赤泥与再生微粉协同调控磷石膏-矿渣基全固废胶凝材料的耐久性能与微观结构研究

doi:10.16552/j.cnki.issn1001-1625.2025.1258

摘要/Abstract

摘要：

本文采用磷石膏、矿渣、再生微粉、赤泥和生石灰制备磷石膏-矿渣基全固废胶凝材料，研究再生微粉和赤泥对胶凝材料力学性能、耐久性能和微观结构的影响及协同效应。结果表明，再生微粉和赤泥的掺入显著增强了胶凝材料的力学性能和耐久性能，复掺10%（质量分数）再生微粉与10%（质量分数）赤泥的试样性能相对较优，28 d抗压强度和抗折强度分别为43.2和7.4 MPa，相较磷石膏-矿渣基体系分别提升57.1%和57.4%，非稳态氯离子迁移系数和干燥收缩分别降低42.5%和43.6%，硫酸盐耐蚀系数由73.6%提高至85.6%。再生微粉兼具物理填充与化学活性，为水化反应提供成核位点和活性组分；同时，赤泥能提高体系碱度并引入额外的硅铝质矿物相，加速前驱体的溶解与聚合，并激发再生微粉潜在的火山灰活性。再生微粉与赤泥协同促进了水化硅（铝）酸钙凝胶的形成，并保持稳定的钙矾石产物数量，从而优化水化产物组成，实现孔隙结构致密化和宏观性能的全面提升。本研究有望为绿色胶凝材料的制备和固体废弃物的资源化利用提供技术借鉴。

关键词: 磷石膏, 全固废胶凝材料, 赤泥, 再生微粉, 耐久性能, 微观结构

Abstract:

In this paper， phosphogypsum-slag-based all-solid-waste cementitious material was developed using phosphogypsum （PG）， slag， recycled cement powder （RCP）， red mud （RM）， and quicklime. The individual and synergistic effects of RCP and RM on mechanical properties， durability， and microstructure were characterized. The results indicate that the incorporation of RCP and RM significantly enhances the mechanical properties and durability of the cementitious material. The specimen with 10% （mass fraction） RCP and 10% （mass fraction） RM exhibits relatively superior performance. In comparison to the PG-slag-based system， the 28 d compressive strength and flexural strength increase by 57.1% and 57.4%， reaching 43.2 and 7.4 MPa， respectively. Simultaneously， the non-steady-state chloride migration coefficient and drying shrinkage decrease by 42.5% and 43.6%， while the sulfate corrosion resistance coefficient is elevated from 73.6% to 85.6%. RCP serves as a physical filler and provides chemical activity， offering nucleation site and active component for the hydration reaction. Additionally， RM raises the alkalinity of the system and introduces extra aluminosilicate minerals， which accelerates the dissolution and polymerization of precursors， and stimulates the potential pozzolanic activity of RCP. RCP and RM synergistically promote the formation of calcium aluminosilicate hydrate gel and maintain a considerable amount of ettringite， consequently optimizing the composition of hydration products， ultimately achieving a comprehensive improvement in pore structure densification and macroscopic performance. This study is expected to provide a technical reference for the development of green cementitious materials and the resource utilization of solid waste.

Key words: phosphogypsum, all-solid-waste cementitious material, red mud, recycled cement powder, durability, microstructure

中图分类号:

TU528

刘鑫, 李明阳, 张细和, 蓝少丁, 高旭. 赤泥与再生微粉协同调控磷石膏-矿渣基全固废胶凝材料的耐久性能与微观结构研究[J]. 硅酸盐通报, 2026, 45(7): 2478-2490.

LIU Xin, LI Mingyang, ZHANG Xihe, LAN Shaoding, GAO Xu. Durability and Microstructure of Phosphogypsum-Slag-Based All-Solid-Waste Cementitious Material Regulated by Red Mud and Recycled Cement Powder[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(7): 2478-2490.

图/表 14

图1 胶凝材料的XRD谱

Fig.1 XRD patterns of cementitious material

表1 胶凝材料的主要化学组成

Table 1 Main chemical composition of cementitious material

Material	Mass fraction/%
Material	CaO	SiO₂	Al₂O₃	SO₃	Na₂O	K₂O	Fe₂O₃	P₂O₅	MgO	LOI
GGBS	33.80	31.00	12.30	2.23	0.59	0.73	1.01	0.03	7.96	2.37
PG	40.78	5.60	0.36	51.88	—	0.09	0.28	0.71	0.06	0.12
RCP	47.53	23.53	8.98	2.41	0.61	0.81	2.02	0.06	1.65	10.12
RM	15.37	21.20	23.42	1.89	9.02	1.86	19.04	0.32	1.64	2.56

图2 胶凝材料的粒径分布

Fig.2 Particle size distribution of cementitious material

表2 磷石膏-矿渣基全固废胶凝材料配合比

Table 2 Mix proportion of phosphogypsum-slag-based all-solid-waste cementitious material

