铁相含量对铁铝酸盐水泥抗侵蚀性能的影响机理研究

doi:10.16552/j.cnki.issn1001-1625.2026.0143

摘要/Abstract

摘要：

铁铝酸盐水泥因烧成温度低、碳排放少，且具备优异的抗侵蚀性能，在海洋工程中具有重要应用前景。本文制备四种不同铁相含量的水泥试样，对其开展氯盐溶液和硫酸盐溶液浸泡试验，结合XRD、TG、MIP、SEM等分析手段，系统研究了铁相含量对水泥试样抗侵蚀性能的影响机理。研究结果表明，随着铁相含量的增加，水泥试样的氯离子扩散系数降低、结合氯离子能力增强，抗硫酸盐侵蚀性能显著提升。当主要矿物无水硫铝酸钙、硅酸二钙与铁相的比例都接近30%时，水泥试样表现出最优的抗侵蚀性能，其结构致密、孔隙率低，水化产物中钙矾石与铁胶、铝胶协同作用，有效阻碍离子渗透，提升耐久性。

关键词: 铁铝酸盐水泥, 铁相, 氯盐侵蚀, 硫酸盐侵蚀, 抗侵蚀机理, 耐久性

Abstract:

Ferrite-aluminate cement holds significant application prospects in marine engineering due to its low clinkering temperature， reduced carbon emissions， and excellent erosion resistance. In this study， four cement samples with different ferrite phase content were prepared. Immersion tests in chloride and sulfate solutions were conducted， and the influence of ferrite phase content on erosion resistance was systematically investigated using analytical techniques such as XRD， TG， MIP， and SEM. The results indicate that as the ferrite phase content increases， the cement exhibits a lower chloride diffusion coefficient， enhanced chloride-binding capacity， and significantly improved sulfate resistance. When the proportions of the main minerals C₄A₃S， C₂S， and ferrite phase all approach 30%， the cement demonstrates optimal erosion resistance. Its dense structure and low porosity， along with the synergistic effects of ettringite， ferric gel， and aluminate gel in the hydration products， effectively impede ion penetration and enhance durability.

Key words: ferrite-aluminate cement, ferrite phase, chloride salt erosion, sulfate salt erosion, erosion resistance mechanism, durability

中图分类号:

TQ172.72

李红轩, 王亚丽, 裴天蕊, 汪智勇, 齐冬有. 铁相含量对铁铝酸盐水泥抗侵蚀性能的影响机理研究[J]. 硅酸盐通报, 2026, 45(8): 2600-2611.

LI Hongxuan, WANG Yali, PEI Tianrui, WANG Zhiyong, QI Dongyou. Influence of Ferrite Phase Content on Erosion Resistance of Ferrite-Aluminate Cement[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(8): 2600-2611.

图/表 15

表1 原材料的主要化学组成

Table 1 Main chemical composition of raw materials

Raw material	Mass fraction/%
Raw material	Loss	SiO₂	Al₂O₃	CaO	Fe₂O₃	MgO	SO₃	TiO₂
Limestone	41.81	1.17	1.17	54.42	0.48	0.46	0.08	0.11
Desulfurized gypsum	0.03	2.25	0.53	37.37	0.29	0.25	57.11	0.07
Bauxite	14.41	10.71	61.59	4.42	2.16	0.48	1.49	3.20
Fly ash	1.29	49.06	38.46	3.10	3.46	0.73	0.67	1.37
Iron ore	7.59	38.17	8.77	1.47	41.28	0.67	0.29	0.25
Anhydrite	0.04	1.46	0.45	40.57	0.05	3.24	53.69	0.02

图1 四组FAC熟料矿物的XRD谱

Fig.1 XRD patterns of four groups of FAC clinker minerals

表2 四组FAC熟料的生料配合比

Table 2 Raw material proportion for four groups of FAC clinker

Group	Mass fraction/%
Group	Limestone	Desulfurized gypsum	Bauxite	Fly ash	Iron ore
A	70.24	5.60	10.66	9.26	4.24
B	68.61	5.55	14.18	5.20	6.46
C	67.00	5.50	17.69	1.14	8.67
D	61.48	5.45	21.16	1.03	10.88

