聚乙烯醇改性矿渣粉-粉煤灰基碱激发胶凝材料水化性能研究

doi:10.16552/j.cnki.issn1001-1625.2025.1009

摘要/Abstract

摘要：

碱激发材料虽具有较低的温室气体排放量，且力学性能与硅酸盐水泥相当，但存在干燥收缩大、易开裂、性能波动明显等问题。通过掺入聚乙烯醇（PVA）可有效降低干燥收缩、提高抗折强度与韧性，并促进结构致密化。本研究系统考察了不同PVA掺量（0%、2.5%、5.0%、7.5%、10.0%，质量分数）对矿渣粉-粉煤灰基碱激发胶凝材料流动度、凝结时间、水化热、抗压强度、抗折强度、干燥收缩、质量损失、pH值、吸水率及微观结构的影响。结果表明：随着PVA掺量增加，浆体流动度降低，终凝时间延长；水化放热速率与累计放热量均下降；抗压强度随着PVA掺量提高而降低，而养护28 d后抗折强度升高，其中PVA掺量为5.0%时，抗折强度最高（6.63 MPa）；当PVA掺量不大于5.0%时，干燥收缩有所减小，当PVA掺量超过5.0%则干燥收缩增大；PVA的引入还会导致浆体pH值下降、吸水率上升。微观分析表明，PVA膜与水化产物相互包裹、填充，形成复合结构，增强了材料的致密性。本研究明确了PVA对碱激发胶凝材料水化行为与宏观性能的调控作用，为其工程应用提供了依据。

关键词: 聚乙烯醇, 碱激发胶凝材料, 水化性能, 干燥收缩, 抗折强度, 微观形貌

Abstract:

Although alkali-activated cementitious materials exhibit lower greenhouse gas emissions and mechanical properties comparable to those of Portland cement， they suffer from problems such as significant drying shrinkage， susceptibility to cracking， and notable performance fluctuations. Incorporating polyvinyl alcohol （PVA） can effectively reduce drying shrinkage， enhance flexural strength and toughness， and promote structural densification. This study systematically investigated the effects of different PVA content （0%， 2.5%， 5.0%， 7.5%， and 10.0%， mass fraction） on the fluidity， setting time， hydration heat， compressive strength， flexural strength， drying shrinkage， mass loss， pH value， water absorption rate， and microstructure of slag-fly ash-based alkali-activated cementitious materials. The results show that as the PVA content increases， the paste fluidity decreases and the final setting time is prolonged； both the hydration heat release rate and cumulative heat release decrease； the compressive strength decreases with higher PVA content， whereas the flexural strength improves after 28 d of curing， with the highest flexural strength （6.63 MPa） achieved at a PVA content of 5.0%； drying shrinkage is reduced when the PVA content does not exceed 5.0%， but increases when the content exceeds 5.0%； the introduction of PVA also leads to a decrease in paste pH value and an increase in water absorption rate. Microstructural analysis indicates that PVA films and hydration products mutually encapsulate and fill each other， forming a composite structure that enhances the microscopic densification of the material. This study clarifies the regulatory effect of PVA on the hydration behavior and macroscopic properties of alkali-activated cementitious materials， providing a basis for their engineering applications.

Key words: polyvinyl alcohol, alkali-activated cementitious material, hydration property, drying shrinkage, flexural strength, microstructure

中图分类号:

TQ177

李秉函, 李世纪, 赵伊萌, 刘云鹏, 许达, 赵淑丽. 聚乙烯醇改性矿渣粉-粉煤灰基碱激发胶凝材料水化性能研究[J]. 硅酸盐通报, 2026, 45(5): 1638-1649.

LI Binghan, LI Shiji, ZHAO Yimeng, LIU Yunpeng, XU Da, ZHAO Shuli. Hydration Properties of Polyvinyl Alcohol-Modified Slag-Fly Ash-Based Alkali-Activated Cementitious Materials[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(5): 1638-1649.