Sample No.	Binder composition/%				Lime content/%	Water-binder ratio	Binder-sand ratio （mortar）	Concrete composition/（kg·m^-3）
Sample No.	PG	GGBS	RCP	RM	Lime content/%	Water-binder ratio	Binder-sand ratio （mortar）	Binder	Fine aggregate	Coarse aggregate
Ref	50	50	—	—	4	0.45	1∶3	450	720	1 080
RP1	40	50	10	—	4	0.45	1∶3	450	720	1 080
RP2	30	50	20	—	4	0.45	1∶3	450	720	1 080
RM1	40	50	—	10	4	0.45	1∶3	450	720	1 080
RM2	30	50	—	20	4	0.45	1∶3	450	720	1 080
RPM1	40	50	5	5	4	0.45	1∶3	450	720	1 080
RPM2	30	50	10	10	4	0.45	1∶3	450	720	1 080

图3 新拌砂浆的工作性能

Fig.3 Workability of fresh mortar

图4 磷石膏-矿渣基全固废砂浆的力学性能

Fig.4 Mechanical properties of phosphogypsum-slag-based all-solid-waste mortar

图5 磷石膏-矿渣基全固废砂浆的抗压强度与抗折强度相关性分析

Fig.5 Relation between compressive strength and flexural strength of phosphogypsum-slag-based all-solid-waste mortar

图6 磷石膏-矿渣基全固废混凝土的抗氯离子渗透性能

Fig.6 Chloride penetration resistance of phosphogypsum-slag-based all-solid-waste concrete

图7 磷石膏-矿渣基全固废砂浆试样的干燥收缩性能

Fig.7 Drying shrinkage property of phosphogypsum-slag-based all-solid-waste mortar

图8 各组磷石膏-矿渣基全固废混凝土试样的硫酸盐侵蚀试验结果

Fig.8 Sulfate attack test results of each phosphogypsum-slag-based solid waste concrete specimens