表3 四组FAC熟料中不同矿物的质量分数

Table 3 Mass fraction of different minerals in four groups of FAC clinker

Group	Mass fraction/%
Group	C₄A₃S	C₂S	C₄AF	C₃A	Amorphous
A	17.30	38.65	13.93	15.17	14.95
B	18.39	32.76	17.67	15.82	15.36
C	21.98	31.24	22.48	11.91	12.39
D	29.74	29.53	28.17	1.39	11.17

图2 四组FAC的Cl-扩散系数

Fig.2 Cl- diffusion coefficient of four groups of FAC

图3 四组FAC的Cl-结合量

Fig.3 Cl- binding capacity of four groups of FAC

图4 不同铁相含量的FAC在Cl-侵蚀后水化产物的变化

Fig.4 Changes in hydration products of FAC with different ferrite phase content after Cl- erosion

图5 FAC在Cl-侵蚀后的孔径分布

Fig.5 Pore size distribution of FAC after Cl- erosion

图6 FAC在Cl-侵蚀后的SEM照片

Fig.6 SEM images of FAC after Cl- erosion

图7 FAC的硫酸盐抗蚀系数

Fig.7 Sulfate resistance coefficient of FAC

图8 FAC硫酸盐侵蚀过程中的膨胀率

Fig.8 Expansion rate during sulfate erosion process of FAC

图9 不同铁相含量的FAC在硫酸盐侵蚀后水化产物的变化

Fig.9 Changes in hydration products of FAC with different ferrite phase content after sulfate erosion

