硅酸盐学报

分散纳米硅酸钙晶核对矿物掺合料早期火山灰反应活性调控机理

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缪剑雄 ¹ , 李炜 ² , 徐文琪 ² , 王荣杰 ² , 洪锦祥 ³

硅酸盐学报 | 研究论文 2026,54(8): 2730-2742

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硅酸盐学报 |研究论文 2026 , 54 (8) : 2730 -2742

分散纳米硅酸钙晶核对矿物掺合料早期火山灰反应活性调控机理

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缪剑雄¹, 李炜², 徐文琪², 王荣杰², 洪锦祥³

作者信息

^1．新加坡国立大学土木与环境工程学院，新加坡 117576

^2．扬州大学土木与交通学院，中国江苏扬州 225127

^3．重大基础设施工程材料全国重点实验室，江苏苏博特新材料股份有限公司，中国南京 211103

通讯作者:

洪锦祥（1976—），男，博士，教授级高级工程师。

作者简介:

缪剑雄（1992—），男，博士。

Regulating Mechanism of Early Pozzolanic Reactivity of Mineral Admixtures by Nano-Sized Calcium-Silicate-Hydrated Nuclei

Jianxiong MIAO¹, Wei LI², Wenqi XU², Rongjie WANG², Jinxiang HONG³

Affiliations

^1.Department of Civil and Environmental Engineering, National University of Singapore 117576, Singapore

^2.School of Civil Engineering and Transportation, Yangzhou University, Yangzhou 225127, Jiangsu, China

^3.State Key Laboratory of Engineering Materials for Major Infrastructure, Sobute New Materials Co . Ltd, Nanjing 211103, China

Corresponding Author:

{HONG} Jinxiang (1976-), male, Ph.D., Professor-level Senior Engineer. E-mail: hjxsbt@126.com

MIAO Jianxiong (1992—), male, Ph.D. E-mail: j_miao01@nus.edu.sg

出版时间: 2026-06-03 doi: 10.14062/j.issn.0454-5648.20250643

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摘要

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为了加快粉煤灰（FA）与偏高岭土（MK）等矿物掺合料的早期火山灰反应进程，采用分散纳米硅酸钙晶核（C-S-H-PCE）调控其在饱和Ca（OH）₂溶液中的火山灰反应活性。通过电导率、电感耦合等离子体-发射光谱（ICP-OES）及pH值探究矿物掺合料的离子溶出过程；通过化学结合水、傅里叶变换红外光谱（FTIR）及氮吸附（BET）研究矿物掺合料的火山灰反应产物；通过抗压强度反映纳米C-S-H-PCE对水泥水化和矿物掺合料火山灰反应的调控效果，并揭示火山灰反应活性的调控机理。随着纳米C-S-H-PCE的增加，MK和FA体系的电导率和pH值均随时间延长而快速下降，Si—O和Al—O键加快断裂；反应24 h后对应的化学结合水含量逐渐增加；硅氧四面体的聚合度不断提高；试样的氮气吸附量、比表面积及抗压强度逐渐增大。上述结果说明纳米C-S-H-PCE加速了矿物掺和料的离子溶出和火山灰反应产物的形成。其调控矿物掺合料火山灰反应活性的机理为：纳米C-S-H-PCE降低了水化硅酸钙（C-S-H）凝胶成核位垒，促进了矿物掺合料溶出的离子在纳米C-S-H-PCE表面成核结晶，快速形成水化产物，并进一步促进了矿物掺合料的离子溶出，从而提高了矿物掺合料的早期火山灰反应活性。

关键词

矿物掺合料 / 火山灰活性 / 纳米硅酸钙晶核

Abstract

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Introduction

To accelerate the progress of pozzolanic reaction of the mineral admixtures, such as fly ash (FA) and metakaolin (MK), dispersed nano-sized hydrated calcium silicate-polycarboxylate superplasticizer (C-S-H-PCE) were employed to regulate their early-age pozzolanic reactivity in saturated Ca(OH)₂ solution. The ion dissolution process of the mineral admixtures was investigated through conductivity determination, inductively coupled plasma optical emission spectroscopy (ICP), and pH value measurement. The pozzolanic reaction products of the mineral admixtures were studied by chemically bound water content analysis, Fourier transform infrared spectroscopy (FTIR), and Brunner-Emmett-Teller (BET) based on nitrogen adsorption. The enhancement effect of nano-sized C-S-H-PCE on the cement-mineral mortar was analyzed by compressive strength, and the regulatory mechanism underlying the pozzolanic reactivity was discussed.

