磷酸基地质聚合物的制备及其性能研究进展

doi:10.16085/j.issn.1000-6613.2022-0918

摘要/Abstract

摘要：

磷酸基地质聚合物是硅铝质前体与磷酸（盐）溶液反应生成的一类新型地质聚合物材料，原料、激发剂用量、水用量以及养护条件是影响磷酸基地质聚合物组成和结构的主要因素，也进一步决定其使用性能。本文综述了磷酸基地质聚合物形成机理及网络结构的发展；总结了不同原料、养护制度、激发剂种类与用量等因素对磷酸基地质聚合物制备的影响；详细论述了多种制备条件对磷酸基地质聚合物力学性能的影响，并简述了磷酸基地质聚合物的耐热、耐腐蚀以及介电等性能特点。此外，文中指出了磷酸基地质聚合物的形成机理研究中对网络结构认识的不足及其制备过程中存在的问题，提出应进一步明确磷酸基地质聚合物的反应机理并建立系统的性能检测标准，展望了磷酸基地质聚合物的高附加值应用及其在固体废物资源化方向的发展前景。

关键词: 磷酸基地质聚合物, 制备工艺, 形成机理, 性能

Abstract:

Phosphobase geopolymer is a new class of geopolymer material formed by the reaction between aluminosilicate precursor and phosphoric acid (salt) solution. Raw materials, amount of activator, amount of water and curing conditions are the main factors that affect the composition and structure of phosphobase geopolymer, and further determine their performance. In this paper, the formation mechanism and network structure development of phosphobase geopolymer are reviewed. The influence of different raw materials, curing systems, types and amounts of activators on phosphobase geopolymer are summarized. The effects of various preparation conditions on the mechanical properties of phosphobase geopolymer are discussed in detail, and a sketch of the heat resistance, corrosion resistance and dielectric properties of phosphobase geopolymer is introduced. In addition, the paper pointed out the insufficient understanding of network structure in the research on formation mechanism and the problems existing in the preparation process of phosphobase geopolymer. It is proposed that the reaction mechanism of phosphobase geopolymer should be further clarified and a systematic performance testing standard should be established. Finally, the high value-added application of phosphobase geopolymer and its development prospect in the direction of solid waste recycling are prospected.

Key words: phosphobase geopolymer, preparation process, formation mechanism, properties

中图分类号:

TQ172

高江雨, 张耀君, 贺攀阳, 刘礼才, 张枫烨. 磷酸基地质聚合物的制备及其性能研究进展[J]. 化工进展, 2023, 42(3): 1411-1425.

GAO Jiangyu, ZHANG Yaojun, HE Panyang, LIU Licai, ZHANG Fengye. Recent progress on the fabrication and properties of phosphobase geopolymer[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1411-1425.

图/表 14

图1 “Al—O层”反应机理示意图[16]

图2 磷酸基地质聚合物形成过程[29]

图3 磷酸基地质聚合物形成机理模型[30]

图4 不同磷酸盐用量的磷酸基地质聚合物的凝结时间和抗压强度[41]

图5 不同养护温度制度的磷酸基地质聚合物样品外观[50]

