改性5A沸石对偏高岭土地聚物微观结构及抗泛碱性能的影响

摘要/Abstract

摘要： 为了降低碱激发偏高岭土地聚物的泛碱程度,采用具备阳离子交换性能的改性5A沸石降低地聚物孔隙中游离碱金属阳离子的含量。通过地聚物的抗压强度测试、孔结构分析(BET)、微观形貌分析(SEM-EDS)等方法探究改性5A沸石对地聚物微观结构和宏观性能的影响。通过电感耦合等离子原子发射光谱仪(ICP-OES)检测浸出液中阳离子含量,利用Image Pro Plus软件计算在固定泛碱模式下地聚物的泛碱面积,评估改性5A沸石对地聚物泛碱程度的影响,并揭示改性5A沸石对地聚物中Na⁺和Ca²⁺迁移规律的影响。结果表明,掺量为4%(质量分数)的改性5A沸石既能通过内养护和微集料效应优化孔结构,增强地聚物的力学性能,又能与孔溶液进行阳离子交换,形成(N,C)-A-S-H凝胶;Na⁺浸出量降低了19.4%,地聚物表观泛碱程度降低了57.3%。

关键词: 5A沸石, 偏高岭土, 地聚物, 阳离子交换, 抗泛碱, 内养护

Abstract: To reduce the degree of efflorescence in the alkali activation metakaolin geopolymer, modified 5A zeolite with cation exchange property was used to reduce the content of free alkali metal cations in the pores of geopolymer. The effect of modified 5A zeolite on the microstructure and properties of geopolymer were investigated by compressive strength test, pore structure analysis (BET) and SEM-EDS. The cation content in the leachate was detected by inductively coupled plasma optical emission spectrometer (ICP-OES), and the efflorescence area of geopolymer was calculated by Image Pro Plus software in the fixed efflorescence mode to evaluate the effect of modified 5A zeolite on the efflorescence degree of the geopolymer and reveal the effect of modified 5A zeolite on the migration patterns of Na⁺ and Ca²⁺ in geopolymer. The results show that the modified 5A zeolite with 4% (mass fraction) content can optimize the pore structure, enhance the mechanical properties of geopolymer through internal curing and micro-aggregate effect, and exchange cation in pore solution to form (N,C)-A-S-H gel. Na⁺ leaching concentration reduces by 19.4% and the efflorescence area of geopolymer reduces by 57.3%.

Key words: 5A zeolite, metakaolin, geopolymer, cation exchange, efflorescence resistance, internal curing

中图分类号:

TU528

罗仁, 芦雨薇, 许源, 樊晋源, 刘怀, 段平. 改性5A沸石对偏高岭土地聚物微观结构及抗泛碱性能的影响[J]. 硅酸盐通报, 2023, 42(10): 3633-3642.

LUO Ren, LU Yuwei, XU Yuan, FAN Jinyuan, LIU Huai, DUAN Ping. Effect of Modified 5A Zeolite on Microstructure and Efflorescence Resistance of Metakaolin Geopolymer[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(10): 3633-3642.

