硫硅酸钙-硫铝酸钙水泥熟料矿物组成的优化研究

摘要/Abstract

摘要： 硫硅酸钙-硫铝酸钙水泥是一种新型低碳水泥,硫硅酸钙矿物的水化活性对水泥性能具有积极作用。本文利用离子掺杂制备了硫硅酸钙-硫铝酸钙水泥,研究了硫硅酸钙、硫铝酸钙矿物以及后掺石膏的配比优化。结果表明,硫硅酸钙-硫铝酸钙水泥熟料的实际矿物组成与设计含量较为一致。硫铝酸钙含量的增加有利于提高水泥的早期强度,其适宜含量范围为30%~40%(质量分数);水泥的强度随着硫硅酸钙含量的增加而提高,当其设计含量增加至48%(质量分数)时,水泥强度降低,该矿物的适宜含量范围为40%~55%(质量分数),其优化含量根据硫铝酸钙的含量而有所不同。石膏的添加有利于硫硅酸钙-硫铝酸钙水泥强度的增长,与天然石膏相比,硬石膏更能促进水泥强度的发展;水泥的后掺石膏优选硬石膏,其优化掺量为8%(质量分数),28 d强度达到76 MPa。硬石膏掺量的增加促进了钙矾石的形成,但过高掺量的硬石膏会抑制硫硅酸钙的水化。

关键词: 硫硅酸钙-硫铝酸钙水泥, 低碳水泥, 矿物优化, 后掺石膏, 抗压强度

Abstract: Ternesite-ye’elimite cement is a new type of low-carbon cement. The hydration reactivity of ternesite has a positive effect on the performance of cement. In this work, ternesite-ye’elimite cement was produced by adding dopants. The optimization of ternesite, ye’elimite and gypsum contents was studied. The results indicate that the phase composition of clinkers is consistent with the designed value. The increase of ye’elimite content improves the early strength of cement pastes, and the appropriate content of ye’elimite is 30% to 40% (mass fraction). With the increase of ternesite content, the compressive strength increases. However, when the theoretical content of ternesite reaches 48% (mass fraction), the compressive strength of cement pastes decreases. The appropriate content of ternesite is 40% to 55% (mass fraction), and the optimized content of ternesite varies according to the content of ye’elimite. The addition of gypsum is beneficial for the strength development of cement pastes. Compared with natural gypsum, anhydrite can better promote the strength development. Therefore, anhydrite is preferentially selected as the added gypsum. The optimized content of anhydrite is 8% (mass fraction), and the cement obtains the compressive strength of 76 MPa at 28 d. The increased content of anhydrite promotes the formation of ettringite, but excessive anhydrite hinders the hydration of ternesite.

Key words: ternesite-ye’elimite cement, low-carbon cement, mineral optimization, added gypsum, compressive strength

中图分类号:

TU525

沈燕, 王培芳, 朱航宇. 硫硅酸钙-硫铝酸钙水泥熟料矿物组成的优化研究[J]. 硅酸盐通报, 2021, 40(12): 3910-3917.

SHEN Yan, WANG Peifang, ZHU Hangyu. Optimization Study on Mineral Composition of Ternesite-Ye’elimite Cement Clinker[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(12): 3910-3917.

