多元组分对磷酸钾镁水泥高温下性能劣化的影响

doi:10.16552/j.cnki.issn1001-1625.2025.1276

摘要/Abstract

摘要：

磷酸钾镁水泥（MKPC）在高温作用下易发生水化产物脱水分解，从而引发强度衰减、体积收缩等劣化行为，限制了其在高温环境下的工程应用。为解决此问题，本文采用正交试验设计，系统研究了水胶比及硅溶胶掺量、膨胀蛭石掺量和玻璃微珠掺量对MKPC高温劣化行为的影响规律，并通过XRD、SEM和TG-DSC等微观测试分析了其作用机理。结果表明，膨胀蛭石与玻璃微珠在高温作用下可有效减缓强度衰减和体积收缩，是抑制MKPC高温下性能劣化的关键组分。当水胶比为0.25，硅溶胶、膨胀蛭石和玻璃微珠的掺量（质量分数）分别为5%、15%和12%时，MKPC在高温下表现出良好的强度稳定性和体积稳定性。微观分析结果表明，膨胀蛭石通过促进耐火硅酸盐相生成构建高温骨架结构，玻璃微珠则通过软化形成玻璃相增强颗粒间连接，二者协同作用，从物相组成和微观结构层面有效提升了MKPC的高温结构稳定性。

关键词: 磷酸钾镁水泥, 膨胀蛭石, 玻璃微珠, 硅溶胶, 耐高温性能, 正交试验

Abstract:

Magnesium potassium phosphate cement （MKPC） is prone to dehydration and decomposition of its hydration products under high-temperature exposure， which leads to strength degradation and volumetric shrinkage， thereby limiting its engineering applications in high-temperature environments. To address this issue， an orthogonal experimental design was employed to systematically investigate the effects of the water-to-binder ratio and the content of silica sol， expanded vermiculite， and glass beads on the performance degradation of MKPC under high-temperature. The underlying mechanisms were further elucidated through microstructural analyses using XRD， SEM， and TG-DSC. The results indicate that expanded vermiculite and glass beads can effectively mitigate strength loss and volumetric shrinkage under high-temperature conditions and are the key components for suppressing the performance degradation of MKPC under high-temperature. When the water-binder ratio is 0.25 and the dosages of silica sol， expanded vermiculite and glass beads are 5%， 15% and 12% （mass fractions）， respectively， MKPC exhibits excellent strength stability and volume stability at high temperatures. Microstructural analyses reveal that expanded vermiculite promotes the formation of refractory silicate phases to construct a stable high-temperature skeleton， while glass beads soften to form a glassy phase that enhances particle bonding. The synergistic effect of these two components effectively improves the high-temperature structural stability of MKPC from both phase composition and microstructural perspectives.

Key words: magnesium potassium phosphate cement, expanded vermiculite, glass beads, silica sol, high-temperature resistance, orthogonal experiment

中图分类号:

TQ526

周正, 周宇通, 赵洲峰, 裘吕超, 张士元, 王莉婷, 彭博, 蹇守卫, 谭洪波. 多元组分对磷酸钾镁水泥高温下性能劣化的影响[J]. 硅酸盐通报, 2026, 45(6): 1864-1875.

ZHOU Zheng, ZHOU Yutong, ZHAO Zhoufeng, QIU Lyuchao, ZHANG Shiyuan, WANG Liting, PENG Bo, JIAN Shouwei, TAN Hongbo. Influences of Multiple Components on Performance Deterioration of Magnesium Potassium Phosphate Cement under High-Temperature[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(6): 1864-1875.

