偏高岭土-磷石膏基复合胶凝材料性能试验研究

摘要/Abstract

摘要： 为扩大磷石膏的综合利用,以原状磷石膏(RPG)和β-半水磷石膏(HPG)为主要原材料,利用偏高岭土(MK)和碱性激发剂(生石灰、水玻璃)改性制备磷石膏基复合胶凝材料。通过单因素试验探究MK掺量、水玻璃掺量及RPG和HPG的相对掺量对偏高岭土-磷石膏基复合胶凝材料(MKPGBM)力学性能、耐水性能和耐干湿性能的影响,并分析其作用机理。结果表明,MK、水玻璃及HPG掺量的增加均能有效提高MKPGBM的强度。MK和水玻璃掺量(以质量分数计)分别为7%~9%和21%~24%时,MKPGBM的力学性能和耐水性能最优。当RPG与HPG相对掺量(质量分数比)为5∶5时,MKPGBM的28 d抗压和抗折强度最优,分别为19.58和7.44 MPa;当RPG与HPG相对掺量为6∶4时,MKPGBM的综合性能较优,其28 d软化系数达到0.796。MK和掺合料的掺入能有效促进水化产物的生成并填充基体之间的孔隙,还能提高RPG内部颗粒的相互接触强度,进而达到改善磷石膏基复合胶凝材料力学性能、耐水性能及耐干湿性能的效果。

关键词: 磷石膏, 偏高岭土, 抗压强度, 抗折强度, 软化系数, 干湿性能, 微观形貌

Abstract: In order to expand the comprehensive utilization of phosphogypsum, raw phosphogypsum (RPG) and β-hemihydrate phosphogypsum (HPG) were used as main raw materials. Besides, metakaolin (MK) and alkaline activators (quicklime, water glass) were used to modify and prepare a kind of phosphogypsum-based composite gelling materials. The effects of MK content, water glass content and the relative ratio of RPG and HPG on mechanical properties, water resistance and dry and wet resistance of metakaolin-phosphogypsum-based composite gelling material (MKPGBM) were investigated by single-factor tests. The mechanism was also analyzed at last. The results show that the strength of MKPGBM can be effectively improved by increasing the content of MK, water glass and HPG. The mechanical properties and water resistance of MKPGBM are optimal when the content of MK and water glass (by mass fraction) are 7%~9% and 21%~24%, respectively. When the relative ratio of RPG and HPG is 5∶5 (mass fraction ratio), the 28 d compressive and flexural strength of MKPGBM are the best, which are 19.58 and 7.44 MPa, respectively. The overall performance of MKPGBM is better when the relative ratio of RPG and HPG is 6∶4, and its 28 d softening coefficient reaches 0.796. The incorporation of MK and admixtures can effectively promote the formation of hydration products and fill the pores between matrix, and can also improve the mutual contact strength of RPG internal particles, thereby improving the mechanical properties,water resistance and dry and wet resistance of phosphogypsum-based composite gelling materials.

Key words: phosphogypsum, metakaolin, compressive strength, flexural strength, softening coefficient, wet and dry property, microscopic appearance

中图分类号:

TU526

邱伟, 孔德文, 崔庚寅, 黄莹蓥, 王玲玲. 偏高岭土-磷石膏基复合胶凝材料性能试验研究[J]. 硅酸盐通报, 2023, 42(9): 3267-3276.

QIU Wei, KONG Dewen, CUI Gengyin, HUANG Yingying, WANG Lingling. Experimental Study on Performance of Metakaolin-Phosphogypsum-Based Composite Gelling Materials[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(9): 3267-3276.

