复配抗霉剂与碱性激发材料制备抗霉型磷石膏及机理研究

doi:10.16552/j.cnki.issn1001-1625.2026.0209

摘要/Abstract

摘要：

磷石膏建材在温热潮湿地区易发生霉菌污染，其综合利用受到制约。针对该问题，本文构建了十四烷基三甲基氯化铵（TTAC）和聚六亚甲基双胍盐酸盐（PHMB）复配的有机抗霉体系，并与CaO-矿渣-铝酸盐水泥碱性激发体系耦合，以协同提升磷石膏的抗霉性能与力学性能；通过微观分析和理论计算建立抗霉模型，探讨霉菌抑制机理。结果表明，TTAC与PHMB通过“破膜-渗透”协同效应，使联合抑菌指数降至0.15~0.75，最低抑菌浓度显著降低。碱性激发体系通过引导钙矾石与水化硅酸钙（C-S-H）凝胶生成，将基体平均孔径细化至0.104 μm，并形成致密的物理屏障。抗霉剂通过“静电锚定-氢键交联”机制稳定固载于凝胶网络中，与孔隙屏障及碱性环境共同形成物理阻隔、化学缓释与代谢抑制三重协同抗霉机制。优化配比后，试块在28 d高湿环境中能保持0级防霉，抗压强度为11.7 MPa，软化系数达0.72，可提升磷石膏墙材品质，促进磷石膏规模化消纳。

关键词: 磷石膏, 抗霉性能, 协同增效, 有机抗霉剂, 碱性激发胶凝材料, 墙体材料

Abstract:

Phosphogypsum building materials are prone to mold contamination in warm and humid regions， which restricts their comprehensive utilization. To address this issue， an organic antifungal system composed of tetradecyltrimethylammonium chloride （TTAC） and polyhexamethylene biguanide hydrochloride （PHMB） was developed in this study， and coupled with a CaO-slag-aluminate cement alkali-activated system to synergistically improve the mold resistance and mechanical performance of phosphogypsum. An antifungal model was established through microstructural analysis and theoretical calculation， and the mold inhibition mechanism was discussed. The results show that the synergistic "membrane disruption-penetration" effect of TTAC and PHMB reduces the combined fungistatic index to 0.15 to 0.75， significantly lowering the minimum inhibitory concentration. The alkali-activated system refines the average pore diameter of the matrix to 0.104 μm by promoting the formation of ettringite and C-S-H gel， forming a dense physical barrier. The antifungal agents are stably immobilized in the gel network via the "electrostatic anchoring-hydrogen bond crosslinking" mechanism， which， together with the pore barrier and alkaline environment， constitutes a triple synergistic antifungal mechanism involving physical barrier， chemical sustained release and metabolic inhibition. After optimization， the specimens maintain Grade 0 mold resistance in a high-humidity environment for 28 d， with a compressive strength of 11.7 MPa and a softening coefficient of 0.72， which improves the quality of phosphogypsum wall materials and promotes the large-scale consumption of phosphogypsum.

Key words: phosphogypsum, mold resistance, synergistic enhancement, organic antifungal agent, alkali-activated cementitious material, wall material

中图分类号:

TQ177.5

彭祝, 李子玲, 丁友, 程金科, 张煜. 复配抗霉剂与碱性激发材料制备抗霉型磷石膏及机理研究[J]. 硅酸盐通报, 2026, 45(9): 3202-3221.

PENG Zhu, LI Ziling, DING You, CHENG Jinke, ZHANG Yu. Preparation and Mechanism of Mold-Resistant Phosphogypsum Using Composite Antifungal Agents and Alkali-Activated Materials[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(9): 3202-3221.

图/表 21

参考文献 34

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Modified system		Modified substance	Relationship between sample number and dosage of modified substances
Modified system		Modified substance	W₁	W₂	W₃	W₄	W₅	W₆	W₇	W₈	W₉	W₁₀	W₁₁	W₁₂
Blank CPG（W₀）		—	—	—	—	—	—	—	—	—	—	—	—	—
Modified system of organic antifungal agents	CPG-TTAC	TTAC	0.25	0.5	1	2	4	—	—	—	—	—	—	—
	CPG-PHMB	PHMB	0.25	0.5	1	2	4	—	—	—	—	—	—	—
	CPG-TTAC-PHMB	TTAC	0.25	0.25	0.25	0.25	0.5	0.5	0.5	0.5	1	1	1	1
	CPG-TTAC-PHMB	PHMB	0.25	0.5	1	2	0.25	0.5	1	2	0.25	0.5	1	2
Modified system of alkali-activated cementitiou materials	CPG-CaO-GGBS-CA	CaO	3	3	—	—	—	—	—	—	—	—	—	—
		GGBS	15	15	—	—	—	—	—	—	—	—	—	—
		CA	6	9	—	—	—	—	—	—	—	—	—	—
Composite synergistic modification system	CPG-TTAC-PHMB-CaO-GGBS-CA	TTAC	0.25	0. 5	0.5	1	0.25	0.5	0.5	1	—	—	—	—
		PHMB	0.5	0.25	2	2	0.5	0.25	2	2	—	—	—	—
		CaO	3	3	3	3	3	3	3	3	—	—	—	—
		GGBS	15	15	15	15	15	15	15	15	—	—	—	—
		CA	6	6	6	6	9	9	9	9	—	—	—	—