图/表 19

表1 矿渣粉、粉煤灰的主要化学组成

Table 1 Main chemical composition of slag and fly ash

Material	Mass fraction/%
Material	SiO₂	Al₂O₃	Fe₂O₃	CaO	TiO₂	K₂O	SO₃	MgO	P₂O₃	Na₂O
Slag	29.43	14.38	0.90	44.50	1.61	0.35	2.34	5.49	0.03	0.28
Fly ash	48.70	35.90	5.06	3.88	0.70	1.36	0.80	0.61	0.50	0.38

表2 聚乙烯醇的性能指标

Table 2 Performance indexes of PVA

Test item

Methylation degree

（mass fraction）/%

Viscosity/（MPa·s）

Volatile matter

（mass fraction）/%

Purity（mass fraction）/%

表3 聚乙烯醇改性矿渣粉-粉煤灰基碱激发胶凝材料的配合比

Table 3 Mix proportion of PVA-modified slag-fly ash-based alkali-activated cementitious materials

Group	Mass/g				Water-binder ratio
Group	Slag	Fly ash	PVA	Na₂O	Water-binder ratio
PVA0	80	20	0	3	0.4
PVA1	80	20	2.5	3	0.4
PVA2	80	20	5.0	3	0.4
PVA3	80	20	7.5	3	0.4
PVA4	80	20	10.0	3	0.4

图1 聚乙烯醇改性矿渣粉-粉煤灰基碱激发复合

Fig.1 Fluidity of PVA-modified slag-fly ash-based alkali-activated composite paste

图2 聚乙烯醇改性矿渣粉-粉煤灰基碱激发复合净浆的流动度净浆的凝结时间

Fig.2 Setting time of PVA-modified slag-fly ash-based alkali-activated composite paste

图3 PVA掺量对聚乙烯醇改性碱激发胶凝材料

Fig.3 Effect of PVA content on hydration heat release rate of PVA-modified alkali-activated cementitious materials

图4 PVA掺量对聚乙烯醇改性碱激发胶凝材料水化放热速率的影响水化放热的影响

Fig.4 Effect of PVA content on hydration heat release of PVA-modified alkali-activated cementitious materials

图5 净浆试块抗压强度随时间变化的发展规律

Fig.5 Development law of compressive strength of neat paste specimens over time

表4 相对抗压强度与相对抗折强度

Table 4 Relative compressive strength and relative flexural strength

Age/d	Sample	CON（strength）	2.5%PVA	5.0%PVA	7.5%PVA	10.0%PVA
3	Compressive strength	1	0.836	0.731	0.485	0.289
3	Flexural strength	1	0.626	0.602	0.579	0.390
7	Compressive strength	1	0.911	0.826	0.604	0.398
7	Flexural strength	1	0.583	0.581	0.604	0.352
14	Compressive strength	1	0.860	0.738	0.635	0.495
14	Flexural strength	1	0.964	1.111	1.054	0.697
28	Compressive strength	1	0.890	0.844	0.686	0.533
28	Flexural strength	1	1.139	1.295	1.230	1.049

图6 聚乙烯醇掺量对矿渣粉-粉煤灰基碱激发净浆

Fig.6 Effect of PVA content on drying shrinkage of slag-fly ash-based alkali-activated paste

图7 聚乙烯醇掺量对矿渣粉-粉煤灰基碱激发净浆干燥收缩的影响质量损失的影响

Fig.7 Effect of PVA content on mass loss of slag-fly ash-based alkali-activated paste

图8 聚乙烯醇掺量对矿渣粉-粉煤灰基碱激发净浆pH值的影响

Fig.8 Effect of PVA content on pH value of slag-fly ash-based alkali-activated paste

表5 PVA1和PVA4的OH-含量

Table 5 OH- content of PVA1 and PVA4

Item	Sample mass/g	c（HCL）/（mol·L^-1）	V₀（Blank）/mL	V₁（EP1）/mL	OH^- content/（mg·g^-1）	Average OH^- content/（mg·g^-1）
PVA1-1	0.512 4	0.1	0.009 5	2.043 2	6.750	6.773
PVA1-2	0.515 4	0.1	0.009 5	2.069 3	6.797	6.773
PVA4-1	0.511 2	0.1	0.009 5	1.044 6	3.444	3.425
PVA4-2	0.499 2	0.1	0.009 5	1.009 2	3.406	3.425

图9 吸水率随PVA掺量变化

Fig.9 Water absorption rate varies with PVA content

图10 聚乙烯醇掺量为0%、2.5%、10.0%的XRD谱

Fig.10 XRD patterns of 0%， 2.5%， and 10.0% with PVA content

图11 PVA掺量为0%的SEM照片

Fig.11 SEM images with 0% PVA content

图12 PVA掺量为2.5%的SEM照片

Fig.12 SEM images with 2.5% PVA content

图13 PVA掺量为10.0%的SEM照片

Fig.13 SEM images with 10.0% PVA content

图14 聚乙烯醇掺量为0%、2.5%、10.0%的红外光谱

Fig.14 FTIR spectra with PVA content of 0%， 2.5%， and 10.0%

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