参考文献

[1] MA L, NING P, ZHENG S, et al. Reaction mechanism and kinetic analysis of the decomposition of phosphogypsum via a solid-state reaction[J]. Industrial & Engineering Chemistry Research, 2010, 49(8): 3597-3602.
[2] TAYIBI H, CHOURA M, LÓPEZ F A, et al. Environmental impact and management of phosphogypsum[J]. Journal of Environmental Management, 2009, 90(8): 2377-2386.
[3] 贾兴文, 吴洲, 马英. 磷石膏建材资源化利用现状[J]. 材料导报, 2013, 27(23): 139-141+146.
JIA X W, WU Z, MA Y. Present status of phosphogypsum utilization in building materials[J]. Materials Review, 2013, 27(23): 139-141+146 (in Chinese).
[4] 石鑫, 杨绍利, 马兰. “三石膏”综合利用现状及其新工艺[J]. 现代化工, 2020, 40(9): 8-13+19.
SHI X, YANG S L, MA L. Present situation of comprehensive utilization of “three-gypsum” and new technologies[J]. Modern Chemical Industry, 2020, 40(9): 8-13+19 (in Chinese).
[5] 袁书成, 刘香玲, 梁危, 等. 磷石膏填充墙研究现状与应用进展[J]. 无机盐工业, 2021, 53(4): 8-13.
YUAN S C, LIU X L, LIANG W, et al. Research status and application progress of phosphogypsum infilled walls[J]. Inorganic Chemicals Industry, 2021, 53(4): 8-13 (in Chinese).
[6] 赵红涛, 包炜军, 孙振华, 等. 磷石膏中杂质深度脱除技术[J]. 化工进展, 2017, 36(4): 1240-1246.
ZHAO H T, BAO W J, SUN Z H, et al. Deep removal of impurities from phosphogypsum[J]. Chemical Industry and Engineering Progress, 2017, 36(4): 1240-1246 (in Chinese).
[7] 张峻, 解维闵, 董雄波, 等. 磷石膏材料化综合利用研究进展[J/OL]. 材料导报, 2023(16): 1-24 [2022-09-15]. http://kns.cnki.net/kcms/detail/50.1078.TB.20220901.1257.014.html.
ZHANG J, XIE W M, DONG X B, et al. Research progress on comprehensive utilization of phosphogypsum for materials: a review[J/OL]. Material Reports, 2023(16): 1-24 [2022-09-15]. http://kns.cnki.net/kcms/detail/50.1078.TB.20220901.1257.014.html (in Chinese).
[8] SADIQUL ISLAM G M, CHOWDHURY F H, RAIHAN M T, et al. Effect of phosphogypsum on the properties of Portland cement[J]. Procedia Engineering, 2017, 171: 744-751.
[9] ZHOU J, LI X Q, ZHAO Y, et al. Preparation of paper-free and fiber-free plasterboard with high strength using phosphogypsum[J]. Construction and Building Materials, 2020, 243: 118091.
[10] 付汝松, 陆跃贤, 安红芳, 等. 半水磷石膏固化原状磷石膏制备胶凝材料及性能研究[J]. 无机盐工业, 2022, 54(6): 109-114.
FU R S, LU Y X, AN H F, et al. Study on preparation of cementitious materials from raw phosphogypsum cured by hemihydrate phosphogypsum and their properties[J]. Inorganic Chemicals Industry, 2022, 54(6): 109-114 (in Chinese).
[11] HUA S D, WANG K J, YAO X, et al. Effects of fibers on mechanical properties and freeze-thaw resistance of phosphogypsum-slag based cementitious materials[J]. Construction and Building Materials, 2016, 121: 290-299.
[12] DAVIDOVITS J. Geopolymers and geopolymeric materials[J]. Journal of Thermal Analysis, 1989, 35(2): 429-441.
[13] SINGH B, GUPTA M, BHATTACHARYYA S K. Geopolymer concrete: a review of some recent developments[J]. Construction and Building Materials, 2015, 85: 78-90.
[14] ZHANG L C, ZHANG A L, LI K, et al. Research on the pretreatment and mechanical performance of undisturbed phosphogypsum[J]. Case Studies in Construction Materials, 2020, 13: e00400.
[15] 贺行洋, 代飞, 苏英, 等. 磷石膏-水泥-矿粉复合材料的性能研究[J]. 硅酸盐通报, 2017, 36(8): 2673-2677.
HE X Y, DAI F, SU Y, et al. Properties of phosphogypsum-Portland cement-slag composites[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(8): 2673-2677 (in Chinese).
[16] HOU J J, NI X Y, LUO X. Analysis of the fractal growth characteristics and nucleation mechanism of phosphogypsum-based materials[J].Journal of Wuhan University of Technology-Mater Sci Ed, 2022, 37(5): 863-875.
[17] 高育欣, 麻鹏飞, 程宝军, 等. 掺和料对磷石膏复合胶凝材料性能影响研究[J]. 非金属矿, 2021, 44(2): 102-106.