表1 磷酸基地质聚合物的制备工艺参数及其力学性能

养护温度制度	养护环境	磷酸质量分数 /%	水用量	磷酸用量	原料性质	抗压强度 /MPa	参考文献
50℃(7d)	潮湿/干燥	85	W/B=0.3	P/Al=0.6~1.0	—	40~117.7	[28]
60℃(24h)、RT(21d)	—	85	W/B=0.25	Si/P=2.25~3.50	d≤125μm	最大37	[31]
60℃(24h)、RT(28d)	—	85	—	Si/P=2.75	d≤125μm、100μm、80μm、63μm	39~54	[34]
RT(24h)、60℃(24h)、RT(28d)	密封	4~14mol/L	L/S=0.8	—	—	36.4~93.8	[36]
RT(5d)、60℃(24h)、RT(28d)	密封	10mol/L	L/S=0.95	—	不同三水铝石含量，d≤90μm	最大54.41	[37]
RT(3~28d)	潮湿	85	H₂O/偏高岭土(MK)=0.4	Si/P=2.75	—	最大51.3	[41]
20℃、40℃和70℃	密封	85	Al/H₂O=0.15~0.62	Al/P=1或4	Si/Al=0.85~1.02，d₅₀=10~6μm	44～120	[43]
60℃或RT(15d)	密封	85	L/S=1	P/Al=1	—	29.9或20.7	[44]
60℃(24h)、RT(28d)	密封	85	$V H 3 P O 4 + H 2 O$ =8mL	P/Al=0.5~2	—	最大2.1	[47]
80℃(24h)、60℃(3d)	密封	—	H₂O/Al₂O₃=4∶1	H₃PO₄/Al₂O₃=1	SiO₂/Al₂O₃=1,d≤45μm	最大89.3	[48]
80℃(24h)、60℃(3d)	密封	—	H₂O/Al₂O₃=2∶1	H₃PO₄/Al₂O₃=1	SiO₂/Al₂O₃=3/1,200~1000℃(2h)	最大60	[48]
40℃(24h)、60℃(24h)	密封	85	L/S=1	P/Al=0.52~0.84	Si/Al=0.96	23.1~123.4	[50]
40℃(24h)、80℃(24h)	密封	85	L/S=1	P/Al=0.52~0.84	Si/Al=0.96	21.6~96.8	[50]
60℃(7d)	—	68	L/S=1.60~1.75	—	—	最大46.3	[51]
70℃(72h)	密封	85	0.45%~0.68%	Al/P=0.9~1.8	Si/Al=1	80~11	[52]
RT(7d)	密封	85	L/S=1	—	SiO₂/Al₂O₃=1.0~2.2	最大13.59	[53]
60℃(24h)、RT(7d、14d、28d)	—	85	L/S=0.67或1.25	P/Al=1	热活化或机械研磨	最大5.5	[55]
RT(7d)	密封	85	L/S=1	H₃PO₄/Al₂O₃=1.0~1.4	—	29	[60]
60℃(24h)、RT(28d)	干燥	10mol/L	L/S=1~1.2	Al/P=0.8~1.0	Si/Al=1.6,700~900℃(2h)	最大67	[64]

表1 磷酸基地质聚合物的制备工艺参数及其力学性能

养护温度制度	养护环境	磷酸质量分数 /%	水用量	磷酸用量	原料性质	抗压强度 /MPa	参考文献
50℃(7d)	潮湿/干燥	85	W/B=0.3	P/Al=0.6~1.0	—	40~117.7	[28]
60℃(24h)、RT(21d)	—	85	W/B=0.25	Si/P=2.25~3.50	d≤125μm	最大37	[31]
60℃(24h)、RT(28d)	—	85	—	Si/P=2.75	d≤125μm、100μm、80μm、63μm	39~54	[34]
RT(24h)、60℃(24h)、RT(28d)	密封	4~14mol/L	L/S=0.8	—	—	36.4~93.8	[36]
RT(5d)、60℃(24h)、RT(28d)	密封	10mol/L	L/S=0.95	—	不同三水铝石含量，d≤90μm	最大54.41	[37]
RT(3~28d)	潮湿	85	H₂O/偏高岭土(MK)=0.4	Si/P=2.75	—	最大51.3	[41]
20℃、40℃和70℃	密封	85	Al/H₂O=0.15~0.62	Al/P=1或4	Si/Al=0.85~1.02，d₅₀=10~6μm	44～120	[43]
60℃或RT(15d)	密封	85	L/S=1	P/Al=1	—	29.9或20.7	[44]
60℃(24h)、RT(28d)	密封	85	$V H 3 P O 4 + H 2 O$ =8mL	P/Al=0.5~2	—	最大2.1	[47]
80℃(24h)、60℃(3d)	密封	—	H₂O/Al₂O₃=4∶1	H₃PO₄/Al₂O₃=1	SiO₂/Al₂O₃=1,d≤45μm	最大89.3	[48]
80℃(24h)、60℃(3d)	密封	—	H₂O/Al₂O₃=2∶1	H₃PO₄/Al₂O₃=1	SiO₂/Al₂O₃=3/1,200~1000℃(2h)	最大60	[48]
40℃(24h)、60℃(24h)	密封	85	L/S=1	P/Al=0.52~0.84	Si/Al=0.96	23.1~123.4	[50]
40℃(24h)、80℃(24h)	密封	85	L/S=1	P/Al=0.52~0.84	Si/Al=0.96	21.6~96.8	[50]
60℃(7d)	—	68	L/S=1.60~1.75	—	—	最大46.3	[51]
70℃(72h)	密封	85	0.45%~0.68%	Al/P=0.9~1.8	Si/Al=1	80~11	[52]
RT(7d)	密封	85	L/S=1	—	SiO₂/Al₂O₃=1.0~2.2	最大13.59	[53]
60℃(24h)、RT(7d、14d、28d)	—	85	L/S=0.67或1.25	P/Al=1	热活化或机械研磨	最大5.5	[55]
RT(7d)	密封	85	L/S=1	H₃PO₄/Al₂O₃=1.0~1.4	—	29	[60]
60℃(24h)、RT(28d)	干燥	10mol/L	L/S=1~1.2	Al/P=0.8~1.0	Si/Al=1.6,700~900℃(2h)	最大67	[64]