参考文献

[1] ZHANG J, SHI C J, ZHANG Z H, et al. Durability of alkali-activated materials in aggressive environments: a review on recent studies[J]. Construction and Building Materials, 2017, 152: 598-613.
[2] 郭勉惠, 陈远超. 碱激发胶凝材料风化抑制的研究现状[J]. 居舍, 2022(32): 40-42.
GUO M H, CHEN Y C. Research status of weathering inhibition of alkali-activated cementitious materials[J]. A Dwelling, 2022(32): 40-42 (in Chinese).
[3] SRINIVASAMURTHY L, CHEVALI V S, ZHANG Z H, et al. Phase changes under efflorescence in alkali activated materials with mixed activators[J]. Construction and Building Materials, 2021, 283: 122678.
[4] CAPPELLETTI G, FERMO P, PINO F, et al. On the role of hydrophobic Si-based protective coatings in limiting mortar deterioration[J]. Environmental Science and Pollution Research, 2015, 22(22): 17733-17743.
[5] XUE X, LIU Y L, DAI J G, et al. Inhibiting efflorescence formation on fly ash-based geopolymer via silane surface modification [J]. Cement and Concrete Composites, 2018, 94: 43-52.
[6] MAGHSOODLOORAD H, ALLAHVERDI A. Efflorescence formation and control in alkali-activated phosphorus slag cement[J]. International Journal of Civil Engineering, 2016, 14(6): 425-438.
[7] ZHANG Z H, PROVIS J L, REID A, et al. Fly ash-based geopolymers: the relationship between composition, pore structure and efflorescence[J]. Cement and Concrete Research, 2014, 64: 30-41.
[8] LONGHI M A, ZHANG Z H, WALKLEY B, et al. Strategies for control and mitigation of efflorescence in metakaolin-based geopolymers[J]. Cement and Concrete Research, 2021, 144: 106431.
[9] NAJAFI K E, ALLAHVERDI A, PROVIS J L. Efflorescence control in geopolymer binders based on natural pozzolan[J]. Cement and Concrete Composites, 2012, 34(1): 25-33.
[10] HE P G, WANG M R, FU S, et al. Effects of Si/Al ratio on the structure and properties of metakaolin based geopolymer[J]. Ceramics International, 2016, 42(13): 14416-14422.
[11] SUN K K, PENG X Q, WANG S P, et al. Effect of nano-SiO₂ on the efflorescence of an alkali-activated metakaolin mortar[J]. Construction and Building Materials, 2020, 253: 118952.
[12] LONGHI M A, RODRÍGUEZ E D, WALKLEY B, et al. Metakaolin-based geopolymers: relation between formulation, physicochemical properties and efflorescence formation[J]. Composites Part B: Engineering, 2020, 182: 107671.
[13] 申少华, 李爱玲, 张术根, 等. A型沸石的水热制备及生长机制研究[J]. 硅酸盐学报, 2003, 31(8): 732-737.
SHEN S H, LI A L, ZHANG S G, et al. Hydrothermal preparation of zeolite a and its growth mechanism[J]. Journal of the Chinese Ceramic Society, 2003, 31(8): 732-737 (in Chinese).
[14] 喻岚, 徐冰峰, 庹婧艺, 等. 改性沸石处理氨氮废水的研究进展[J]. 工业安全与环保, 2021, 47(9): 88-92.
YU L, XU B F, TUO J Y, et al. Research progress on treatment of ammonia nitrogen wastewater by modified zeolite[J]. Industrial Safety and Environmental Protection, 2021, 47(9): 88-92 (in Chinese).
[15] 安金鹏, 卢忠远, 严云. 沸石改性粉煤灰地聚物水泥固化材料的研究[J]. 核化学与放射化学, 2008, 30(3): 134-141.
AN J P, LU Z Y, YAN Y. Fly ash based geopolymers solidification material modified by blending with natural zeolite[J]. Journal of Nuclear and Radiochemistry, 2008, 30(3): 134-141 (in Chinese).
[16] GUO L, WU Y Y, XU F, et al. Sulfate resistance of hybrid fiber reinforced metakaolin geopolymer composites[J]. Composites Part B: Engineering, 2020, 183: 107689.
[17] 傅博, 程臻赟, 韩静云, 等. 碱偏高岭土矿渣地聚合物砂浆强度及新拌性能研究[J]. 硅酸盐通报, 2019, 38(12): 4013-4020.