图/表 18

表1 原材料的主要化学组成

Table 1 Main chemical composition of raw materials

Material	Mass fraction/%
Material	MgO	SiO₂	CaO	Fe₂O₃	Al₂O₃	K₂O	Na₂O	LOI
Dead-burned MgO	89.717	3.409	1.979	1.684	0.893	0.037	—	1.808
Glass beads	—	82.353	8.897	0.136	0.123	0.006	1.381	6.944
Expanded vermiculite	12.378	44.079	3.358	13.624	17.253	5.238	—	4.057

图1 原材料的XRD谱

Fig.1 XRD patterns of raw materials

表2 MKPC正交试验因素水平设计

Table 2 Factor level design for MKPC orthogonal tests

Factor	Level 1	Level 2	Level 3
Water-binder ratio （A）	0.25	0.30	0.35
Silica sol content （B）/%	3	4	5
Expanded vermiculite content （C）/%	5	10	15
Glass beads content （D）/%	4	8	12

表3 MKPC正交试验配合比设计

Table 3 Mix ratio design for MKPC orthogonal tests

Number	Sample	Mass/g			A	B/%	C/%	D/%
Number	Sample	KH₂PO₄	MgO	Borax	A	B/%	C/%	D/%
1	A1B1C1D1	2 118.4	1 881.6	320	0.25	3	5	4
2	A1B2C2D2				0.25	4	10	8
3	A1B3C3D3				0.25	5	15	12
4	A2B1C2D3				0.30	3	10	12
5	A2B2C3D1				0.30	4	15	4
6	A2B3C1D2				0.30	5	5	8
7	A3B1C3D2				0.35	3	15	8
8	A3B2C1D3				0.35	4	5	12
9	A3B3C2D1				0.35	5	10	4

图2 不同因素对MKPC工作性能的影响规律

Fig.2 Influences of different factors on working performance of MKPC

表4 不同因素对MKPC工作性能影响的极差分析

Table 4 Range analysis of influences of different factors on working performance of MKPC

Experimental index	R_A	R_B	R_C	R_D	Influence sequence
Initial setting time/min	59.58	12.34	10.40	19.50	A>D>B>C
Final setting time/min	105.74	33.69	55.55	56.03	A>D>C>B
Fluidity/mm	27.00	11.00	33.33	9.67	C>A>B>D

图3 不同因素对MKPC力学性能的影响

Fig.3 Influences of different factors on mechanical properties of MKPC

表5 不同因素对MKPC力学性能的极差分析

Table 5 Range analysis of influences of different factors on mechanical properties of MKPC

Experimental index	R_A	R_B	R_C	R_D	Influence sequence
Compressive strength/MPa	5.07	2.38	1.57	3.07	A>D>B>C
Bonding strength/MPa	0.26	0.08	0.15	0.21	A>D>C>B

图4 高温处理后不同因素对MKPC抗压强度的影响

Fig.4 Influences of different factors on compressive strength of MKPC after high-temperature treatment

表6 不同因素对MKPC高温处理后抗压强度的极差分析

Table 6 Range analysis of influences of different factors on compressive strength of MKPC after high-temperature treatment

Temperature/℃	Compressive strength/MPa				Influence sequence
Temperature/℃	R_A	R_B	R_C	R_D	Influence sequence
800	1.29	0.38	0.94	0.98	A>D>C>B
1 000	1.55	0.53	1.15	2.37	D>A>C>B
1 200	1.21	0.50	0.58	0.73	A>D>C>B

图5 不同因素对高温处理后MKPC体积收缩率的影响

Fig.5 Influences of different factors on volume shrinkage rate of MKPC after high-temperature treatment

表7 不同因素对MKPC高温处理后体积收缩率影响的极差分析

Table 7 Range analysis of influences of different factors on volume reduction rate of MKPC after high-temperature treatment

Temperature/℃	Volume reduction rate/%				Influence sequence
Temperature/℃	R_A	R_B	R_C	R_D	Influence sequence
800	0.84	0.43	1.37	0.93	C>D>A>B
1 000	0.58	0.12	1.78	1.26	C>D>A>B
1 200	0.96	0.30	1.52	0.63	C>A>D>B

图6 不同温度处理后A1B3C3D3样品的XRD谱

Fig.6 XRD patterns of A1B3C3D3 samples after heat treatment at different temperatures

