Effect of Calcium Nitrate on Performance of Ferroaluminate Cement at -10 ℃

doi:10.16552/j.cnki.issn1001-1625.2025.0876

Abstract

Abstract:

This study systematically investigated the effect of calcium nitrate content on the mechanical properties and microstructure of ferroaluminate cement under the curing condition of -10 ℃， aiming to address the issues of slow hydration and limited strength development of cement-based materials under sub-zero temperatures conditions. A series of tests were conducted to evaluate the fluidity， setting time， freezing point， and compressive strength at -10 ℃ of cement pastes with different calcium nitrate content. Microstructure was characterized by X-ray diffraction （XRD）， scanning electron microscopy （SEM） and mercury intrusion porosimetry （MIP）. The results show that as the calcium nitrate content increases， the fluidity of the cement paste gradually improves and the setting time shortens. When the calcium nitrate content increases from 0% to 12% （mass fraction）， the fluidity of the cement paste increases from 159 mm to 181 mm， the initial setting time shortens from 53 min to 18 min， and the final setting time shortens from 74 min to 23 min. Moreover， the content of calcium nitrate effectively lowers the freezing point of the ferroaluminate cement paste， ensuring continuous hydration under sub-zero temperatures. Under curing conditions of -10 ℃， the content of calcium nitrate promotes the early hydration reaction of cement and improves the compressive strength of the paste. At 28 d， the compressive strength exhibits a trend of increasing first and then decreasing with the increase in calcium nitrate content， reaching a maximum value of 47.2 MPa at a calcium nitrate content of 8%， which is about 11.4 times higher than the control group. Microstructural analysis reveals that an appropriate amount of calcium nitrate refines the pore structure， enhances the compactness of the system， and thereby improves mechanical properties. However， when the content exceeds 8%， microcracks are prone to form within the paste， and the morphology of ettringite （AFt） crystals is disrupted， leading to decreased structural compactness and a subsequent reduction in mechanical properties of the paste.

Key words: ferroaluminate cement, sub-zero temperature, calcium nitrate, mechanical property, microstructure

CLC Number:

TQ172

XU Kaiqin, LIAO Yishun, ZHANG Pu, ZHANG Dong, QI Dongyou. Effect of Calcium Nitrate on Performance of Ferroaluminate Cement at -10 ℃[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(2): 380-389.

Figures/Tables 12

Table 1 Chemical composition of FAC

Composition	CaO	Al₂O₃	SO₃	SiO₂	Fe₂O₃	MgO	K₂O	Loss
Mass fraction/%	42.23	24.10	18.34	5.43	7.88	1.03	0.56	0.43

Fig.1 XRD pattern of FAC

Table 2 Mix proportion of cement paste

Sample	Mass fraction/%			W/C
Sample	FAC	CN	PCE	W/C
CN0	100	0	0.1	0.3
CN6	94	6	0.1	0.3
CN8	92	8	0.1	0.3
CN10	90	10	0.1	0.3
CN12	88	12	0.1	0.3

Fig.2 LT-DSC curve of FAC paste

Fig.3 Effect of calcium nitrate content on fluidity of FAC paste

Fig.4 Effect of calcium nitrate content on setting time of FAC paste

Fig.5 Effect of calcium nitrate content on compressive strength of FAC paste at -10 ℃

