Effects of Dissolution Characteristics of Gypsum on Hydration Process of Anhydrous Calcium Sulfoaluminate

Abstract

Abstract: The solubility and dissolution rate of gypsum have important effects on the hydration and properties of anhydrous calcium sulfoaluminate. In this paper, isothermal calorimeter, XRD, TG-DTG and other test methods were used to study the dissolution characteristics of hemihydrate gypsum, dihydrate gypsum and anhydrite and their effects on the hydration process of anhydrous calcium sulfoaluminate. Based on Krstulovic-Dabic and Kondo model, the kinetic parameters of each stage of hydration reaction were calculated. The results show that the solubility of hemihydrate gypsum, dihydrate gypsum and anhydrite in pure water is 2.74, 2.30, 2.38 g/L, respectively. The dissolution rate of hemihydrate gypsum is the maximum, followed by dihydrate gypsum, and the minimum is anhydrite (1 h solubility is 1.19 g/L). The addition of gypsum shortens the induction period of hydration of anhydrous calcium sulfoaluminate and accelerates the process of hydration, where hemihydrate behaves most significantly, with the hydration heat curve having almost no induction period, followed by dihydrate, and anhydrite having the least effect on the induction period. At the beginning of the acceleration period, the hydration rate constant from small to large is anhydrite system, dihydrate system, hemihydrate system. The dissolution rate and solubility of gypsum affect the formation process of ettringite. The gypsum with large dissolution rate prompts the appearance of ettringite precipitation at the early stage of hydration and the amount reaches the maximum value quickly. And in the same time, the system with the addition of gypsum with high solubility has a large amount of ettringite production. At 1 h of hydration, the amount of ettringite produced in the hemihydrate system is about 15.77% (mass fraction) of the total sample, 13.28% (mass fraction) in the dihydrate system and only 3.60% (mass fraction) in the anhydrite system.

Key words: gypsum, anhydrous calcium sulfoaluminate, dissolution characteristic, hydration process, ettringite, hydration kinetics

CLC Number:

TQ172.1

HUANG Bingyin, CUI Suping, WANG Yali, CHEN Zhifeng, WANG Jianfeng. Effects of Dissolution Characteristics of Gypsum on Hydration Process of Anhydrous Calcium Sulfoaluminate[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(5): 1804-1813.

