外加剂对磷石膏霉变的影响机制研究

doi:10.16552/j.cnki.issn1001-1625.2026.0180

摘要/Abstract

摘要：

磷石膏制品霉变不仅会威胁人体健康，还会导致材料本身性能显著劣化。本文从磷石膏制品生产中常见的外加剂出发，研究了外加剂种类及掺量对磷石膏霉变的影响规律，通过XRF、EA、SEM、静态接触角等测试方法进行表征，进而初探磷石膏霉变机理。结果表明：减水剂掺量越高，磷石膏霉变率越高，在相同掺量条件下，萘系减水剂相较于聚羧酸减水剂更容易使磷石膏产生霉变；防水剂掺量越高，磷石膏霉变率越低，防水剂在一定程度上可提高防霉性能；磷石膏表面环境pH值越高，实验所选的六种菌种更易生长，磷石膏更易产生霉变；外加剂掺入所引入的C元素是加速霉变的主要元素，其次是N元素，K、Mg、Al、P作为微生物生长所需的大量元素对霉变有一定影响，但作用较小。

关键词: 磷石膏, 减水剂, 防水剂, 生石灰, 霉变机理, 霉变率

Abstract:

Mildew on phosphogypsum products not only poses a threat to human health but also causes significant deterioration of material properties. This study was investigated the influence mechanism of additive types and dosages on the mildew of phosphogypsum， based on commonly using additives in the production of phosphogypsum products. The samples were characterized using XRF， EA， SEM， and static contact angle measurements to preliminarily explore the mildew mechanism of phosphogypsum. The results indicate that a higher dosage of water reducer accelerates the mildew rate of phosphogypsum. At the same dosage， naphthalene-based water reducer is more likely to induce mildew on phosphogypsum compared to polycarboxylate-based water reducer. A higher dosage of waterproofing agent slightly reduces the mildew rate， suggesting that waterproofing agent can improve mildew resistance to a certain extent. Increasing the surface environmental pH of phosphogypsum promotes the growth of the six selected fungal strains， making the material more susceptible to mildew. The carbon （C） element introduced by additives is the primary factor accelerating mildew， followed by nitrogen （N）. Elements such as K， Mg， Al， and P， which are macronutrients required for microbial growth， have a certain influence on mildew， but their effects are relatively minor.

Key words: phosphogypsum, water reducer, waterproofing agent, quicklime, mildew mechanism, mildew rate

中图分类号:

TQ177

程晓, 武发德, 王宏霞, 宋晓光, 高春勇, 郭君华, 李帆. 外加剂对磷石膏霉变的影响机制研究[J]. 硅酸盐通报, 2026, 45(8): 2839-2849.

CHENG Xiao, WU Fade, WANG Hongxia, SONG Xiaoguang, GAO Chunyong, GUO Junhua, LI Fan. Influence Mechanism of Additives on Mildew of Phosphogypsum[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(8): 2839-2849.

图/表 22

表1 磷石膏的主要化学组成

Table 1 Main chemical composition of phosphogypsum

Composition	CaO	SO₃	SiO₂	Al₂O₃	P₂O₅	Fe₂O₃	Na₂O	F	K₂O	TiO₂	MgO	SrO
Mass fraction/%	40.80	48.90	5.65	0.77	0.72	0.42	0.37	0.37	0.21	0.14	0.12	0.10

图1 磷石膏的XRD谱

Fig.1 XRD pattern of phosphogypsum

表2 实验菌种类型

Table 2 Bacterial type used in experiment

Name	Bacterial No.
黑曲霉（Aspergillus niger）	AS3.4463
土曲霉（Aspergillus terreus）	AS3.3935
宛氏拟青霉（Paecilomyces Varioti）	AS3.4253
绳状青霉（Penicillium funicolosum）	AS3.3875
出芽短梗霉（Aureobasium Pullulans）	AS3.3984
球毛壳（Chaetoomium globsum）	AS3.4254

表3 营养盐培养液成分

Table 3 Composition of nutrient salt culture solution

Ingredient	NaNO₃	KH₂PO₄	K₂HPO₄	KCl	MgSO₄·7H₂O	FeSO₄·7H₂O	Sucrose
Mass/g	2.00	0.70	0.30	0.50	0.50	0.01	5.00

