乙二胺四亚甲基膦酸对高贝利特硫铝酸盐水泥早期水化硬化的影响

doi:10.16552/j.cnki.issn1001-1625.2024.1614

摘要/Abstract

摘要： 针对快凝快硬型高贝利特硫铝酸盐(HB-CSA)水泥凝结时间快、工作性差的问题,探究了乙二胺四亚甲基膦酸(EDTMP)对HB-CSA水泥凝结时间、流动度及力学性能的影响,并结合水化热、X射线衍射、热重及压汞等测试分析了EDTMP在HB-CSA水泥中的作用机制。结果表明:EDTMP能有效延缓HB-CSA水泥的凝结时间,提高流动度,当EDTMP掺量为1.00%(质量分数)时可以使HB-CSA水泥初凝时间延长至62 min,终凝时间延长至76 min。EDTMP主要通过抑制HB-CSA水泥无水硫铝酸钙(C₄A₃$\overline{\mathrm{s}}$)矿物和石膏相反应,抑制水泥早期水化产物钙矾石(AFt)的快速生成,使HB-CSA水泥缓凝。

关键词: 乙二胺四亚甲基膦酸, 高贝利特硫铝酸盐水泥, 钙矾石, 水化, 缓凝

Abstract: Aiming at the problem of fast setting time and poor workability of fast-setting and fast-hardening high belite calcium sulfoaluminate (HB-CSA) cement, the effect of ethylenediamine tetramethylene phosphonic acid (EDTMP) on the setting time, fluidity and mechanical properties of HB-CSA cement was investigated by hydration heat, X-ray diffraction, thermogravimetric and mercuric pressed tests. The mechanism of action of EDTMP in HB-CSA cement was analyzed. The results show that EDTMP can effectively retard the setting time of calcium sulfoaluminate cement and improve the fluidity. When the EDTMP contnet is 1.00% (mass fraction), it can prolong the initial setting time of HB-CSA cement to 62 min and prolong the final setting time of HB-CSA cement to 76 min. EDTMP can inhibit the reaction between anhydrous calcium sulfoaluminate (C₄A₃$\overline{\mathrm{s}}$) mineral and gypsum phase of HB-CSA cement in order to inhibit the rapid generation of ettringite (AFt), which is an early hydration product of cement, so that HB-CSA cement retarding can be achieved.

Key words: ethylenediamine tetramethylene phosphonic acid, high belite calcium sulfoaluminate cement, ettringite, hydration, retardation

中图分类号:

TQ172

唐芮枫, 王子明, 崔素萍, 赵思雪, 芮雅峰. 乙二胺四亚甲基膦酸对高贝利特硫铝酸盐水泥早期水化硬化的影响[J]. 硅酸盐通报, 2025, 44(6): 1988-1995.

TANG Ruifeng, WANG Ziming, CUI Suping, ZHAO Sixue, RUI Yafeng. Effect of Ethylenediamine Tetramethylene Phosphonic Acid on EarlyHydration-Hardening of High Belite Calcium Sulfoaluminate Cement[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(6): 1988-1995.