参考文献

[1] 杨南如.非传统胶凝材料化学[M].武汉:武汉理工大学出版社,2018.
YANG N R. Chemistry of non-traditional cementing materials[M]. Wuhan: Wuhan University of Technology Press, 2018 (in Chinese).
[2] 沈燕,朱航宇,王培芳,等.锂盐对硼砂在硫铝酸盐水泥中作用的影响[J].硅酸盐通报,2021,40(2):377-383.
SHEN Y, ZHU H Y, WANG P F, et al. Effect of lithium salt on function of borax in sulphoaluminate cement[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(2): 377-383 (in Chinese).
[3] 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: Beijing University of Technology Press, 1999 (in Chinese).
[4] SELUK N, SONER, SELUK E. Synthesis of special cement with fluidised bed combustion ashes[J]. Advances in Cement Research, 2010, 22(2): 107-113.
[5] 沈燕.利用磷石膏制备高硫型贝利特硫铝酸盐水泥的研究[D].重庆:重庆大学,2015.
SHEN Y. Synthesis of sulfate-rich belite sulfoaluminate cement with phosphogypsum[D]. Chongqing: Chongqing University, 2015 (in Chinese).
[6] SHERMAN N, BERETKA J, SANTORO L, et al. Long-term behaviour of hydraulic binders based on calcium sulfoaluminate and calcium sulfosilicate[J]. Cement and Concrete Research, 1995, 25(1): 113-126.
[7] BERETKA J, DE VITO B, SANTORO L, et al. Hydraulic behaviour of calcium sulfoaluminate-based cements derived from industrial process wastes[J]. Cement and Concrete Research, 1993, 23(5): 1205-1214.
[8] SHEN Y, QIAN J S, HUANG Y B, et al. Synthesis of belite sulfoaluminate-ternesite cements with phosphogypsum[J]. Cement and Concrete Composites, 2015, 63: 67-75.
[9] BULLERJAHN F, SCHMITT D, BEN HAHA M. Effect of raw mix design and of clinkering process on the formation and mineralogical composition of (ternesite) belite calcium sulphoaluminate ferrite clinker[J]. Cement and Concrete Research, 2014, 59: 87-95.
[10] MONTES M, PATO E, CARMONA-QUIROGA P M, et al. Can calcium aluminates activate ternesite hydration? [J]. Cement and Concrete Research, 2018, 103: 204-215.
[11] CARMONA-QUIROGA P M, MONTES M, PATO E, et al. Study on the activation of ternesite in CaO·Al₂O₃ and 12CaO·7Al₂O₃ blends with gypsum for the development of low-CO₂ binders[J]. Journal of Cleaner Production, 2021, 291: 125726.
[12] SHEN Y, CHEN X, ZHANG W, et al. Influence of ternesite on the properties of calcium sulfoaluminate cements blended with fly ash[J]. Construction and Building Materials, 2018, 193: 221-229.
[13] SHEN Y, CHEN X, ZHANG W, et al. Effect of ternesite on the hydration and properties of calcium sulfoaluminate cement[J]. Journal of Thermal Analysis and Calorimetry, 2019, 136(2): 687-695.
[14] 陈玺.硫硅酸钙-硫铝酸钙水泥的制备研究[D].扬州:扬州大学,2020.
CHEN X. Study on the preparation of ternesite-calcium sulfoaluminate cement[D]. Yangzhou: Yangzhou University, 2020 (in Chinese).
[15] 刘永毅,任尊超,袁连旺,等.响应曲面法优化高强硅酸盐水泥熟料矿物组成的研究[J].硅酸盐通报,2021,40(4):1088-1096.
LIU Y Y, REN Z C, YUAN L W, et al. Optimizing mineral composition of high strength Portland cement clinker based on response surface methodology[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(4): 1088-1096 (in Chinese).
[16] 李娟,周春英,杨亚晋.高贝利特硫铝酸盐熟料矿物组成优化[J].硅酸盐学报,2012,40(11):1618-1624.
LI J, ZHOU C Y, YANG Y J. Optimization of mineral composition of high belite-sulphoaluminate clinker[J]. Journal of the Chinese Ceramic Society, 2012, 40(11): 1618-1624 (in Chinese).
[17] 沈燕,朱航宇,王培芳,等.不同养护条件下硫硅酸钙-硫铝酸钙水泥的性能研究[J/OL].材料导报:1-11[2021-07-30].http://kns.cnki.net/kcms/detail/50.1078.TB.20210705.1724.002.html.
SHEN Y, ZHU H Y, WANG P F, et al. Study on properties of calcium sulphosilicate-calcium sulphoaluminate cement under different curing conditions[J/OL]. Material review: 1-11 [2021-07-30]. http://kns.cnki.net/kcms/detail/50.1078.TB.20210705.1724.002.html (in Chinese).
[18] CHEN I A, HARGIS C W, JUENGER M C G. Understanding expansion in calcium sulfoaluminate-belite cements[J]. Cement and Concrete Research, 2012, 42(1): 51-60.
[19] 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).
[20] IOANNOU S, REIG L, PAINE K, et al. Properties of a ternary calcium sulfoaluminate-calcium sulfate-fly ash cement[J]. Cement and Concrete Research, 2014, 56: 75-83.
[21] WINNEFELD F, MARTIN L H J, MLLER C J, et al. Using gypsum to control hydration kinetics of CSA cements[J]. Construction and Building Materials, 2017, 155: 154-163.
[22] 黄永波.磷石膏制备硫硅酸钙-硫铝酸盐水泥[D].重庆:重庆大学,2018.
HUANG Y B. Utilization of phosphogypsum for the preparation of ternesite-calcium sulfoaluminate cement[D]. Chongqing: Chongqing University, 2018 (in Chinese).
[23] SHEN Y, WANG P F, CHEN X, et al. Synthesis, characterisation and hydration of ternesite[J]. Construction and Building Materials, 2021, 270: 121392.
[24] SKALAMPRINOS S, JEN G, GALAN I, et al. The synthesis and hydration of ternesite, Ca₅(SiO₄)₂SO₄[J]. Cement and Concrete Research, 2018, 113: 27-40.
[25] HAHA M B, BULLERJAHN F, ZAJAC M. On the reactivity of ternesite[C]//14^th International Congress on the Chemistry of Cement. Beijing, 2015.