丁向群， 李星宇， 刘旭， 支煦鹭
沈阳建筑大学 材料科学与工程学院，辽宁 沈阳110168
引用格式：
丁向群， 李星宇， 刘旭， 等. 磷酸改性三乙醇胺对水泥砂浆性能影响［J］. 中国粉体技术， 2025， 31（6）： 1-10.
DING Xiangqun， LI Xingyu， LIU Xu， et al. Effects of phosphoric acid-modified triethanolamine on the properties of cement mortar［J］. China Powder Science and Technology， 2025， 31（6）： 1-10.
DOI：10.13732/j.issn.1008-5548.2025.06.015
收稿日期： 2024-01-26， 修回日期： 2025-04-26， 上线日期： 2025-09-24。
基金项目：国家自然科学基金项目，编号：52108235。
第一作者简介：丁向群（1970—），男，教授，博士，硕士生导师，研究方向为高性能混凝土。E-mail：xiangqunding@126.com
摘要：【目的】 研究磷酸（H3PO4）改性三乙醇胺（triethanolamine，TEA）对水泥砂浆力学性能及抗渗性能的影响。【方法】 将H3PO4作为改性组分，在H3PO4和TEA质量比分别为0.8、1、1.2时制备改性TEA，添加改性TEA后水泥砂浆的强度、收缩率及氯离子渗透量，分析水泥砂浆力学性能和抗渗性能，利用X射线衍射仪（X⁃ray diffraction，XRD）、扫描电子显微镜（scanning electron microscopy，SEM）分析改性TEA对胶凝材料水化产物及微观形貌的影响，并对水泥水化后的矿物含量进行半定量分析，借助压汞法（mercury intrusion porosimetry，MIP）技术分析水泥砂浆孔隙变化规律。【结果】 在H3PO4和TEA质量比为0.8时，合成的改性TEA显著地改善了水泥砂浆的强度和抗渗性能，并且随着掺量（质量分数，下同）的增加，水泥砂浆的抗压强度先增大后减小，氯离子渗透量先减小后增大；在掺量为0.04%时，水泥砂浆的3、28 d抗压强度分别提高21.4%、13.4%，氯离子渗透量减小25.3%。【结论】 H3PO4改性TEA能够提高水泥的水化程度，促进水化产物的生长，调控水化产物的形貌，提高结构密实度，改善孔隙结构，提高水泥砂浆的强度和抗渗性能。
关键词： 改性三乙醇胺； 水泥砂浆； 抗压强度； 抗渗性
Abstract
Objective Abstract Objective To investigate the effects of phosphoric acid （H3PO4）-modified triethanolamine（TEA）on the mechanical properties and impermeability of cement mortar， with the aim of addressing the performance limitations of conventional TEA in cement-based systems.
Methods H3PO4 was used as a modifying agent and modified TEA was synthesized by reacting H3PO4 with TEA at molar ratios of 0.8， 1.0， and 1.2. The mechanical properties and impermeability of cement mortar were evaluated by measuring compressive strength， drying shrinkage， and chloride ion permeability after incorporating the modified TEA. The effects of modified TEA on the hydration products and microstructure of the cement matrix were analyzed using X-ray diffraction （XRD） and scanning electron microscopy （SEM）. A semi-quantitative analysis of hydration product content was performed using Jade9 software， and mercury intrusion porosimetry （MIP）was employed to examine changes in pore structure.