图9 试样的XRD谱

Fig.9 XRD patterns of specimens

图10 试样的TG-DTG曲线

Fig.10 TG-DTG curves of specimens

图11 净浆试样的FTIR谱

Fig.11 FTIR spectra of paste specimens

图12 不同全固废体系的SEM照片和EDS测试结果

Fig.12 SEM images and EDS results of different all-solid waste systems

参考文献 30

[1]	CHEN L， LUAN X Y， HAN F， et al. Life cycle environmental and economic assessment of phosphogypsum utilization in China［J］. Resources， Conservation and Recycling， 2025， 212： 107938.
[2]	QU F L， ZHANG Y Y， LI M D， et al. Resource recycling of industrial waste phosphogypsum in cementitious materials： pretreatment， properties， and applications［J］. Journal of Environmental Management， 2025， 376： 124291. DOI URL
[3]	XIA Y， WANG L， ZHAO R L， et al. Industrial gypsum-driven in-situ ettringite formation for enhanced all-solid-waste alkali-activated materials［J］. Composites Part B： Engineering， 2026， 309： 113077.
[4]	SONG Y P， ZHANG J X， WU H S， et al. All-solid-waste alkali-activated materials： a critical review of multi-waste synergy， heavy metal stabilization， and sustainable engineering applications［J］. Journal of Environmental Chemical Engineering， 2025， 13（6）： 119204. DOI URL
[5]	MURALI G， WONG L S， ABDULKADIR I， et al. Sustainable transformation of waste phosphogypsum into geopolymer concrete： comprehensive review on strength， durability， and microstructural characteristics［J］. Journal of Building Engineering， 2025， 111： 113597. DOI URL
[6]	WANG Y G， LIANG Y， SHANG W Z， et al. Revealing the evolution of mechanical performance， environmental performance and microstructure in red mud cementitious materials［J］. Journal of Building Engineering， 2025， 110： 113083. DOI URL
[7]	MA T L， DONG Y B， LIN H. Red mud-based all-solid-waste cementitious materials： a review of synthesis， heavy metals immobilization and feasibility application［J］. Journal of Environmental Chemical Engineering， 2025， 13（5）： 117999. DOI URL
[8]	XU J， XU F， WU Y， et al. Investigation on properties and mechanism of non-calcined Bayer red mud-phosphogypsum cementitious binder［J］. Journal of Cleaner Production， 2022， 379： 134661. DOI URL
[9]	SUN C B， CHEN X， LU L Z， et al. Synergistic recycling of ground granulated blast furnace slag-red mud-phosphogypsum for developing low-carbon composite cementitious material： performance characterization and process optimization［J］. Construction and Building Materials， 2025， 473： 141025. DOI URL
[10]	LI Z， BIAN Y D， ZHAO J H， et al. Recycled concrete fine powder （RFP） as cement partial replacement： influences on the physical properties， hydration characteristics， and microstructure of blended cement［J］. Journal of Building Engineering， 2022， 62： 105326. DOI URL
[11]	WANG C， YU Q J， ZHAN B G， et al. Activity quantification and assessment of recycled concrete powder based on the contributions of the dilution effect， physical effect and chemical effect［J］. Journal of Cleaner Production， 2024， 442： 140918. DOI URL
[12]	AQUINO ROCHA J H， TOLEDO FILHO R D. The utilization of recycled concrete powder as supplementary cementitious material in cement-based materials： a systematic literature review［J］. Journal of Building Engineering， 2023， 76： 107319. DOI URL
[13]	ZHAI W Q， SUN R M， XIE Y D， et al. Thermal-activated recycled cement powder synergized with fly ash as supplementary cementitious in Portland cement： strength， microstructure and environmental benefits［J］. Construction and Building Materials， 2025， 474： 141018. DOI URL
[14]	MA Z M， LIU X， HU R H， et al. Using recycled aggregate and powder from high-strength mortar waste for durable cement-based materials： microstructure and chloride transport［J］. Journal of Cleaner Production， 2023， 417： 137998. DOI URL
[15]	LIN R S， HUANG G， MA F Y， et al. Investigation of phosphogypsum-based cementitious materials： the effect of lime modification［J］. Developments in the Built Environment， 2024， 18： 100477. DOI URL
[16]	TANG L， HE Z Y， XIA Y H， et al. Development of phosphogypsum-based full-solid-waste cementitious materials： mechanical properties， hydration mechanisms， and pollutant stabilization mechanisms［J］. Journal of Building Engineering， 2025， 110： 113100. DOI URL
[17]	REN Z S， WANG L， WANG H， et al. Carbonation behavior of solidified/stabilized cadmium in phosphogypsum slag-based cementitious materials［J］. Construction and Building Materials， 2024， 437： 136848. DOI URL
[18]	WANG Y F， LIU P， KONG D W， et al. Investigation of the properties and microscopic mechanism of red mud-phosphogypsum-based composite cementitious materials［J］. Journal of Building Engineering， 2025， 101： 111962. DOI URL
[19]	HOU S D， HU R H， XU L， et al. Understanding the chloride migration in recycled powder concrete： effects of recycled powder type， replacement rate and substitution pattern［J］. Construction and Building Materials， 2024， 436： 136825. DOI URL
[20]	CHEN K L， LIN W T， LIU Q， et al. Micro-characterizations and geopolymerization mechanism of ternary cementless composite with reactive ultra-fine fly ash， red mud and recycled powder［J］. Construction and Building Materials， 2022， 343： 128091. DOI URL
[21]	SUN H， XIE M X， JIA L T， et al. Development of low-carbon binders from ground granulated blast furnace slag activated by red mud， phosphogypsum， and calcium carbide slag： mechanical and hydration properties［J］. Journal of Building Engineering， 2025， 111： 113229. DOI URL
[22]	PEREZ-CORTES P， ESCALANTE-GARCIA J I. Gel composition and molecular structure of alkali-activated metakaolin-limestone cements［J］. Cement and Concrete Research， 2020， 137： 106211. DOI URL
[23]	LAN S D， ELMAASRAWY M， CHEN J Y， et al. Microstructure and macro performance characterization of low-slag alkali-activated UHPC based on simplex centroid design method［J］. Construction and Building Materials， 2025， 494： 143386. DOI URL
[24]	MA B H， LI Y Q， LAN T， et al. Hydration mechanism and mechanical properties of slag-phosphogypsum solid waste-based cementitious composite incorporated silica fume［J］. Construction and Building Materials， 2025， 485： 141923. DOI URL
[25]	MA Y W， GONG J H， OUYANG X W， et al. Roles of recycled concrete powder on the properties of alkali-activated slag： reaction products and microstructure development［J］. Composites Part B： Engineering， 2025， 301： 112493.
[26]	TAO H Y， TANG J Y， ZHANG C J， et al. Synergistic utilization of recycle cement powder and glass powder to prepare low-carbon and environmentally friendly mortar： mechanical properties， microstructure， and environmental assessment［J］. Materials Today Sustainability， 2025， 32： 101228. DOI URL
[27]	ZHANG W， XUE C H， ZHAO D Z， et al. Chloride leaching and strength development of alkali-activated materials with municipal solid waste incineration fly ash， red mud and carbide slag［J］. Journal of Environmental Management， 2025， 392： 126766. DOI URL
[28]	FANG Y， ZHANG L， HU T， et al. A comprehensive review on shrinkage behaviors of alkali-activated metakaolin-blast furnace slag cementitious materials： shrinkage mechanism， properties and mitigate strategies［J］. Case Studies in Construction Materials， 2025， 22： e04391.
[29]	GAO Q， LI X G， SHI X D， et al. Clean and high-value recycling approach for waste concrete powder： mechano-chemical activation of pozzolanic activity［J］. Powder Technology， 2025， 458： 120988. DOI URL
[30]	MAO X Q， QU W J， ZHU P， et al. Influence of recycled powder on chloride penetration resistance of green reactive powder concrete［J］. Construction and Building Materials， 2020， 251： 119049. DOI URL