FU B, CHENG Z Y, HAN J Y, et al. Strength and fresh properties of alkali activated metakaolin slag geopolymer mortar[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(12): 4013-4020 (in Chinese).
[18] 高黎明, 王永宝, 郭天天, 等. 偏高岭土地聚物力学性能研究进展[J]. 混凝土, 2022(2): 116-120+126.
GAO L M, WANG Y B, GUO T T, et al. Research status of mechanical properties of metakaolin geopolymer[J]. Concrete, 2022(2): 116-120+126 (in Chinese).
[19] 廉慧珍. 沸石岩火山灰活性的研究[J]. 硅酸盐学报, 2002, 30(4): 411-416.
LIAN H Z. Studies on pozzolanic activity of zeolite-tuff[J]. Journal of the Chinese Ceramic Society, 2002, 30(4): 411-416 (in Chinese).
[20] WANG J B, LI F S, ZHOU Z H, et al. Effect of zeolite on waste based alkali-activated inorganic binder efflorescence[J]. Construction and Building Materials, 2018, 158: 683-690.
[21] TEMUUJIN J, VAN R A, WILLIAMS R. Influence of calcium compounds on the mechanical properties of fly ash geopolymer pastes[J]. Journal of Hazardous Materials, 2009, 167(1/2/3): 82-88.
[22] ISLAM M S, MOHR B, VANDENBERGE D. Performance of natural clinoptilolite zeolite in the cementitious materials: a comparative study with metakaolin, fly ash, and blast furnace slag[J]. Journal of Building Engineering, 2022, 53: 104535.
[23] YIP C K, LUKEY G C, PROVIS J L, et al. Effect of calcium silicate sources on geopolymerisation[J]. Cement and Concrete Research, 2008, 38(4): 554-564.
[24] 何月, 李星辰, 丁锐. 碱激发胶凝材料的进展[J]. 北方建筑, 2020, 5(4): 47-51.
HE Y, LI X C, DING R. Progress of alkali-activated cementitious materials[J]. Northern Architecture, 2020, 5(4): 47-51 (in Chinese).
[25] HUANG Y, HAN M F, YI R R. Microstructure and properties of fly ash-based geopolymeric material with 5A zeolite as a filler[J]. Construction and Building Materials, 2012, 33: 84-89.
[26] 高亚, 李玉香, 马雪, 等. 模拟高盐高碱低中水平放射性废液水泥固化工艺的研究[J]. 辐射防护, 2014, 34(4): 218-223.
GAO Y, LI Y X, MA X, et al. Cement solidification of simulated high saline-alkali low and intermediate-low level radioactive liquid waste[J]. Radiation Protection, 2014, 34(4): 218-223 (in Chinese).
[27] HUANG X, HU S G, WANG F Z, et al. Properties of alkali-activated slag with addition of cation exchange material[J]. Construction and Building Materials, 2017, 146: 321-328.
[28] 刘岩, 叶涛萍, 曹万林. 地聚物混凝土结构研究与发展[J]. 自然灾害学报, 2020, 29(4): 8-19.
LIU Y, YE T P, CAO W L. Research and development of geopolymer concrete structure[J]. Journal of Natural Disasters, 2020, 29(4): 8-19 (in Chinese).
[29] ODLER I, RÖßLER M. Investigations on the relationship between porosity, structure and strength of hydrated Portland cement pastes. II. Effect of pore structure and of degree of hydration[J]. Cement and Concrete Research, 1985, 15(3): 401-410.
[30] 谈云志, 柯睿, 陈君廉, 等. 偏高岭土增强石灰-水泥固化淤泥的耐久性研究[J]. 岩土力学, 2020, 41(4): 1146-1152.
TAN Y Z, KE R, CHEN J L, et al. Enhancing durability of lime-cement solidified sludge with metakaolin[J]. Rock and Soil Mechanics, 2020, 41(4): 1146-1152 (in Chinese).
[31] XU W T, LO Y T, OUYANG D, et al. Effect of rice husk ash fineness on porosity and hydration reaction of blended cement paste[J]. Construction and Building Materials, 2015, 89: 90-101.
[32] LI Z, LIU L L, YAN S H, et al. Properties of microscopic particle morphology and particle contact of renewable construction waste mixtures[J]. Construction and Building Materials, 2019, 207: 190-205.