潘文浩， 苗朝阳， 唐宁， 李法敬， 崔值源

沈阳建筑大学 材料科学与工程学院， 辽宁 沈阳 110168

引用格式：

潘文浩， 苗朝阳， 唐宁， 等. 钢渣助磨剂的共聚合成与应用［J］. 中国粉体技术， 2026， 32（3）： 1-10.

PAN Wenhao， MIAO Chaoyang， TANG Ning， et al. Copolymerization and application of steel slag-based grinding aids［J］. China Powder Science and Technology， 2026， 32（3）： 1-10.

DOI：10.13732/j.issn.1008-5548.2026.03.007

摘要： 【目的】 针对钢渣硬度高、体积安定性差等特性，开发了一种复合助磨剂，解决钢渣传统处理方式存在的粉磨效率低、活性利用率差等问题，便于钢渣的大规模资源化利用，解决造成环境污染和资源浪费问题。【方法】 通过甲基丙烯酸与乙二醇的酯化反应制备含双键酯单体，其中酸醇质量比为1：1.3， 110 ℃反应6 h，进一步与异戊烯醇聚氧乙烯醚自由基聚合，合成兼具极性基团与长侧链的高分子聚合物；将所合成的聚合物与质量分数分别为71%的硫酸钠、15%的碳酸钠、4%的氯化钙复配成复合助磨剂；对助磨剂的含量进行研究；利用GB/T 20491—2017《用于水泥和混凝土中的钢渣粉》方法对处理后钢渣粉性能进行检测。通过扫描电子显微镜分析其水化产物的微观形貌。【结果】 极差分析结果表明，反应时间是影响酯化率的主要因素；处理后钢渣粉性能指标均达到一级标准。当复合助磨剂的质量分数为3.8%时，能显著提高钢渣粉的活性指标；傅里叶红外光谱证实产物含酯键、醚键及羟基结构特征。【结论】 合成的复合助磨剂能提升钢渣的粉磨效率，改善钢渣粉的性能，显著提升钢渣资源化利用效率。

关键词： 助磨剂； 粉磨； 自由基聚合； 钢渣粉

Abstract

Objective Steel slag， generated at a rate of 10%~15% of crude steel production in China， has been accumulating in large quantities due to less efficient processing compared to developed countries. This stockpiling results in ecological risks， threatens human and animal health， and occupies valuable land resources. Although steel slag shares chemical similarities with Portland cement clinker and exhibits potential hydraulic and alkali-activated properties， its utilization remains limited. This is mainly due to its high content of inert phases such as iron oxides and RO phases， its dense crystalline structure， and poor grindability. Additionally， the presence of free calcium oxide （f-CaO） and magnesium oxide （f-MgO） in steel slag leads to volume instability. Existing grinding aids for steel slag are primarily adapted from cement additives and are not specifically designed to address the unique properties of steel slag. This study aims to develop a novel polymer-based composite grinding aid to enhance the grindability of steel slag， improve its cementitious activity， and mitigate volume instability， thereby promoting its large-scale and efficient utilization.

Methods A polymer-based composite grinding aid was synthesized through a two-step process. First， ester monomers were produced by the esterification of methacrylic acid and ethylene glycol， followed by free radical polymerization with isopentanol polyoxyethylene ether （TPEG） to form the polymer component. The esterification reaction conditions （acid-alcohol molar ratio： 1∶1.1~1∶1.3； reaction time： 3~5 h； temperature： 90~130 ℃） were optimized using a three-factor and three-level orthogonal experimental design， with the esterification rate as the evaluation metric. Methanesulfonic acid was employed as the catalyst， combined with a binary inhibitor system （methoxyphenol-phenothiazine） to prevent self-polymerization of methacrylic acid. The synthesized polymer was then mixed with sodium sulfate （71%）， sodium carbonate （15%）， and calcium chloride （4%） to prepare the composite grinding aid. Steel slag powder prepared with 3.8% of the grinding aid was evaluated according to GB/T 20491—2017 standards. Key parameters， including specific surface area （503 m²/kg）， density （3.39 g/cm³）， free CaO content （3.12%）， and activity indices （7 d，80.28%； 28 d，83.42%）， were determined. Laser particle size analysis and scanning electron microscopy （SEM） were used to assess grindability and hydration product morphology. Fourier-transform infrared spectroscopy （FTIR） confirmed the structural integrity of the ester monomers and polymers， with characteristic adsorption peaks for ester carbonyl groups （1 718 cm^-1）， hydroxyl groups （3 115~3 655 cm^-1）， and ether bonds （1 107 cm^-1）.

Results and Discussion Orthogonal experiments revealed that reaction time had the strongest influence on the esterification rate （R=3.78）， followed by the acid-alcohol ratio （R=3.48） and temperature （R=3.23）. The optimal conditions—an acid-alcohol ratio of 1：1.3， reaction time of 6 h， and temperature of 110 ℃—produced high-purity ester monomers， confirmed by sharp ester carbonyl peaks （1 718 cm^-1） and retained C═C double bond signals （1 638 cm^-1） in the FTIR spectra. Subsequent polymer synthesis via free radical polymerization successfully integrated hydroxyl， ester， and ether functional groups， aligning with the intended molecular design. The composite grinding aid significantly improved the grinding efficiency of steel slag. Laser diffraction analysis demonstrated a 66.77% cumulative distribution of 0-30 μm particles in the treated group， compared to 54.36% for the control group. This enhancement was attributed to the polymer’s hydroxyl groups neutralizing surface charges on fractured slag particles， reducing agglomeration， while its long side chains provided steric hindrance to help disperse fine particles. SEM analysis showed that the treated group developed denser microstructures with abundant ettringite crystals interwoven with calcium hydroxide and calcium silicate hydrate （C-S-H） gels， filling pore spaces and reducing porosity. In contrast， the control group exhibited sparse ettringite formation and higher porosity， which corresponded with lower mechanical strength. Performance testing confirmed that the prepared steel slag powder complied with Grade I steel slag powder standards， with a specific surface area of 503 m²/kg， a 28-day activity index of 83.42%， a fluidity ratio of 98%， and stable volume stability （2.0 mm expansion in the boiling test）. The polymer’s dual functionality—stabilizing particle surfaces through chemical bonds and promoting particle dispersion via steric effects—effectively addressed the challenges of poor grindability and low hydration activity in steel slag.

Conclusion This study proposes a systematic approach for synthesizing a high-efficiency polymer-based composite grinding aid tailored for steel slag. The optimized esterification conditions （1∶1.3 acid-alcohol ratio， 6 h reaction time， 110 ℃） maximize ester monomer yield while maintaining key double bonds. Subsequent free radical polymerization successfully integrates hydroxyl， ester， and ether functional groups into the polymer backbone， enabling synergistic effects of charge neutralization and steric stabilization. The resulting composite grinding aid （10% polymer， 71% Na₂SO₄， 15% Na₂CO₃， 4% CaCl₂） enhances the grinding efficiency of steel slag， increasing the 0~30 μm particle fraction by 12.41% compared to untreated slag. It meets the Grade I standards， with improved specific surface area， activity indices， and volume stability. Microstructural analyses validate the formation of dense hydration products with reduced porosity， attributed to higher ettringite and calcium hydroxide content. Overall， this study provides a technically viable and economically feasible solution for the valorization of steel slag， addressing both environmental concerns and resource utilization challenges in the steel industry.

Keywords： slag grinding aid； slag grinding； free radical polymerization； steel slag powder

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