图6 27Al核磁共振谱去卷积法确定的原料和不同磷铝比样品中的Al结构单元[50]

图7 Al/P=1的具有不同水用量的样品XRD图谱[52]

图8 不同龄期的抗压强度分布

表2 金属氧化物增强磷酸基地质聚合物

原料	激发剂	氧化物	反应生成物	最大抗压强度/MPa	参考文献
偏高岭土	Al(H₂PO₄)₃	MgO（镁砂）	磷镁石（MgHPO₄·3H₂O）	53.07	[20]
偏高岭土	Al(H₂PO₄)₃	MgO（镁砂）	磷镁石（MgHPO₄·3H₂O）	53.07	[42]
偏高岭土	H₃PO₄（10mol/L）	Fe₂O₃（矿物相）	P—O—Si—O—Fe—O	56.4	[56]
富铁红土	H₃PO₄（10mol/L）	Fe₂O₃（矿物相）	无定形磷酸铁相	65	[57]
偏高岭土	Al(H₂PO₄)₃	MgO（重烧氧化镁）	镁磷石和无定形磷酸铝镁	13.6	[65]
偏高岭土	H₃PO₄(85%)	MgO	无定形凝胶相，掺量多则产生镁磷石	58.03	[66]
偏高岭土	H₃PO₄(85%)	Fe₃O₄	无定形凝胶	62.81	[66]
偏高岭土	Al(H₂PO₄)₃	Al₂O₃（纳米氧化铝）	非晶相磷酸铝	70.2	[67]

表3 纤维增强磷酸基地质聚合物

原料	激发剂	纤维	最佳掺量	抗压强度/MPa	抗弯强度/MPa	参考文献
偏高岭土	磷酸铝溶液	聚乙烯醇（PVA）短纤维	1.5%	—	13.86	[42]
偏高岭土	磷酸铝溶液	碳纤维片材	3层	—	31.32	[42]
偏高岭土	H₃PO₄（85%）	PI纤维（碳纳米管修饰）	1.5%	110.4	37.9	[68]
偏高岭土	H₃PO₄（85%）	玄武岩纤维	0.5%	3.4	0.7867	[69]
偏高岭土	H₃PO₄（85%）	玻璃纤维	1.3%	3.45	0.825	[69]
偏高岭土	H₃PO₄（85%）	杉木纤维	10%	—	13.7	[70]

图9 煅烧前后磷酸基地质聚合物样品的SEM图[66]

表4 磷酸基地质聚合物多孔材料

发泡剂	总孔隙率/%	热导率/W·m^-1·K^-1	抗压强度/MPa	体积密度/g·cm^-3	高温试验温度/℃	参考文献
石灰石粉	30.5~32.1	0.133	最大6	1.316~1.274	1000	[25]
H₂O₂(MnO₂)	42~56	0.17	2.09	0.66~0.76	1100	[69]
铝粉	40~83	—	6~13.7	—	1450	[71]
Triton X-100	78.3	—	0.64	0.43	1100	[74]
H₂O₂(MnO₂)	42~56	最小0.17	最大2.73	0.68~0.73	1100	[76]
H₂O₂	55~64	—	最大1.17	最小0.336	1100	[77]
石灰石粉	69~76	0.07~0.09	—	0.6~0.73	1000	[78]

图10 磷酸基地质聚合物样品在不同介质中浸泡28天后的外观[66]

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