水成膜泡沫（Aqueous film-forming foam, AFFF）是扑灭液体火灾最有效的灭火技术，然而其核心组分——长链氟碳表面活性剂被证实存在环境危害。开发适用于液体火灾的不含氟碳表面活性剂的新型环保泡沫灭火剂具有重要的意义。本文以有机硅/碳氢表面活性剂复配体系为起泡剂，纳米颗粒为稳泡剂，协同构建无氟泡沫，旨在从根本上杜绝使用氟碳表面活性剂，促进生态环境的可持续发展。

首先，通过文献调研，筛选了性能优异的表面活性剂和纳米颗粒。所选有机硅表面活性剂为非离子型CoatOsil-77，纳米颗粒为Mg(OH)₂、Al(OH)₃和SiO₂三种。研究了有机硅表面活性剂分别与非离子型（APG-0810）、阴离子型（AOS）和两性离子型（BS-12）等典型碳氢表面活性剂的复配体系的表面活性和起泡性能。优选出了表面活性高、起泡性能好的有机硅/碳氢表面活性剂复配体系（CoatOsil-77/BS-12）作为起泡剂，以Mg(OH)₂、Al(OH)₃和SiO₂三种纳米颗粒为稳泡剂，构建了无氟泡沫体系。

其次，研究了三种纳米颗粒的浓度变化和SiO₂的比表面积变化对无氟泡沫混合液电导率、表面活性和粘度三种性质的影响，分析了不同纳米颗粒与表面活性剂的相互作用。研究发现，相较于Mg(OH)₂和Al(OH)₃，SiO₂的浓度变化对无氟泡沫混合液性质的影响最大。在四种比表面积的SiO₂中，300m²/gSiO₂对无氟泡沫混合液性质影响最大。此外，三种纳米颗粒与表面活性剂的相互作用有明显差异。Mg(OH)₂与两种表面活性剂均没有强烈的相互作用；Al(OH)₃仅与碳氢表面活性剂有强烈的相互作用；而SiO₂与两种表面活性剂均存在强烈的相互作用。

再次，深入研究了三种纳米颗粒的浓度变化和SiO₂的比表面积变化对无氟泡沫起泡性、泡沫析液和粗化的影响。研究发现，SiO₂对无氟泡沫起泡性能影响最大，浓度大于1%或比面积大于200m²/g的SiO₂会大幅降低无氟泡沫的起泡性能。此外，浓度为1%的Mg(OH)₂或比表面积小于300m²/g的SiO₂会加速泡沫析液和粗化，降低泡沫稳定性。浓度大于1%的Mg(OH)₂通过紧密排列在Plateau边界来延缓泡沫析液和粗化，提高泡沫稳定性。Al(OH)₃通过分布在Plateau边界和增强液膜弹性两种作用来共同延缓泡沫析液和粗化，进一步提高泡沫稳定性。浓度大于1%或比表面积大于200m²/g的SiO₂通过在液膜和Plateau边界处形成稳定的网状结构，延缓泡沫析液和粗化，大幅度提高泡沫稳定性。

最后，基于上述研究结果，优选了性能优异的无氟泡沫配方，对比研究了无氟泡沫与AFFF的灭火性能。研究发现，以配比为1%CoatOsil-77/1%BS-12/2%SiO₂为代表的无氟泡沫有极强的控火能力。但从灭火和抗烧两个方面来看，无氟泡沫的灭火性能仍然与AFFF有一定差距。本课题的研究结果表明有机硅/碳氢表面活性剂与纳米颗粒构建的无氟泡沫具有作为新型环保泡沫灭火剂的研究潜力。

Aqueous film-forming foam (AFFF) is the most effective fire-fighting technology for extinguishing flammable liquid fires. However, the core component of AFFF, long-chain fluorocarbon surfactants, has been shown to be environmentally hazardous. Therefore, it is meaningful to develop new environmental-friendly foam extinguishing agent without fluorocarbon surfactants applicable to liquid fires. In this paper, the mixed system of silicone and hydrocarbon surfactants is used as foaming agents and nanoparticles as foam stabilizers to construct a fluorine-free foam. The aim is to fundamentally avoid the use of fluorocarbon surfactants and promote sustainable development of ecological environment.

Firstly, the surfactants and nanoparticles with excellent properties were screened through literature research. The selected silicone surfactant was the nonionic CoatOsil-77, and the nanoparticles were Mg(OH)₂, Al(OH)₃, and SiO₂. The surface activity and foaming ability of the mixed systems of silicon surfactant with typical hydrocarbon surfactants such as nonionic (APG-0810), anionic (AOS), and amphoteric (BS-12) were investigated, respectively. A silicone/hydrocarbon surfactant mixed system (CoatOsil-77/BS-12) with high surface activity and good foaming ability was preferred as a foaming agent, and three nanoparticles of Mg(OH)₂, Al(OH)₃, and SiO₂ were used as stabilizers to construct the fluorine-free foam system.

Secondly, the effects of the variation of the concentration of three nanoparticles and the variation of the specific surface area of SiO₂ on the conductivity, surface activity and viscosity of fluorine-free foam dispersions were investigated. The interactions between different nanoparticles and surfactants were analyzed. It was found that the concentration variation of SiO₂ had the greatest effect on the properties of the fluorine-free foam dispersion compared to Mg(OH)₂ and Al(OH)₃. Among the four specific surface areas of SiO₂, 300 m²/g SiO₂ had the greatest effect on the properties of fluorine-free foam dispersion. Furthermore, the interactions of the three nanoparticles with surfactants were significantly different. Mg(OH)₂ had no strong interactions with two surfactants; Al(OH)₃ only had strong interactions with hydrocarbon surfactant; and SiO₂ had strong interactions with both surfactants.

Thirdly, the effects of the variation of the concentration of three nanoparticles and the variation of the specific surface area of SiO₂ nanoparticles on the foaming ability, foam drainage and foam coarsening of fluorine-free foams were investigated. It was found that SiO₂ had the greatest effect on the foaming ability of fluorine-free foam. SiO₂ with a concentration greater than 1% or a specific area greater than 200m²/g would significantly decrease the foaming ability of fluorine-free foam. Besides, Mg(OH)₂ with a concentration of 1% or SiO₂ with specific surface area less than 300m²/g accelerated foam drainage and coarsening, and thus decreased foam stability. Mg(OH)₂ with a concentration greater than 1% can closely arrange at the Plateau border, and delay foam drainage and coarsening, thus improving foam stability. On the one hand, Al(OH)₃ can delay the foam drainage and coarsening by distributing at the Plateau border. On the other hand, Al(OH)₃ also can adsorb on the liquid film to delay the foam drainage and coarsening by enhanceing the elasticity of the foam film. The two effects together can further improve the foam stability. SiO₂ with a concentration greater than 1% or a specific surface area greater than 200m²/g substantially improve the foam stability by forming a stable mesh structure at the liquid film and Plateau border.

Finally, according to the above research results, the fluorine-free foam formulations with excellent properties were selected, and the fire extinguishing performance of fluorine-free foam and AFFF was studied in comparison. It was found that the fluorine-free foam represented by the formulation ratio with 1% CoatOsil-77/1% BS-12/2% SiO₂ has excellent fire control ability. However, the fire extinguishing performance of fluorine-free foam still has a certain gap with AFFF in the terms of fire extinguishing and burn-back. The results of this study indicate that the fluorine-free foam constructed by silicon/hydrocarbon surfactants and nanoparticles has the potential to be used as a new environmental-friendly foam extinguishing agent.

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