Results and Discussion Compared to the control group， all types of modified TEA improved the 3-day and 28-day flexural and compressive strengths of the cement mortar. The strengths exhibited a trend of first increasing and then decreasing with increasing dosage. For flexural strength， the optimal dosage was identified as 0.02% for all modifiers. At this dosage， the modifier synthesized at an H₃PO₄：TEA molar ratio of 1 exhibited the greatest improvement （a 15.7% increase at 3 days， 7.5% at 28 days）， followed by the modifier at a ratio of 0.8 （11.0% at 3 days and 4.6% at 28 days）， and then the modifier at a ratio of 1.2 （9.2% at 3 days and 5.4% at 28 days）. For compressive strength， the optimal dosage shifted to 0.04%. The modifier synthesized at an H₃PO₄：TEA molar ratio of 0.8 showed the most significant enhancement （a 21.4% increase at 3 days and 13.4% at 28 days）， followed by the ratio 1 modifier （16.9% at 3 days and 8.5% at 28 days）， and then the ratio 1.2 modifier （15.0% at 3 days and 7.4% at 28 days）. Notably， the modifier with an H₃PO₄：TEA molar ratio of 0.8 achieved the highest strength values at its optimal dosage， effectively mitigating the long-term strength decline typically observed with unmodified TEA. All modified TEA significantly reduced chloride ion permeability. The modifier synthesized at an H₃PO₄：TEA molar ratio of 0.8 again showed the most pronounced effect. For this modifier， the chloride ion permeability first decreased and then increased with increasing dosage， reaching its minimum value （a 25.3% reduction compared to the control） at a dosage of 0.04%. The modifiers at molar ratios of 1 and 1.2 also reduced permeability by 17.9% and 15.6%， respectively， at the same dosage. When the dosage exceeded 0.06%， the permeability of the modifiers at ratios 1 and 1.2 continued to decrease gradually. Compared to the control， the incorporation of modified TEA reduced drying shrinkage at various ages， though shrinkage still increased over time. The modifier synthesized at an H₃PO₄：TEA molar ratio of 0.8 resulted in the lowest shrinkage， with a 12.1% reduction at a dosage of 0.04%. The modifiers at molar ratios of 1 and 1.2 reduced shrinkage by 10.6% and 3.2%， respectively， at the same 0.04% dosage. This reduction in shrinkage was associated with a decrease in capillary porosity. XRD analysis confirmed that modified TEA did not produce new hydration products. However， semi-quantitative analysis of 28-day samples revealed that the modifier synthesized at an H₃PO₄：TEA molar ratio of 0.8 increased the contents of hydration products （monosulfate， ettringite， and calcium hydroxide） and reduced the contents of unhydrated clinker minerals compared to the control. Early-age （3 day） XRD patterns showed higher peak intensities of AFt and Ca（OH）₂ in samples containing the 0.8-ratio modifier， indicating accelerated hydration of both C₃A and C₃S. SEM micrographs illustrated microstructural refinement induced by the modifier synthesized with a ratio of 0.8. At 3 days， the sample exhibited a denser structure with interwoven C-S-H gel， AFt， and embedded Ca（OH）₂ crystals filling the pores， in contrast to the relatively loose and porous structure of the control. At 28 days， the sample displayed a tightly packed microstructure with minimal visible pores， in stark contrast to that of the control group. MIP analysis showed that the modifier synthesized at an H₃PO₄：TEA molar ratio of 0.8 significantly improved the pore structure at a 0.04% dosage， total porosity was reduced by 15.9%， and average pore diameter was reduced by 21.5%. Crucially， the proportions of harmful pores （50~200 nm） and larger harmful pores （>200 nm） decreased， while the proportions of less harmful pores （20~50 nm） and harmless pores （<20 nm） increased. Similar improvements， though less pronounced， were also observed for modifiers synthesized at molar ratios of 1 and 1.2. This refinement in pore structure directly contributed to the enhancements in strength and impermeability.
Conclusion Phosphoric acid modification effectively enhances the performance of TEA as an admixture for cement mortar. At a molar ratio of 0.8， the modified TEA significantly improved both the early-age （3 day） and later-age （28 day） compressive strength of cement mortar， and also enhanced flexural strength at their respective optimal dosages （0.02% for flexural and 0.04% for compressive strength）. The modified TEA， particularly at the H₃PO₄：TEA molar ratio of 0.8， markedly improved the mortar’s impermeability by significantly reducing chloride ion permeability at a 0.04% dosage. It also effectively reduced drying shrinkage， which was associated with a reduction in capillary porosity. The morphology of hydration products was modified， promoting the formation of a denser， more interconnected microstructure with fewer visible pores. A significant refinement of the pore structure was achieved， characterized by reductions in total porosity and average pore diameter， particularly through a decrease in the proportion of harmful pores （>50 nm） and an increase in the proportions of less harmful and harmless pores （<50 nm）.
Keywords： modified triethanolamine； cement mortar； compressive strength； impermeability
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