参考文献

[1] 王燕谋, 苏慕珍, 张量. 硫铝酸盐水泥[M]. 北京: 北京工业大学出版社, 1999.
WANG Y M, SU M Z, ZHANG L. Sulphoaluminate cement[M]. Beijing: Press of Beijing University of Technology, 1999 (in Chinese).
[2] LV L Y, LUO S T, ŠAVIJA B, et al. Effect of particle size distribution on the pre-hydration, hydration kinetics, and mechanical properties of calcium sulfoaluminate cement[J]. Construction and Building Materials, 2023, 398: 132497.
[3] GARTNER E. Industrially interesting approaches to “low-CO₂” cements[J]. Cement and Concrete Research, 2004, 34(9): 1489-1498.
[4] 何欢, 杨荣俊, 文俊强, 等. PVA纤维增强快硬硫铝酸盐水泥基ECC材料性能的研究[J]. 硅酸盐通报, 2019, 38(5): 1484-1490+1496.
HE H, YANG R J, WEN J Q, et al. Study on the rapid hardening sulphoaluminate-based engineered cementitious composites reinforced with PVA fiber[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(5): 1484-1490+1496 (in Chinese).
[5] HU C L, HOU D S, LI Z J. Micro-mechanical properties of calcium sulfoaluminate cement and the correlation with microstructures[J]. Cement and Concrete Composites, 2017, 80: 10-16.
[6] HARGIS C W, LOTHENBACH B, MÜLLER C J, et al. Carbonation of calcium sulfoaluminate mortars[J]. Cement and Concrete Composites, 2017, 80: 123-134.
[7] 崔天龙, 王里, 马国伟, 等. HB-CSA与膨胀剂对3D打印混凝土收缩开裂性能的影响[J]. 材料导报, 2022, 36(2): 76-82.
CUI T L, WANG L, MA G W, et al. Effect of HB-CSA and expansion agent on shrinkage and cracking performance of 3D printing concrete[J]. Materials Reports, 2022, 36(2): 76-82 (in Chinese).
[8] WANG L, MA H, LI Z J, et al. Cementitious composites blending with high belite sulfoaluminate and medium-heat Portland cements for largescale 3D printing[J]. Additive Manufacturing, 2021, 46: 102189.
[9] MOELICH G M, KRUGER P J, COMBRINCK R. Mitigating early age cracking in 3D printed concrete using fibres, superabsorbent polymers, shrinkage reducing admixtures, B-CSA cement and curing measures[J]. Cement and Concrete Research, 2022, 159: 106862.
[10] 兰明章, 项斌峰, 周健, 等. 快凝快硬高贝利特硫铝酸盐水泥熟料水化机理研究[J]. 硅酸盐通报, 2017, 36(8): 2720-2724+2742.
LAN M Z, XIANG B F, ZHOU J, et al. Hydration mechanism of rapid setting and hardening high belite calcium sulfoaluminate cement[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(8): 2720-2724+2742 (in Chinese).
[11] 张五怡, 聂松, 徐名凤, 等. 高贝利特硫铝酸盐水泥活化研究进展[J]. 硅酸盐通报, 2022, 41(9): 2979-2992.
ZHANG W Y, NIE S, XU M F, et al. Research progress on activation of high belite calcium sulphoaluminate cement[J]. Bulletin of the Chinese Ceramic Society, 2022, 41(9): 2979-2992 (in Chinese).
[12] GLASSER F P, ZHANG L. High-performance cement matrices based on calcium sulfoaluminate-belite compositions[J]. Cement and Concrete Research, 2001, 31(12): 1881-1886.
[13] 唐芮枫, 王子明, 兰明章, 等. 柠檬酸与聚羧酸减水剂在高贝利特硫铝酸盐水泥中的复合效应[J]. 硅酸盐学报, 2021, 49(5): 893-900.
TANG R F, WANG Z M, LAN M Z, et al. Hybird effect of citric acid and polycarboxylate superplasticizer on high belite calcium sulphoaluminate cement[J]. Journal of the Chinese Ceramic Society, 2021, 49(5): 893-900 (in Chinese).
[14] 唐芮枫. 高贝利特硫铝酸盐水泥与化学外加剂相容性研究[D]. 北京: 北京工业大学, 2019: 17-19.
TANG R F. Study on the compatibility of high belite sulfoaluminate cement with chemical admixtures[D]. Beijing: Beijing University of Technology, 2019: 17-19 (in Chinese).
[15] LIU F, LU X H, YANG W, et al. Optimizations of inhibitors compounding and applied conditions in simulated circulating cooling water system[J]. Desalination, 2013, 313: 18-27.
[16] SHEN L, WANG F Q, TIAN L, et al. High-performance thin-film composite membranes with surface functionalization by organic phosphonic acids[J]. Journal of Membrane Science, 2018, 563: 284-297.
[17] 吕兴栋, 王学斌, 李北星. 有机膦酸类化合物在混凝土工程中的应用及缓凝机理研究进展[J]. 材料导报, 2020, 34(15): 15184-15189.
LYU X D, WANG X B, LI B X. Research progress on application of organic phosphonic acid compounds in concrete engineering and their retarding mechanism[J]. Materials Reports, 2020, 34(15): 15184-15189 (in Chinese).
[18] GU P, PAMACHANDRAN V S, BEAUNDOIN J J, et al. Electrichemical behavior of Portland cement pastes containing phosphonates[J]. Advanced Cement Based Materials, 1995, 2(5): 182-188.
[19] 唐芮枫, 王子明, 兰明章, 等. 缓凝剂对高贝利特硫铝酸盐水泥水化和性能的影响[J]. 硅酸盐通报, 2020, 39(12): 3763-3769.
TANG R F, WANG Z M, LAN M Z, et al. Effects of retarders on hydration and properties of high-belite calcium sulphoaluminate cement[J]. Bulletin of the Chinese Ceramic Society, 2020, 39(12): 3763-3769 (in Chinese).
[20] RAMACHANDRAN V S, LOWERY M S, WISE T, et al. The role of phosphonates in the hydration of Portland cement[J]. Materials and Structures, 1993, 26(7): 425-432.
[21] 林炎坤, 张德琛, 许建钊. 磷酸盐/膦及其盐缓凝剂的作用机理及性能[J]. 商品混凝土, 2018(8): 25-28.
LIN Y K, ZHANG D C, XU J Z. The mechanism and performance of phosphate/phosphine and its salt retarders[J]. Commercial Concrete, 2018(8): 25-28 (in Chinese).
[22] 齐志刚, 王瑞和, 徐依吉, 等. 油井水泥缓凝剂乙二胺四亚甲基膦酸盐的研制与应用[J]. 中国石油大学学报(自然科学版), 2008, 32(2): 63-67.
QI Z G, WANG R H, XU Y J, et al. Synthesis and application of ethylene diamine tetra methytene phosphonate as oil well cement retarder[J]. Journal of China University of Petroleum (Edition of Natural Science), 2008, 32(2): 63-67 (in Chinese).
[23] SU T, KONG X M, TIAN H W, et al. Effects of comb-like PCE and linear copolymers on workability and early hydration of a calcium sulfoaluminate belite cement[J]. Cement and Concrete Research, 2019, 123: 105801.
[24] 李北星, 吕兴栋, 魏运权, 等. 氨基三亚甲基膦酸对水泥水化的影响[J]. 建筑材料学报, 2016, 19(3): 417-423.
LI B X, LV X D, WEI Y Q, et al. Effect of amino trimethylene phosphonic acid on hydration of Portland cement[J]. Journal of Building Materials, 2016, 19(3): 417-423 (in Chinese).
[25] WEI J J, FANG C L, ZHOU B, et al. Effect of organic phosphonate types on performance of alkali-activated slag-based materials and its mechanism[J]. Cement and Concrete Composites, 2024, 151: 105597.
[26] LONG W J, WU Z R, WEI J J, et al. The enhanced lead (Ⅱ) ions stabilization of alkali-activated salg-based materials with appropriate addition of phosphonate[J]. Materials Report, 2023, 37: 113-120.