图10 FAC在硫酸盐侵蚀后的孔径分布

Fig.10 Pore size distribution of FAC after sulfate erosion

图11 FAC在硫酸盐侵蚀后的SEM照片

Fig.11 SEM images of FAC after sulfate erosion

图12 FAC抗侵蚀机理示意图

Fig.12 Schematic diagram of FAC erosion resistance mechanism

参考文献 40

[1]	LI H W， LIU F， PAN Z Z， et al. Use of issueary cementitious materials in seawater-sea sand concrete： state-of-the-art review［J］. Construction and Building Materials， 2024， 425： 136009.
[2]	王燕谋. 推广铁铝酸盐水泥破解海洋工程中水泥混凝土腐蚀的世界难题［J］. 中国建材， 2020（10）： 16-17.
	WANG Y M. Popularizing ferric aluminate cement to solve the world’s difficult problem of cement concrete corrosion in marine engineering［J］. China Building Materials， 2020（10）： 16-17 （in Chinese）.
[3]	刘华杰，朱海威，范从军，等. 海洋环境下现浇混凝土结构耐久性提升技术研究［J］. 建筑结构， 2023， 53（增刊2）： 1329-1335.
	LIU H J， ZHU H W， FAN C J， et al. Study on the durability enhancement techniques of cast-in-place concrete structures under marine environment［J］. Building Structure， 2023， 53（issue 2）： 1329-1335 （in Chinese）.
[4]	张玮. 海工混凝土合成纤维混凝土抗裂技术试验研究［J］. 安徽建筑， 2006， 13（3）： 112-115.
	ZHANG W. Anticrack technique test research of the synthetic fiber maritime concrete［J］. Anhui Architecture， 2006， 13（3）： 112-115 （in Chinese）.
[5]	ZHENG M， HUANG J G， YANG M Q， et al. A composite low-carbon cement strategy： high ferrite cement with addition of ferroaluminate cement［J］. Construction and Building Materials， 2024， 456： 139250.
[6]	WANG J L， YANG L F， ZHAO J Q， et al. Modelling and verification for dual time-dependent chloride diffusion of circular concrete columns in marine environment［J］. Journal of Building Engineering， 2023， 76： 107149.
[7]	CHENG Z R， ZHAO J H， CUI L Y. Exploration of hydration and durability properties of ferroaluminate cement with compare to Portland cement［J］. Construction and Building Materials， 2022， 319： 126138.
[8]	姚永刚. 固废基高铁硫铝系海洋工程胶凝材料的制备及抗侵蚀特性试验研究［D］. 济南：山东大学， 2020.
	YAO Y G. Preparation of solid-waste-based ferric-rich sulfoaluminate marine engineering cementitious material and research on its anti-erosion property［D］. Jinan： Shandong University， 2020 （in Chinese）.
[9]	谈慧，王长生. 铁铝酸盐水泥抗蚀性能的研究［J］. 四川水泥， 1999（2）： 6-7.
	TAN H， WANG C S. Study on corrosion resistance of ferroaluminate cement［J］. Sichuan Cement， 1999（2）： 6-7 （in Chinese）.
[10]	DU P， LI X M， ZHOU Z H， et al. Preparation and properties of alite-modified calcium sulfoaluminate cement［J］. Advances in Cement Research， 2021， 33（3）： 135-143.
[11]	CSIZMADIA J， BALÁZS G， TAMÁS F D. Chloride ion binding capacity of aluminoferrites［J］. Cement and Concrete Research， 2001， 31（4）： 577-588.
[12]	XUE J W， LI S M， ZHANG Z H， et al. Hydration， mechanical properties， and corrosion resistance of ferroaluminate cement in the presence of FA and GGBS［J］. Journal of Building Engineering， 2025， 102： 111974.
[13]	ZIBARA H. Binding of external chlorides by cement pastes［D］. Toronto： University of Toronto， 2001.
[14]	HUANG X， TAO Y， YANG L， et al. Chloride adsorption capacity of monocarbonate： the importance of iron doping［J］. ACS Sustainable Chemistry & Engineering， 2022， 10（17）： 5621-5632.
[15]	刘赞群，裴敏，张丰燕，等. 半浸泡在Na₂SO₄溶液中水泥净浆不同部位化学侵蚀产物对比［J］. 建筑材料学报， 2020， 23（3）： 485-492.
	LIU Z Q， PEI M， ZHANG F Y， et al. Comparison of chemical attack products in different zones of cement paste partially immersed in Na₂SO₄ solution［J］. Journal of Building Materials， 2020， 23（3）： 485-492 （in Chinese）.
[16]	MENG F P， LU D C， WANG G S， et al. Experimental study on pore structures and mechanical properties of ferroaluminate cement under sulfate attack［J］. Journal of Building Engineering， 2024， 97： 110905.
[17]	GAO Y R， SHAO Y L， ZHANG X， et al. Insight into the sulfate resistance mechanism of Portland cement with different Fe/Al ratios of ferrite phases［J］. Construction and Building Materials， 2026， 506： 144865.
[18]	BASHEER P A M， ANDREWS R J， ROBINSON D J， et al. ‘PERMIT’ ion migration test for measuring the chloride ion transport of concrete on site［J］. NDT & E International， 2005， 38（3）： 219-229.
[19]	ZHANG K C， LU Y， RAO M J， et al. Understanding the role of brownmilerite on corrosion resistance［J］. Construction and Building Materials， 2020， 254： 119262.
[20]	BLACK L， BREEN C， YARWOOD J， et al. In situ Raman analysis of hydrating C₃A and C₄AF pastes in presence and absence of sulphate［J］. Advances in Applied Ceramics， 2006， 105（4）： 209-216.