Modified system		Modified substance	Relationship between sample number and dosage of modified substances
Modified system		Modified substance	W₁	W₂	W₃	W₄	W₅	W₆	W₇	W₈	W₉	W₁₀	W₁₁	W₁₂
Blank CPG（W₀）		—	—	—	—	—	—	—	—	—	—	—	—	—
Modified system of organic antifungal agents	CPG-TTAC	TTAC	0.25	0.5	1	2	4	—	—	—	—	—	—	—
	CPG-PHMB	PHMB	0.25	0.5	1	2	4	—	—	—	—	—	—	—
	CPG-TTAC-PHMB	TTAC	0.25	0.25	0.25	0.25	0.5	0.5	0.5	0.5	1	1	1	1
	CPG-TTAC-PHMB	PHMB	0.25	0.5	1	2	0.25	0.5	1	2	0.25	0.5	1	2
Modified system of alkali-activated cementitiou materials	CPG-CaO-GGBS-CA	CaO	3	3	—	—	—	—	—	—	—	—	—	—
		GGBS	15	15	—	—	—	—	—	—	—	—	—	—
		CA	6	9	—	—	—	—	—	—	—	—	—	—
Composite synergistic modification system	CPG-TTAC-PHMB-CaO-GGBS-CA	TTAC	0.25	0. 5	0.5	1	0.25	0.5	0.5	1	—	—	—	—
		PHMB	0.5	0.25	2	2	0.5	0.25	2	2	—	—	—	—
		CaO	3	3	3	3	3	3	3	3	—	—	—	—
		GGBS	15	15	15	15	15	15	15	15	—	—	—	—
		CA	6	6	6	6	9	9	9	9	—	—	—	—

Mold	MIC/（μg·mL^-1）				FICI	Synergistic interaction
Mold	TTAC	PHMB	TTAC+PHMB（TTAC）	TTAC+PHMB（PHMB）	FICI	Synergistic interaction
Aspergills niger	100	12.5	12.5	0.78	0.156 2	Synergism
Trichodema virid	3.13	25	0.39	6.25	0.376 4	Synergism
Penicillim citrinum	12.5	25	6.25	6.25	0.750 0	Additivity

Mold	MIC/（μg·mL^-1）				FICI	Synergistic interaction
Mold	TTAC	PHMB	TTAC+PHMB（TTAC）	TTAC+PHMB（PHMB）	FICI	Synergistic interaction
Aspergills niger	100	12.5	12.5	0.78	0.156 2	Synergism
Trichodema virid	3.13	25	0.39	6.25	0.376 4	Synergism
Penicillim citrinum	12.5	25	6.25	6.25	0.750 0	Additivity

Modified system	PHMB dosage/%	Antifungal agent ratio （m（TTAC）∶m（PHMB））	7 d		14 d		21 d		28 d
Modified system	PHMB dosage/%	Antifungal agent ratio （m（TTAC）∶m（PHMB））	I_r/%	Level	I_r/%	Level	I_r/%	Level	I_r/%	Level
CPG	—	—	100.00	4	100.00	4	100.00	4	100.00	4
CPG-0.25%TTAC- PHMB	0.062 5	4∶1	35.10	2	60.07	3	66.82	4	67.25	4
	0.125	2∶1	30.14	2	59.63	3	62.41	4	63.77	4
	0.25	1∶1	27.61	2	57.15	3	65.20	4	65.83	4
	0.5	1∶2	39.43	3	44.32	3	52.71	3	56.53	3
	1	1∶4	9.31	1	20.97	2	25.34	2	26.02	2
CPG-0.5%TTAC- PHMB	0.125	4∶1	42.03	3	45.61	3	34.51	3	58.34	3
	0.25	2∶1	26.91	2	41.43	3	41.62	3	45.82	3
	0.5	1∶1	17.35	2	33.25	3	36.09	3	37.41	3
	1	1∶2	11.52	2	13.24	2	15.21	2	17.33	2
	2	1∶4	0	0	0	0	0	0	0	0
CPG-1%TTAC-PHMB	0.25	4∶1	0	0	2.41	1	2.63	1	2.74	1
	0.5	2∶1	0	0	0.77	1	0.82	1	0.91	1
	1	1∶1	0	0	0.28	1	0.23	1	0.42	1
	2	1∶2	0	0	0.17	1	0.18	1	0.26	1
	4	1∶4	0	0	0	0	0	0	0	0
CPG-2%TTAC-PHMB	0.5	4∶1	0	0	1.52	1	1.76	1	2.43	1
	1	2∶1	0	0	0.72	1	0.76	1	0.84	1
	2	1∶1	0	0	0	0	0.33	1	0.46	1
	4	1∶2	0	0	0	0	0	0	0	0
	8	1∶4	0	0	0	0	0	0	0	0
CPG-4%TTAC-PHMB	1	4∶1	0.65	1	0.70	1	0.75	1	0.77	1
	2	2∶1	0	0	0.36	1	0.48	1	0.57	1
	4	1∶1	0	0	0.27	1	0.32	1	0.40	1
	8	1∶2	0	0	0	0	0	0	0	0
	16	1∶4	0	0	0	0	0	0	0	0