图7 不同温度处理后A1B3C3D3样品的SEM照片

Fig.7 SEM images of A1B3C3D3 samples after heat treatment at different temperatures

图8 1 000 ℃处理后A1B3C3D3样品的EDS照片

Fig.8 EDS image of A1B3C3D3 sample after heat treatment at 1 000 ℃

表8 EDS点扫描元素含量分布

Table 8 EDS point scan element content distribution

Element	Mass fraction/%
Element	Point 1	Point 2	Point 3	Point 4	Point 5
O	44.49	38.15	30.23	46.76	29.45
Mg	31.01	13.91	26.26	10.76	24.88
Al	0.27	0.21	1.26	—	1.87
Si	20.10	0.28	20.68	—	28.98
P	1.02	20.86	0.95	14.93	0.80
K	1.73	25.44	6.13	27.55	6.22
Ca	0.19	0.84	3.27	—	2.88
Fe	1.18	0.31	11.23	—	4.93

图9 A1B3C3D3样品的TG-DSC曲线

Fig.9 TG-DSC curve of A1B3C3D3 sample

图10 磷酸钾镁耐高温性能提升机理

Fig.10 Mechanism for improving high-temperature resistance of magnesium potassium phosphate

参考文献 24

[1]	DAI X B， REN W X， QIN J H， et al. Influence and mechanism of borax on the physico-mechanical properties of magnesium potassium phosphate cement exposed to high temperatures［J］. Construction and Building Materials， 2023， 376： 131015. DOI URL
[2]	QIAN W Y， SUN W， GUO S， et al. Effect of temperature variation on bonding properties of magnesium potassium phosphate cement： a multiscale analysis［J］. Case Studies in Construction Materials， 2024， 21： e03993.
[3]	唐浩. 磷酸镁水泥基材料的钢筋防护性能与机理研究［D］. 重庆：重庆大学， 2021.
	TANG H. Study on steel bar protection performance and mechanism of magnesium phosphate cement-based materials［D］. Chongqing： Chongqing University， 2021 （in Chinese）.
[4]	LAI Z Y， CHEN J W， YU Y P， et al. Effect of magnesium hydroxide on the properties of fireproof coatings for steel structure based on magnesium phosphate cement［J］. Case Studies in Construction Materials， 2024， 21： e03853.
[5]	艾红红. 磷酸钾镁水泥防火板性能及机理研究［D］. 福州：福州大学， 2016.
	AI H H. Study on properties and mechanism of magnesium potassium phosphate cement fireproof board［D］. Fuzhou： Fuzhou University， 2016 （in Chinese）.
[6]	LI Y， WANG N， LONG S R， et al. Research on the properties of brucite-based magnesium phosphate cement fire resistive coating for steel structures［J］. Construction and Building Materials， 2024， 449： 138481. DOI URL
[7]	WANG D Q， YUE Y F， MI T W， et al. Effect of magnesia-to-phosphate ratio on the passivation of mild steel in magnesium potassium phosphate cement［J］. Corrosion Science， 2020， 174： 108848. DOI URL
[8]	FANG B D， HU Z J， SHI T， et al. Research progress on the properties and applications of magnesium phosphate cement［J］. Ceramics International， 2023， 49（3）： 4001-4016. DOI URL
[9]	李军. 侵蚀环境下磷酸铵镁水泥基涂料的耐久性能及机理研究［D］. 徐州：中国矿业大学， 2018.
	LI J. Study on durability performance and mechanism of magnesium ammonium phosphate cement-based coating in corrosive environment［D］. Xuzhou： China University of Mining and Technology， 2018 （in Chinese）.
[10]	YAN K， YU X， REN P F， et al. Experimental research on fire resistance of the concrete beams strengthened with the CFRP sheets pasted by magnesium phosphate inorganic adhesive［J］. Engineering Structures， 2025， 330： 119946. DOI URL
