硅酸盐学报

矿渣、电石渣协同制备赤泥-Ⅱ级粉煤灰地聚物力学与微观特性

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聂庆科 ¹^,² , 李华伟 ¹^,³ , 杨海朋 ¹^,² , 张日华 ¹^,³ , 孔德朋 ⁴ , 张海清 ¹^,⁵

硅酸盐学报 | 低碳水泥与固废资源化利用专题—研究论文 2026,54(5): 1524-1535

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硅酸盐学报 |低碳水泥与固废资源化利用专题—研究论文 2026 , 54 (5) : 1524 -1535

矿渣、电石渣协同制备赤泥-Ⅱ级粉煤灰地聚物力学与微观特性

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聂庆科¹^,², 李华伟¹^,³, 杨海朋¹^,², 张日华¹^,³, 孔德朋⁴, 张海清¹^,⁵

作者信息

^1．中冀建勘集团有限公司，石家庄 050227

^2．河北省岩土技术创新中心，石家庄 050227

^3．河北省工业固体废弃物综合利用重点实验室，石家庄 050227

^4．北京交通大学土木建筑工程学院，北京 100044

^5．河北大学建筑工程学院，河北保定 071002

通讯作者:

张海清（1984—），男，博士，副教授。

作者简介:

聂庆科（1965—），男，教授级高级工程师。

Mechanical and Microstructural Characteristics of Red Mud-class II Fly Ash Based Geopolymer Synergistically Prepared with Ground Granulated Blast Furnace Slag and Calcium Carbide Slag

Qingke NIE¹^,², Huawei LI¹^,³, Haipeng YANG¹^,², Rihua ZHANG¹^,³, Depeng KONG⁴, Haiqing ZHANG¹^,⁵

Affiliations

^1.China Hebei Construction & Geotechnical Investigation Group Ltd., Shijiazhuang 050227, China

^2.Geotechnical Engineering Technology Research Center of Hebei Province, Shijiazhuang 050227, China

^3.Key Laboratory for Industrial Solid Waste Comprehensive Utilization of Hebei Province, Shijiazhuang 050227, China

^4.School of Civil Engineering, Beijing Jiaotong University, Beijing 100044, China

^5.College of Civil Engineering and Architecture, Hebei University, Baoding 071002, Hebei, China

Corresponding Author:

ZHANG Haiqing (1984-), male, Ph.D., Associate Professor. E-mail: haiqzhang@hbu.edu.cn

NIE Qingke (1965-), male, Professor. E-mail: nieqingke@126.com

出版时间: 2025-08-12 doi: 10.14062/j.issn.0454-5648.20250109

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摘要

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赤泥（RM）、粉煤灰（FA）、矿渣（GGBS）和电石渣（CS）是造成严重环境问题的工业废物，制备地质聚合物新型胶凝材料是实现其资源化综合利用的有效途径之一。通过抗压强度试验、X射线衍射（XRD）、傅立叶变换红外光谱（FTIR）和扫描电子显微镜-能谱仪（SEM-EDS）研究了GGBS和CS复掺条件下赤泥-Ⅱ级粉煤灰地聚物（RFG）强度形成与微观反应机理。结果表明：1）单掺GGBS相比单掺CS更有利于RFG的强度形成。2）复掺GGBS和CS条件下，主要生成了水化铝酸钙（C-A-H）、水化硅酸钙（C-S-H）、水化硅酸铝钙（C-A-S-H）单聚体胶凝，以及钙矾石、聚铝硅酸盐硅氧体［（—Si—O—Al—Si—O—）_n］和水铝钙石，是构成RFG强度的主要成分。3）Ca、Si或Al的含量对地聚物强度形成具有重要影响，Ca含量偏高时，主要产物为C-S-H；Si或Al含量较高时，Si、Al等成分首先在碱性环境中溶解，形成C-S-H、C-A-H、C-A-S-H等凝胶，凝胶在强碱环境下再进行溶解和缩聚形成Si—O—Al—O和Si—O—Al—Si—O等长链多聚体，随时间排除水分，凝结聚合生成地质聚合物。

关键词

地质聚合物 / 强度 / 反应机理 / 赤泥 / 粉煤灰

Abstract

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Introduction

Red mud (RM) as a highly alkaline solid waste generated during alumina production presents significant environmental challenges due to its massive annual output and stockpiling, including land occupation and pollution. The utilization of RM in combination with other solid wastes or minerals to produce geopolymer cementitious materials becomes one of the effective approaches for its resource recovery. However, Bayer-processed RM exhibits a low Si/Al molar ratio and a poor reactivity, making it difficult to form a stable aluminosilicate polymer structure. Most RM-based geopolymers require mechanical/thermal activation pretreatment or high-temperature curing to enhance early strength. The existing studies typically involve either low RM incorporation ratios or result in a low geopolymer strength at high RM dosages. Based on previous research and the concept of multi-source solid waste synergy, this study was to introduce highly reactive ground granulated blast-furnace slag (GGBS) and calcium-rich carbide slag (CS) into an RM-Class II fly ash (FA) geopolymer system. The influence of GGBS and CS composite dosages on the mechanical properties of the geopolymer was investigated. Furthermore, the microstructure of the geopolymer was analyzed from multiple perspectives to elucidate the synergistic reaction mechanism and strength development under the co-incorporation of GGBS and CS.

Methods

In this study, RM, FA, GGBS, and CS were used as raw materials at a RM/FA mass ratio of 1.0/1.0. A mixed alkaline activator solution consisting of NaOH solution (NH) and water glass (WG) was used at an NH/WG mass ratio of 1.0/2.5. The NaOH solution had a molarity of 10 mol/L, and the liquid-to-solid ratio (L/S) was 0.65. Different dosages of GGBS and CS were used as the experimental variables.