Fig.6 LT-DSC curves of FAC paste with different calcium nitrate content

Fig.7 Effect of calcium nitrate content on melting heat of FAC paste

Fig.8 XRD patterns of FAC paste with different calcium nitrate content at -10 ℃

Fig.9 SEM images of FAC paste after 28 d curing at -10 ℃

Fig.10 Changes in pore structure of cement paste after 28 d curing at -10 ℃

References 46

[1]	ZHANG G， YANG Y Z， LI H M. Calcium-silicate-hydrate seeds as an accelerator for saving energy in cold weather concreting［J］. Construction and Building Materials， 2020， 264： 120191. DOI URL
[2]	ALZAZA A， OHENOJA K， ISTERI V， et al. Blending eco-efficient calcium sulfoaluminate belite ferrite cement to enhance the physico-mechanical properties of Portland cement paste cured in refrigerated and natural winter conditions［J］. Cement and Concrete Composites， 2022， 129： 104469. DOI URL
[3]	KHAN J， SANTHA KUMAR G. Influence of binary antifreeze admixtures on strength performance of concrete under cold weather conditions［J］. Journal of Building Engineering， 2021， 34： 102055. DOI URL
[4]	LIU J， LI Y， YANG Y Q， et al. Effect of low temperature on hydration performance of the complex binder of silica fume-Portland cement［J］. Journal of Wuhan University of Technology-Mater Sci Ed， 2014， 29（1）： 75-81. DOI URL
[5]	KARAGOL F， DEMIRBOGA R， KHUSHEFATI W H. Behavior of fresh and hardened concretes with antifreeze admixtures in deep-freeze low temperatures and exterior winter conditions［J］. Construction and Building Materials， 2015， 76： 388-395. DOI URL
[6]	WANG X J， SUN D Q， LI J W， et al. Properties and hydration characteristics of an iron-rich sulfoaluminate cementitious material under cold temperatures［J］. Cement and Concrete Research， 2023， 168： 107152. DOI URL
[7]	QIN L， GAO X J， ZHANG A L. Potential application of Portland cement-calcium sulfoaluminate cement blends to avoid early age frost damage［J］. Construction and Building Materials， 2018， 190： 363-372. DOI URL
[8]	王燕谋，齐冬有. 北极建设中应推广铁铝酸盐水泥［J］. 中国建材， 2022， 71（11）： 116-119.
	WANG Y M， QI D Y. Iron aluminate cement should be popularized in Arctic construction［J］. China Building Materials， 2022， 71（11）： 116-119 （in Chinese）.
[9]	汪智勇，吴升国，齐冬有，等. 铁相对铁铝酸盐水泥熟料形成的影响［J］. 硅酸盐通报， 2023， 42（5）： 1561-1568.
	WANG Z Y， WU S G， QI D Y， et al. Effect of ferrite phase on formation of ferroaluminate cement clinker［J］. Bulletin of the Chinese Ceramic Society， 2023， 42（5）： 1561-1568 （in Chinese）.
[10]	WANG X J， ZHANG Z L， LI J W， et al. Quantification of CO₂ emission from the preparation and utilization of solid waste-based sulphoaluminate cementitious materials［J］. Journal of Cleaner Production， 2022， 376： 134054. DOI URL
[11]	张晨. 外加剂对硫铝酸盐水泥负温性能影响及作用机理研究［D］. 哈尔滨：哈尔滨工业大学， 2022.
	ZHANG C. The effect of admixtures on the negative temperature performance of sulphoaluminate cement and its mechanism［D］. Harbin： Harbin Institute of Technology， 2022 （in Chinese）.
[12]	RAMACHANDRAN V S. Concrete admixtures handbook： properties， science and technology［M］. 2nd ed. New Jersey： Noyes Publications， 1995： 111-189.
[13]	CULLU M， ARSLAN M. The effects of antifreeze use on physical and mechanical properties of concrete produced in cold weather［J］. Composites Part B： Engineering， 2013， 50： 202-209.
[14]	张鸿飞，叶家元，任俊儒，等. -10 ℃条件下氯化钙溶液对硫铝酸盐水泥性能的影响［J］. 硅酸盐学报， 2022， 50（11）： 2834-2843.
	ZHANG H F， YE J Y， REN J R， et al. Effect of calcium chloride solution on performance of calcium sulphoaluminate cement at -10 ℃［J］. Journal of the Chinese Ceramic Society， 2022， 50（11）： 2834-2843 （in Chinese）.