图2 霉变实验试样放置示意图

Fig.2 Schematic diagram of placement of mildew test specimens

图3 FDN掺量对磷石膏14 d霉变率的影响

Fig.3 Effect of FDN dosage on 14 d mildew rate of phosphogypsum

图4 不同掺量FDN试样第14天霉变情况

Fig.4 Mildew condition of specimens with different FDN dosages at 14 d

图5 PCE掺量对磷石膏14 d霉变率的影响

Fig.5 Effect of PCE dosage on 14 d mildew rate of phosphogypsum

图6 不同掺量PCE试样第14天霉变情况

Fig.6 Mildew condition of specimens with different PCE dosages at 14 d

表4 试样霉变前后有机物元素EA测试分析结果

Table 4 EA test analysis results of organic elements in specimens before and after mildew

Specimen category	Element content/%
Specimen category	N	C	H	S	O
Blank control group	0	0.29	1.65	16.24	36.58
0.5% FDN specimen before mildew	0.03	0.58	1.91	10.53	36.60
0.5% FDN specimen after mildew	0	0	1.53	13.40	29.66
0.5% PCE specimen before mildew	0.05	0.42	2.02	8.28	40.13
0.5% PCE specimen after mildew	0	0	1.57	6.92	30.14

表5 试样霉变前后XRF测试分析结果

Table 5 XRF test analysis results of specimens before and after mildew

Specimen category	Element content/%
Specimen category	Ca	S	Si	Fe	K	P	Mg	Al	Sr	Y
Blank control group	53.948	37.995	1.582	0.608	0.575	0.956	0.315	0.231	0.187	0.010
0.5% FDN specimen before mildew	60.235	35.983	1.391	0.665	0.576	0.408	0.338	0.210	0.184	0.011
0.5% FDN specimen after mildew	61.632	35.446	1.177	0.643	0.388	0.182	0.151	0.180	0.190	0.011
0.5% PCE specimen before mildew	61.154	35.919	1.074	0.692	0.378	0.309	0.155	0.124	0.185	0.010
0.5% PCE specimen after mildew	61.057	35.620	1.190	0.695	0.377	0.361	0.121	0.136	0.186	0.012

图7 掺入0.5%减水剂的试样霉变前后的SEM照片

Fig.7 SEM images of specimens with 0.5% water reducer before and after mildew

图8 不同掺量防水剂试样的接触角

Fig.8 Contact angles of specimens with different waterproofing agent dosages

图9 防水剂掺量对磷石膏14 d霉变率的影响

Fig.9 Effect of waterproofing agent dosage on 14 d mildew rate of phosphogypsum

图10 不同掺量防水剂试样第14天霉变情况

Fig.10 Mildew condition of specimens with different waterproofing agent dosages at 14 d

表6 试样霉变前后有机物元素EA测试分析结果

Table 6 EA test analysis results of organic elements in specimens before and after mildew

Specimen category	Element content/%
Specimen category	N	C	H	S	O
Blank control group	0	0.29	1.65	16.24	36.58
1.00% waterproofing agent specimen before mildew	0.09	0.45	2.05	15.45	39.42
1.00% waterproofing agent specimen after mildew	0	0	1.86	11.73	29.69

表7 试样霉变前后XRF测试分析结果

Table 7 XRF test analysis results of specimens before and after mildew

Specimen category	Element content/%
Specimen category	Ca	S	Si	Fe	K	P	Mg	Al	Sr	Y
Blank control group	53.948	37.995	1.582	0.608	0.575	0.956	0.315	0.231	0.187	0.010
1.00% waterproofing agent specimen before mildew	58.248	35.303	2.781	0.640	0.917	0.602	0.728	0.594	0.177	0.010
1.00% waterproofing agent specimen after mildew	60.302	35.396	2.486	0.652	0.268	0.301	0.093	0.308	0.183	0.010

图11 掺入1.00%防水剂的试样霉变前后的SEM照片

Fig.11 SEM images of specimens with 1.00% waterproofing agent before and after mildew

表8 不同掺量pH调节剂试样的pH值

Table 8 pH values of specimens with different pH regulator dosages

Dosage/%	0	0.1	0.2	0.3	0.4	0.5
pH value	5.40	6.02	6.33	7.43	9.52	10.52

图12 pH调节剂掺量对磷石膏14 d霉变率的影响

Fig.12 Effect of pH regulator dosage on 14 d mildew rate of phosphogypsum

图13 不同掺量pH调节剂试样第14天霉变情况

Fig.13 Mildew condition of specimens with different pH regulator dosages at 14 d

图14 掺入0.5% pH调节剂的试样霉变前后的SEM照片

Fig.14 SEM images of specimens with 0.5% pH regulator before and after mildew

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