References

[1] 沈燕, 张伟, 陈玺, 等. 硫铝酸盐水泥改性的研究进展[J]. 硅酸盐通报, 2019, 38(3): 683-687.
SHEN Y, ZHANG W, CHEN X, et al. Research progress of sulfoaluminate cement modification[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(3): 683-687 (in Chinese).
[2] WINNEFELD F, MARTIN L H J, MÜLLER C J, et al. Using gypsum to control hydration kinetics of CSA cements[J]. Construction and Building Materials, 2017, 155: 154-163.
[3] JANSEN D, SPIES A, NEUBAUER J, et al. Studies on the early hydration of two modifications of ye’elimite with gypsum[J]. Cement and Concrete Research, 2017, 91: 106-116.
[4] 王硕, 常钧, 季娟, 等. 硫铝酸盐水泥胶凝膨胀性能与石膏种类的关系[J]. 新世纪水泥导报, 2019, 25(1): 69-72.
WANG S, CHANG J, JI J, et al. Influence of gypsum types on expansion performance of sulphoaluminate cement[J]. Cement Guide for New Epoch, 2019, 25(1): 69-72 (in Chinese).
[5] 贾韶辉, 陈彦翠, 刘恒波, 等. 石膏种类及掺量对硫铝酸盐水泥性能的影响研究[J]. 建材发展导向, 2015, 13(12): 59-61.
JIA S H, CHEN Y C, LIU H B, et al. Study on the influence of gypsum type and dosage on the properties of sulphoaluminate cement[J]. Development Guide to Building Materials, 2015, 13(12): 59-61 (in Chinese).
[6] GARCÍA-MATÉ M, DE LA TORRE A G, LEÓN-REINA L, et al. Effect of calcium sulfate source on the hydration of calcium sulfoaluminate eco-cement[J]. Cement and Concrete Composites, 2015, 55: 53-61.
[7] ALLEVI S, MARCHI M, SCOTTI F, et al. Hydration of calcium sulphoaluminate clinker with additions of different calcium sulphate sources[J]. Materials and Structures, 2016, 49(1): 453-466.
[8] ZHANG J W, GUAN X M, WANG X, et al. Microstructure and properties of sulfoaluminate cement-based grouting materials: effect of calcium sulfate variety[J]. Advances in Materials Science and Engineering, 2020, 2020: 1-8.
[9] WINNEFELD F, BARLAG S. Influence of calcium sulfate and calcium hydroxide on the hydration of calcium sulfoaluminate clinker[J]. Zkg International, 2009, 62: 42-53.
[10] WINNEFELD F, LOTHENBACH B. Hydration of calcium sulfoaluminate cements—experimental findings and thermodynamic modelling[J]. Cement and Concrete Research, 2010, 40(8): 1239-1247.
[11] 杨敏. 磷石膏的溶解度研究[J]. 广州化工, 2016, 44(15): 62-63+72.
YANG M. Study on solubility of phosphogypsum[J]. Guangzhou Chemical Industry, 2016, 44(15): 62-63+72 (in Chinese).
[12] 杨柳, 冯富宁, 刘振华, 等. 浅析半水石膏含量对水泥性能的影响[J]. 水泥, 2020(s1): 97-104.
YANG L, FENG F N, LIU Z H, et al. Analysis on the influence of gypsum hemihydrate content on cement properties[J]. Cement, 2020(s1): 97-104 (in Chinese).
[13] 崔素萍, 张彦林, 王子明, 等. 石膏品种对硅酸盐—硫铝酸盐复合体系水泥性能的影响[J]. 水泥工程, 2005(1): 38-40+59.
CUI S P, ZHANG Y L, WANG Z M, et al. Influence of different gypsum on performance of Portland-sulphoalminate composite cement system[J]. Cement Engineering, 2005(1): 38-40+59 (in Chinese).
[14] WINNEFELD F, BARLAG S. Calorimetric and thermogravimetric study on the influence of calcium sulfate on the hydration of ye’elimite[J]. Journal of Thermal Analysis and Calorimetry, 2009, 101(3): 949-957.
[15] 李继野. C₄A₃$\bar{S}$-C₂S二元体系的烧成与水化机理研究[D]. 大连: 大连理工大学, 2019.
LI J Y. Study on the sintering and hydration mechanism of C₄A₃$\bar{S}$-C₂S binary system[D]. Dalian: Dalian University of Technology, 2019 (in Chinese).
[16] 耿永娟. 石油焦脱硫灰渣制备硫铝酸盐水泥的反应动力学、水化动力学及性能研究[D]. 青岛: 青岛理工大学, 2018.
GENG Y J. Study on reaction kinetics, hydration kinetics and properties of sulphoaluminate cement prepared from petroleum coke desulfurization slag[D]. Qingdao: Qingdao Tehcnology University, 2018 (in Chinese).
[17] HE Z, YANG H M, LIU M Y. Hydration mechanism of sulphoaluminate cement[J]. Journal of Wuhan University of Technology-Mater Sci Ed, 2014, 29(1): 70-74.
[18] KNUDSEN T. On particle size distribution in cement hydration[C]//Proceeding of 7th International Congress on the Chemistry of Cement. Paris, 1980: 170.
[19] KONDO R, UEDA S. Kinetics and mechanism of the hydration of cements[C]//Proceedings of the Fifth International Symposium on the Chemistry of Cement, Part II Hydration of Cements. Tokyo, 1968: 203-255.
[20] KRSTULOVIİAĆ R, DABIİAĆ P. A conceptual model of the cement hydration process[J]. Cement and Concrete Research, 2000, 30(5): 693-698.
[21] DABIČ P, KRSTULOVIČ R, RUšIČ D. A new approach in mathematical modelling of cement hydration development[J]. Cement and Concrete Research, 2000, 30(7): 1017-1021.
[22] 徐冠立, 孙遥, 林金辉. 含钡硫铝酸盐水泥的水化动力学与热力学研究[J]. 材料导报, 2013, 27(12): 126-130.
XU G L, SUN Y, LIN J H. Study on kinetics and thermodynamics of hydration of Ba-bearing sulphoaluminate cement[J]. Materials Review, 2013, 27(12): 126-130 (in Chinese).
[23] 吴学权. 矿渣水泥水化动力学研究[J]. 硅酸盐学报, 1988, 16(5): 423-429.
WU X Q. Kinetic study on hydration of blast furnace slag cement[J]. Journal of the Chinese Ceramic Society, 1988, 16(5): 423-429 (in Chinese).
[24] PADILLA-ENCINAS P, PALOMO A, BLANCO-VARELA M T, et al. Monitoring early hydration of calcium sulfoaluminate clinker[J]. Construction and Building Materials, 2021, 295: 123578.