[15]	WANG Y F， LEI L， LIU J H， et al. Accelerators for normal concrete： a critical review on hydration， microstructure and properties of cement-based materials［J］. Cement and Concrete Composites， 2022， 134： 104762. DOI URL
[16]	陈云，郑文博，付前旺. 氯盐环境下钢筋混凝土腐蚀机理及防腐蚀技术研究进展［J］. 材料导报， 2025， 39（11）： 132-145.
	CHEN Y， ZHENG W B， FU Q W. Research progress on corrosion mechanism and corrosion prevention technology of reinforced concrete under chloride erosion environment［J］. Materials Reports， 2025， 39（11）： 132-145 （in Chinese）.
[17]	范磊. 聚乙烯醇对水泥基材料抗冻性影响的研究［D］. 哈尔滨：哈尔滨工业大学， 2023.
	FAN L. Effect of polyvinyl alcohol on frost resistance of cement-based materials［D］. Harbin： Harbin Institute of Technology， 2023 （in Chinese）.
[18]	CHEN Z， LIAO Y S， DENG F， et al. Effect of calcium nitrate on hydration properties and strength development of calcium sulfoaluminate cement［J］. Construction and Building Materials， 2024， 421： 135770. DOI URL
[19]	HUANG G P， PUDASAINEE D， GUPTA R， et al. The performance of calcium sulfoaluminate cement for preventing early-age frost damage［J］. Construction and Building Materials， 2020， 254： 119322. DOI URL
[20]	KARAGÖL F， DEMIRBOĞA R， KAYGUSUZ M A， et al. The influence of calcium nitrate as antifreeze admixture on the compressive strength of concrete exposed to low temperatures［J］. Cold Regions Science and Technology， 2013， 89： 30-35. DOI URL
[21]	OGUNBODE E， HASSAN I. Effect of addition of calcium nitrate on selected properties of concrete containing volcanic ash［J］. Leonardo Electronic Journal of Practicesand Technologies， 2011， 19： 29-38.
[22]	姚燕，王宏霞，刁桂芝，等. 硝酸钙对铝酸盐水泥强度及水化性能的影响［J］. 硅酸盐学报， 2019， 47（2）： 207-213.
	YAO Y， WANG H X， DIAO G Z， et al. Effect of calcium nitrate on strength and hydration of calcium aluminate cement［J］. Journal of the Chinese Ceramic Society， 2019， 47（2）： 207-213 （in Chinese）.
[23]	MA X B， HU S L， SUN H Y， et al. Exploring the influence of sodium nitrite on the early-age freeze resistance of low-carbon sulphoaluminate cement （SAC）［J］. Journal of Building Engineering， 2024， 84： 108489. DOI URL
[24]	SUN D Q， WANG X J， WANG H H， et al. Influence of antifreeze， accelerator， and pre-curing on properties and hydration of iron-rich calcium sulfoaluminate cement under cold temperatures［J］. Construction and Building Materials， 2025， 471： 140728. DOI URL
[25]	ZHANG S Y， ZHAO Y L， DING H X， et al. Effect of sodium chloride concentration and pre-curing time on the properties of cemented paste backfill in a sub-zero environment［J］. Journal of Cleaner Production， 2021， 283： 125310. DOI URL
[26]	DAMASCENI A， DEI L， FRATINI E， et al. A novel approach based on differential scanning calorimetry applied to the study of tricalcium silicate hydration kinetics［J］. The Journal of Physical Chemistry B， 2002， 106（44）： 11572-11578. DOI URL
[27]	BULLARD J W， JENNINGS H M， LIVINGSTON R A， et al. Mechanisms of cement hydration［J］. Cement and Concrete Research， 2011， 41（12）： 1208-1223. DOI URL
[28]	BURRIS L E， KURTIS K E. Influence of set retarding admixtures on calcium sulfoaluminate cement hydration and property development［J］. Cement and Concrete Research， 2018， 104： 105-113. DOI URL
[29]	张文生，曹立学，郅晓，等. 低钙水泥熟料矿物水化活性、性能及其制备熟料的发展［J］. 硅酸盐学报， 2023， 51（9）： 2465-2477.
	ZHANG W S， CAO L X， ZHI X， et al. Development on hydration activity， properties of low-calcium minerals and its clinkers［J］. Journal of the Chinese Ceramic Society， 2023， 51（9）： 2465-2477 （in Chinese）.
[30]	祝海龙. 无水硫铝酸钙及其水化产物结构研究［D］. 济南：济南大学， 2014.
	ZHU H L. Study on structure of anhydrous calcium sulphoaluminate and hydration products［D］. Jinan： University of Jinan， 2014 （in Chinese）.