GAO Y X, MA P F, CHENG B J, et al. Investigation on effect of admixture to the performance of phosphogypsum composite binders[J]. Non-Metallic Mines, 2021, 44(2): 102-106 (in Chinese).
[18] 张太玥, 谢凡, 郭君渊. 磷石膏基复合胶凝材料的性能优化及机理研究[J]. 无机盐工业, 2022, 54(9): 136-142.
ZHANG T Y, XIE F, GUO J Y. Study on performance optimization and mechanism of phosphogypsum based composite cementitious materials[J]. Inorganic Chemicals Industry, 2022, 54(9): 136-142 (in Chinese).
[19] 张建刚, 皇志威, 苏向东, 等. 磷石膏添加量对赤泥基复合材料性能影响研究[J]. 中国有色冶金, 2023, 52(1): 121-130.
ZHANG J G, HUANG Z W, SU X D, et al. Effect of phosphogypsum addition on properties of red mud-phosphogypsum composites[J]. China Nonferrous Metallurgy, 2023, 52(1): 121-130 (in Chinese).
[20] 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).
[21] PILLAY D L, OLALUSI O B, KILISWA M W, et al. Engineering performance of metakaolin based concrete[J]. Cleaner Engineering and Technology, 2022, 6: 100383.
[22] AL-AKHRAS N M. Durability of metakaolin concrete to sulfate attack[J]. Cement and Concrete Research, 2006, 36(9): 1727-1734.
[23] 姜关照, 吴爱祥, 王贻明, 等. 生石灰对半水磷石膏充填胶凝材料性能影响[J]. 硅酸盐学报, 2020, 48(1): 86-93.
JIANG G Z, WU A X, WANG Y M, et al. Effect of lime on properties of filling cementitious material prepared by hemihydrate phosphogypsum[J]. Journal of the Chinese Ceramic Society, 2020, 48(1): 86-93 (in Chinese).
[24] 姚源. 脱硫石膏-粉煤灰胶凝体系性能研究[D]. 西安: 西安建筑科技大学, 2014.
YAO Y. Study on properties of desulfurization gypsum-fly ash cementitious system[D]. Xi'an: Xi'an University of Architecture and Technology, 2014 (in Chinese).
[25] 宁波, 刘苗苗, 王文飞. 偏高岭土混凝土的耐久性与水化特性分析[J]. 矿产综合利用, 2022(6): 49-54+60.
NING B, LIU M M, WANG W F. Analysis of durability and hydration characteristics of metakaolin concrete[J]. Multipurpose Utilization of Mineral Resources, 2022(6): 49-54+60 (in Chinese).
[26] FRÍAS M, MARTÍNEZ-RAMÍREZ S, BLASCO T, et al. Evolution of mineralogical phases by ²⁷Al and ²⁹Si NMR in MK-Ca(OH)₂ system cured at 60℃[J]. Journal of the American Ceramic Society, 2013, 96(7): 2306-2310.
[27] 郑娟荣, 覃维祖, 张涛. 碱-偏高岭土胶凝材料的凝结硬化性能研究[J]. 湖南大学学报(自然科学版), 2004, 31(4): 60-63+76.
ZHENG J R, QIN W Z, ZHANG T. The setting and hardening characteristics of alkali-activated metakaolin cementitious materials[J]. Journal of Hunan University (Natural Sciences), 2004, 31(4): 60-63+76 (in Chinese).
[28] 蒙海宁, 朱祥, 左李萍, 等. 偏高岭土基土聚物水泥的制备及性能研究[J]. 砖瓦, 2017(5): 36-39.
MENG H N, ZHU X, ZUO L P, et al. Study on preparation and properties of metakaolin geopolymer cement[J]. Block-Brick-Tile, 2017(5): 36-39 (in Chinese).
[29] KOMLJENOVIÄ M, BAŠČAREVIÄ Z, BRADIÄ V. Mechanical and microstructural properties of alkali-activated fly ash geopolymers[J]. Journal of Hazardous Materials, 2010, 181(1/2/3): 35-42.
[30] 彭晖, 崔潮, 蔡春声, 等. 激发剂浓度对偏高岭土基地聚物性能的影响机制[J]. 复合材料学报, 2016, 33(12): 2952-2960.
PENG H, CUI C, CAI C S, et al. Mechanism of activator concentration influencing properties of metakaolin-based geopolymer[J]. Acta Materiae Compositae Sinica, 2016, 33(12): 2952-2960 (in Chinese).
[31] 王亚超. 碱激发粉煤灰基地质聚合物强化增韧及耐久性能研究[D]. 西安: 西安建筑科技大学, 2014.
WANG Y C. Study on strengthening, toughening and durability of alkali-activated fly ash-based polymer[D]. Xi'an: Xi'an University of Architecture and Technology, 2014 (in Chinese).
[32] 兰文涛, 吴爱祥, 王贻明, 等. 半水磷石膏充填强度影响因素试验[J]. 哈尔滨工业大学学报, 2019, 51(8): 128-135.
LAN W T, WU A X, WANG Y M, et al. Experimental study on influencing factors of the filling strength of hemihydrate phosphogypsum[J]. Journal of Harbin Institute of Technology, 2019, 51(8): 128-135 (in Chinese).