Methods

As a kind of commercial product, nano-sized C-S-H-PCE was provided by Jiangsu Sobute New Materials Co., Ltd., China. The synthetic C-S-H was dispersed via the adsorption of the comb-like PCE on its surface, and then the final C-S-H-PCE with the particle sizes of 50-100 nm was obtained via ultrasonic treatment. The mass concentration of nano-sized C-S-H-PCE was 12%. The conductivity, inductively coupled plasma optical emission spectroscopy (ICP), pH value measurement, chemical bound water analysis, Fourier transform infrared spectroscopy (FTIR) and N₂ adsorption were applied to characterize the samples in this investigation.

Results and discussion

As the dosage of nano-sized C-S-H-PCE increasing, the conductivity of MK and FA systems decreased, indicating that the concentration of free ions in the system gradually decreased, and the conductivity of MK system decreased more significantly in relative to the FA system with the addition of nano-sized C-S-H-PCE. The pH values of both MK and FA systems rapidly decrease with time, and the corresponding OH^- consumption increases with the addition of nano-sized C-S-H-PCE after 24 h reaction. The results of conductivity and pH value indicated that nano-sized C-S-H-PCE promoted ion dissolution from mineral admixtures and thus enhancing the pozzolanic activity.

As the dosage of nano C-S-H-PCE increases, the chemically bound water content corresponding to both MK and FA systems gradually increases, and the chemically bound water content corresponding to MK system was significantly higher than that of corresponding to FA system. The FTIR spectra indicated that the polymerization degree of silicon oxygen tetrahedra in mineral admixtures MK and FA in saturated Ca (OH)₂ solution continuously increased with the addition of nano-sized C-S-H-PCE, and the corresponding Si—O bond stretching vibration peak number and integral area of MK system were higher. The results of nitrogen adsorption showed that the nitrogen adsorption capacity and specific surface area of MK and FA samples increase with the increase of nano-sized C-S-H-PCE content, promoting the progress of pozzolanic reaction.

The mechanism of nano C-S-H-PCE regulating the pozzolanic reactivity of mineral admixtures was that nano-sized C-S-H-PCE reduced the free energy ∆G required for the nucleation barrier and nucleation of C-S-H gel, that is, the ions dissolved from mineral admixtures can nucleate and crystallize on the surface of nano-sized C-S-H-PCE at a lower saturation concentration, thus quickly forming hydration products. The formation of hydration products on the surface of nano-sized C-S-H-PCE reduced the ion concentration in the solution, leading to an increase in ion unsaturation and further promoting the ion dissolution from mineral admixtures, thereby accelerating the pozzolanic reactivity of mineral admixtures.

Conclusions

The results showed that the conductivity and pH values of the MK and FA systems both could decrease as the amount of nano-sized C-S-H-PCE increased, accompanying with an accelerated breakage of Si—O and Al—O bonds. After 24 h reaction, the chemically bound water content gradually increased, while the polymerization degree of silicate tetrahedrons continuously increased. In addition, the nitrogen adsorption capacity and specific surface area of the samples gradually expanded. The aforementioned results indicated that nano-sized C-S-H-PCE accelerated the ion dissolution from mineral admixtures and the formation of pozzolanic reaction products. Nano-sized C-S-H-PCE reduced the nucleation energy barrier of C-S-H gel, facilitating the nucleation and crystallization of ions dissolved from mineral admixtures on the surface of nano-sized C-S-H-PCE, thereby accelerating the formation of hydration products. This process could promote the dissolution of ions from mineral admixtures, ultimately enhancing their pozzolanic reactivity.

Key words

mineral admixtures / pozzolanic reactivity / nano hydrated calcium silicate seeds

引用本文

缪剑雄, 李炜, 徐文琪, 王荣杰, 洪锦祥. 分散纳米硅酸钙晶核对矿物掺合料早期火山灰反应活性调控机理. 硅酸盐学报, 2026 , 54 (8) : 2730 -2742 . DOI: 10.14062/j.issn.0454-5648.20250643

Jianxiong MIAO, Wei LI, Wenqi XU, Rongjie WANG, Jinxiang HONG. Regulating Mechanism of Early Pozzolanic Reactivity of Mineral Admixtures by Nano-Sized Calcium-Silicate-Hydrated Nuclei[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (8) : 2730 -2742 . DOI: 10.14062/j.issn.0454-5648.20250643

基金

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国家自然科学基金(52578330)
重大基础设施工程材料全国重点实验室开放基金(2022CEM001)

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2026年第54卷第8期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250643

接收时间：2025-08-31
首发时间：2026-10-22
出版时间：2026-06-03

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出版历史

收稿日期：2025-08-31
修回日期：2026-01-05

基金

国家自然科学基金(52578330)

重大基础设施工程材料全国重点实验室开放基金(2022CEM001)

作者信息

^1．新加坡国立大学土木与环境工程学院，新加坡 117576

^2．扬州大学土木与交通学院，中国江苏扬州 225127

^3．重大基础设施工程材料全国重点实验室，江苏苏博特新材料股份有限公司，中国南京 211103

通讯作者:

洪锦祥（1976—），男，博士，教授级高级工程师。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250643

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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