[31]	关嘉琪，王传林，郑跃群，等. 海盐阳离子对硫铝酸盐水泥性能的影响研究［J］. 汕头大学学报（自然科学版）， 2024， 39（3）： 48-60.
	GUAN J Q， WANG C L， ZHENG Y Q， et al. Research on influence of sea salt cation on properties of sulfoaluminate cement［J］. Journal of Shantou University （Natural Science Edition）， 2024， 39（3）： 48-60 （in Chinese）.
[32]	王楚乔，王光阳，宋远明. AFm阴离子类型对普通硅酸盐水泥水化产物钙矾石稳定性的影响［J］. 烟台大学学报（自然科学与工程版）， 2022， 35（2）： 242-247.
	WANG C Q， WANG G Y， SONG Y M. Effect of AFm anion type on stability of ettringite generated from ordinary Portland cement hydration［J］. Journal of Yantai University （Natural Science and Engineering Edition）， 2022， 35（2）： 242-247 （in Chinese）.
[33]	WU M， JOHANNESSON B， GEIKER M. Determination of ice content in hardened concrete by low temperature calorimetry： influence of baseline calculation and heat of fusion of confined water［J］. Journal of Thermal Analysis and Calorimetry， 2014， 115（2）： 1335-1351. DOI URL
[34]	LIU Y P， YANG S， LI J H， et al. Effect of w/c ratio and antifreeze admixture on the frost damage of sulfoaluminate cement concrete at -20 ℃［J］. Construction and Building Materials， 2022， 347： 128457. DOI URL
[35]	RENAUDIN G， RAPIN J P， HUMBERT B， et al. Thermal behaviour of the nitrated AFm phase Ca₄Al₂（OH）₁₂（NO₃）₂·4H₂O and structure determination of the intermediate hydrate Ca₄Al₂（OH）₁₂（NO₃）₂·2H₂O［J］. Cement and Concrete Research， 2000， 30（2）： 307-314. DOI URL
[36]	LECHEVALLIER A， CHAOUCHE M， SOUDIER J， et al. An in-depth investigation of AFm-NO₃ hydrates： Fe to Al substitution， hydration levels and anionic exchange capabilities［J］. Cement and Concrete Research， 2024， 186： 107680. DOI URL
[37]	MATSCHEI T， LOTHENBACH B， GLASSER F P. The AFm phase in Portland cement［J］. Cement and Concrete Research， 2007， 37（2）： 118-130. DOI URL
[38]	FALZONE G， BALONIS M， SANT G. X-AFm stabilization as a mechanism of bypassing conversion phenomena in calcium aluminate cements［J］. Cement and Concrete Research， 2015， 72： 54-68. DOI URL
[39]	张鸿飞，任俊儒，叶家元，等. 负温条件下不同溶液拌合硫铝酸盐水泥性能演化规律及机制［J］. 硅酸盐学报， 2024， 52（2）： 624-640.
	ZHANG H F， REN J R， YE J Y， et al. Performance evolution laws and mechanisms of calcium sulphoaluminate cement mixed with different solutions at sub-zero temperature［J］. Journal of the Chinese Ceramic Society， 2024， 52（2）： 624-640 （in Chinese）.
[40]	PAVOINE A， BRUNETAUD X， DIVET L. The impact of cement parameters on delayed ettringite formation［J］. Cement and Concrete Composites， 2012， 34（4）： 521-528. DOI URL
[41]	ÁLVAREZ-AYUSO E， NUGTEREN H W. Synthesis of ettringite： a way to deal with the acid wastewaters of aluminium anodising industry［J］. Water Research， 2005， 39（1）： 65-72. DOI URL
[42]	LI C， LI J Q， TELESCA A， et al. Effect of polycarboxylate ether on the expansion of ye’elimite hydration in the presence of anhydrite［J］. Cement and Concrete Research， 2021， 140： 106321. DOI URL
[43]	YU C， SUN W， SCRIVENER K. Mechanism of expansion of mortars immersed in sodium sulfate solutions［J］. Cement and Concrete Research， 2013， 43： 105-111. DOI URL
[44]	GU Y S， DANGLA P， MARTIN R P， et al. Modeling the sulfate attack induced expansion of cementitious materials based on interface-controlled crystal growth mechanisms［J］. Cement and Concrete Research， 2022， 152： 106676. DOI URL
[45]	WANG J L， LONG G C， XIANG Y， et al. Influence of rapid curing methods on concrete microstructure and properties： a review［J］. Case Studies in Construction Materials， 2022， 17： e01600.
[46]	YANG Z H， XIE Y J， HE J H， et al. A comparative study on the mechanical properties and microstructure of cement-based materials by direct electric curing and steam curing［J］. Materials， 2021， 14（23）： 7407. DOI URL