[11]	WANG X， HU X， YANG J M， et al. Research progress on interfacial bonding between magnesium phosphate cement and steel： a review［J］. Construction and Building Materials， 2022， 342： 127925. DOI URL
[12]	邵晓燕. 磷酸钾镁水泥基钢结构防火涂料的制备研究［D］. 福州：福州大学， 2017.
	SHAO X Y. Study on preparation of magnesium potassium phosphate cement-based fireproof coating for steel structure［D］. Fuzhou： Fuzhou University， 2017 （in Chinese）.
[13]	FANG Y， YIN X H， CUI P， et al. Properties of magnesium potassium phosphate cement-expanded perlite composites applied as fire resistance coating［J］. Construction and Building Materials， 2021， 293： 123513. DOI URL
[14]	YANG Y Q， LIU Y， YAN Z Z， et al. High-temperature resistance of modified potassium magnesium phosphate cement［J］. Materials， 2022， 15（24）： 8967. DOI URL
[15]	温婧. MKPC基钢结构防火涂料组成结构设计及其防火性能评价［D］. 淮南：安徽理工大学， 2020.
	WEN J. Composition and structure design of MKPC-based fireproof coating for steel structure and its fireproof performance evaluation［D］. Huainan： Anhui University of Science and Technology， 2020 （in Chinese）.
[16]	FANG C， WEN J， LI Y， et al. Effects of the modified expanded perlite materials on magnesium phosphate cement-based fireproof mortars： mechanical property， thermal conductivity and microstructure［J］. Case Studies in Construction Materials， 2025， 22： e04140.
[17]	张爱莲. 磷酸镁水泥的耐高温改性及粘贴碳纤维布面内剪切性能研究［D］. 哈尔滨：哈尔滨工业大学， 2017.
	ZHANG A L. Study on high-temperature modification of magnesium phosphate cement and in-plane shear performance of bonded carbon fiber cloth［D］. Harbin： Harbin Institute of Technology， 2017 （in Chinese）.
[18]	陈新，陈士堃，闫东明，等. 磷酸镁涂层高温后力学性能研究［J］. 硅酸盐通报， 2022， 41（3）： 1031-1038.
	CHEN X， CHEN S K， YAN D M， et al. Mechanical properties of magnesium phosphate coatings after high temperature［J］. Bulletin of the Chinese Ceramic Society， 2022， 41（3）： 1031-1038 （in Chinese）.
[19]	李晓，赵莹莹，故丽孜巴·阿不都热西提，等. 磷酸镁水泥高温性能研究进展［J］. 材料导报， 2024， 38（17）： 41-48.
	LI X， ZHAO Y Y， GULIZIBA‧ABUDUREXITI， et al. Research progress on high-temperature performance of magnesium phosphate cement［J］. Materials Reports， 2024， 38（17）： 41-48 （in Chinese）.
[20]	刘志. 基于CFD-FEM的钢结构桥梁火灾响应研究［D］. 南京：东南大学， 2021.
	LIU Z. Study on fire response of steel structure bridge based on CFD-FEM［D］. Nanjing： Southeast University， 2021 （in Chinese）.
[21]	黄迪. 基于火灾随机性的高大空间钢结构建筑多风险分析［D］. 徐州：中国矿业大学， 2019.
	HUANG D. Multi-risk analysis of tall and large space steel structure buildings based on fire randomness［D］. Xuzhou： China University of Mining and Technology， 2019 （in Chinese）.
[22]	GARDNER L J， WALLING S A， CORKHILL C L， et al. Temperature transformation of blended magnesium potassium phosphate cement binders［J］. Cement and Concrete Research， 2021， 141： 106332. DOI URL
[23]	BANERJEE R H， NELWAMONDO S M M， RAJE N， et al. Radiation stability testing of hydrated and heat-treated magnesium potassium phosphates for back end nuclear fuel cycle applications［J］. Ceramics International， 2024， 50（1）： 2405-2414. DOI URL
[24]	GAO X J， ZHANG A L， LI S X， et al. The resistance to high temperature of magnesia phosphate cement paste containing wollastonite［J］. Materials and Structures， 2016， 49（8）： 3423-3434. DOI URL