[21]	ROSE J， BÉNARD A， MRABET SEL， et al. Evolution of iron speciation during hydration of C₄AF［J］. Waste Management， 2006， 26（7）： 720-724.
[22]	EMANUELSON A， HENDERSON E， HANSEN S. Hydration of ferrite Ca₂AlFeO₅ in the presence of sulphates and bases［J］. Cement and Concrete Research， 1996， 26（11）： 1689-1694.
[23]	DILNESA B Z， LOTHENBACH B， RENAUDIN G， et al. Synthesis and characterization of hydrogarnet Ca₃（Al_x Fe_1-_x）₂（SiO₄）_y（OH）_4（3-_y_）［J］. Cement and Concrete Research， 2014， 59： 96-111.
[24]	LOTHENBACH B， PELLETIER-CHAIGNAT L， WINNEFELD F. Stability in the system CaO-Al₂O₃-H₂O［J］. Cement and Concrete Research， 2012， 42（12）： 1621-1634.
[25]	SEO J， JANG D， BAE J H， et al. Transformations in the reaction products and properties of carbonation-cured CSA cements exposed to a sulfate attack［J］. Journal of CO2 Utilization， 2024， 89： 102964.
[26]	GUO X L， YUAN S T， XU Y F， et al. Effects of phosphorus and iron on the composition and property of Portland cement clinker utilized incinerated sewage sludge ash［J］. Construction and Building Materials， 2022， 341： 127754.
[27]	LI R， XUE L T， YU W Q， et al. Preparation of iron-rich belite-sulfoaluminate cement utilizing iron tailings and fluorogypsum［J］. Environmental Research， 2025， 286： 122778.
[28]	WANG Y C， LI Y， WANG F J， et al. Resistivity and chloride diffusion coefficient of cement-based materials characterized by non-contact electrical resistivity method and resistivity model［J］. Construction and Building Materials， 2024， 426： 136156.
[29]	SEKHAR DAS C， AHMAD M R， ZHAO X L， et al. Influences of temperatures on the physical and chemical chloride binding of calcium silicate hydrate and Friedel salt at different chloride concentrations［J］. Construction and Building Materials， 2025， 476： 141303.
[30]	YAZDI MALI， GRUYAERT E， VAN TITTELBOOM K， et al. New findings on the contribution of Mg-Al-NO₃ layered double hydroxides to the hydration and chloride binding capacity of cement pastes［J］. Cement and Concrete Research， 2023， 163： 107037.
[31]	ECTORS D， NEUBAUER J， GOETZ-NEUNHOEFFER F. The hydration of synthetic brownmillerite in presence of low Ca-sulfate content and calcite monitored by quantitative in-situ-XRD and heat flow calorimetry［J］. Cement and Concrete Research， 2013， 54： 61-68.
[32]	CHENG Z R， JI L Y， WANG Z， et al. Exploration of the chloride binding behavior of anhydrous calcium sulfoaluminate under dual chloride ingress modes［J］. Materials， 2025， 18（21）： 4949.
[33]	MARTı́N-PÉREZ B， ZIBARA H， HOOTON R D， et al. A study of the effect of chloride binding on service life predictions［J］. Cement and Concrete Research， 2000， 30（8）： 1215-1223.
[34]	YANG H， ZHANG Y Y， DING S Q， et al. Carbonation of ettringite and monosulfate： product evolution， microstructure， and comparison［J］. Cement and Concrete Composites， 2025， 164： 106297.
[35]	ZHANG Y Y， ZHAO Q X， GAO Z M， et al. Nanostructural evolution of Al（OH）₃ gel formed by the cubic and orthorhombic ye’elimite clinkers of calcium sulfoaluminate cements in an ultra-wide hydration temperature range［J］. Cement and Concrete Research， 2021， 150： 106607.
[36]	张忠飞. 高铁低钙硅酸盐海工水泥的制备及抗蚀性研究［D］. 桂林：桂林理工大学， 2021.
	ZHANG Z F. Preparation and corrosion resistance of high-lron low-calcium silicate marine cement［D］. Guilin： Guilin University of Technology， 2021 （in Chinese）.
[37]	HUANG X， HU S G， WANG F Z， et al. Enhanced sulfate resistance： the importance of iron in aluminate hydrates［J］. ACS Sustainable Chemistry & Engineering， 2019， 7（7）： 6792-6801.
[38]	MRAK M， WINNEFELD F， LOTHENBACH B， et al. The influence of calcium sulfate content on the hydration of belite-calcium sulfoaluminate cements with different clinker phase compositions［J］. Materials and Structures， 2021， 54（6）： 212.
[39]	郭勇，苏慕珍，邓君安，等. 铁铝酸盐水泥中铁相水化特征的研究［J］. 硅酸盐学报， 1989， 17（4）： 296-301.
	GUO Y， SU M Z， DENG J A， et al. A study on hydration characteristics of ferrite phase in ferroaluminate cement［J］. Journal of the Chinese Ceramic Society， 1989， 17（4）： 296-301 （in Chinese）.
[40]	刘向楠，唐新军，苏建彪，等. 硫铝酸盐水泥混凝土抗高浓度硫酸镁侵蚀性能研究［J］. 水利与建筑工程学报， 2015， 13（5）： 161-167.
	LIU X N， TANG X J， SU J B， et al. Study on the resistance to high concentration of magnesium sulfate attack on sulfate aluminate cement concrete［J］. Journal of Water Resources and Architectural Engineering， 2015， 13（5）： 161-167 （in Chinese）.