The RM, FA, GGBS, and CS were manually mixed for 30 s, followed by blending the solid powder mixture with alkaline activator in a cement paste mixer for 3 min. The resulting slurry was then cast into triple molds with internal dimensions of 70.7 mm × 70.7 mm × 70.7 mm. The specimens were cured at 20 ℃ and 95% relative humidity for 24 h before demolding, after they continued to cure under standard conditions.

The compressive strength tests were conducted at different curing ages of 7, 14, 28, 45 d, and 60 d. The collected fragments taken from the center of the specimens were stored in vials and immersed in anhydrous ethanol to halt further reaction. The chemical composition, microstructure, and mineral phases on the geopolymer's strength were determined by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS). Prior to testing, the samples were dried at 60 ℃ for 24 h and ground for subsequent characterization.

Results and discussion

All the specimens exhibit a strength development trend with increasing curing age. Among them, the geopolymer RFGC-1 with CS as sole additive shows the lowest strength, reaching only 1.8 MPa at 60 d. In contrast, RFGC-5 with GGBS as sole additive demonstrates the highest strength among the five formulations, achieving 11.6 MPa at 60 d, indicating that GGBS is more effective than CS in enhancing the strength of RM-Class II FA-based geopolymers.

For the samples RFGC-2, RFGC-3, and RFGC-4 incorporated both GGBS and CS, the 60-d compressive strengths are 5.8, 8.8 MPa, and 6.5 MPa, respectively. The strength initially increases and then decreases with increasing GGBS content and decreasing CS content, indicating that the relative proportions of GGBS and CS must be carefully controlled to optimize the geopolymer strength. At a total additive content of ≤12%, the RM-FA geopolymer with GGBS alone exhibits a superior strength, compared to those with CS alone or GGBS/CS combinations.

The microstructural characterization reveasl that, in addition to the original mineral phases (i.e., hematite (Fe₂O₃) and quartz (SiO₂)), the primary cementitious products in the geopolymers include calcium aluminate hydrate (C-A-H), calcium silicate hydrate (C-S-H), calcium aluminosilicate hydrate (C-A-S-H), ettringite (AFt), aluminosilicate oligomers (—Si—O—Al—Si—O—)_n, and hydrotalcite. For RFGC-1 (CS only), the microstructure is relatively loose, with the limited formation of amorphous C-S-H and insufficient conversion into C-A-S-H or (—Si—O—Al—Si—O—)_n, resulting in a low strength. As the GGBS content increases and CS decreases, intermediate products (C-S-H, C-A-H) further react to form C-A-S-H, AFt, and (—Si—O—Al—Si—O—)_n. The gel phases envelop adjacent particles, forming interconnected coatings and enhancing the aluminosilicate and SiO₄ tetrahedral networks, thereby strengthening the geopolymer matrix.

Conclusions

The incorporation of GGBS alone was more conducive to strength development in the RM-Class II FA based geopolymers, compared to CS alone. In the case of co-incorporating GGBS and CS, the primary cementitious products included C-A-H), C-S-H, C-A-S-H monomers, as well as ettringite, aluminosilicate oligomers (—Si—O—Al—Si—O—)_n, and hydrotalcite, which collectively contributed to the strength of the geopolymers. The addition of GGBS and CS to the RM-Class II FA system modulated the contents of Ca, Si, and Al in the composite system, significantly influencing geopolymer strength development. At a higher content of Ca, C-S-H became the dominant product. Conversely, at a higher content of Si or Al, these components first dissolved in the alkaline environment to form gels such as C-S-H, C-A-H, and C-A-S-H. These gels subsequently underwent dissolution and polycondensation under strong alkaline conditions, forming long-chain polymers like Si—O—Al—O and Si—O—Al—Si—O. For overtime, water was expelled, leading to coagulation and polymerization, ultimately resulting in the formation of dense and stable geopolymer structures.

Key words

geopolymer / strength / reaction mechanism / red mud / fly ash

引用本文

聂庆科, 李华伟, 杨海朋, 张日华, 孔德朋, 张海清. 矿渣、电石渣协同制备赤泥-Ⅱ级粉煤灰地聚物力学与微观特性. 硅酸盐学报, 2026 , 54 (5) : 1524 -1535 . DOI: 10.14062/j.issn.0454-5648.20250109

Qingke NIE, Huawei LI, Haipeng YANG, Rihua ZHANG, Depeng KONG, Haiqing ZHANG. Mechanical and Microstructural Characteristics of Red Mud-class II Fly Ash Based Geopolymer Synergistically Prepared with Ground Granulated Blast Furnace Slag and Calcium Carbide Slag[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (5) : 1524 -1535 . DOI: 10.14062/j.issn.0454-5648.20250109

基金

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中央引导地方科技发展资金项目(246Z3804G)
河北省重点研发计划项目(19211505D)
河北省博士后科研项目择优资助计划(B2020005008)

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2026年第54卷第5期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250109

接收时间：2025-02-20
首发时间：2026-09-20
出版时间：2025-08-12

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收稿日期：2025-02-20
修回日期：2025-03-14

基金

中央引导地方科技发展资金项目(246Z3804G)

河北省重点研发计划项目(19211505D)

河北省博士后科研项目择优资助计划(B2020005008)

作者信息

^1．中冀建勘集团有限公司，石家庄 050227

^2．河北省岩土技术创新中心，石家庄 050227

^3．河北省工业固体废弃物综合利用重点实验室，石家庄 050227

^4．北京交通大学土木建筑工程学院，北京 100044

^5．河北大学建筑工程学院，河北保定 071002

通讯作者:

张海清（1984—），男，博士，副教授。

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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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