations

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