硅橡胶泡沫（SiFs）是由硅橡胶发泡而来的高分子弹性材料，既具有硅橡胶绝缘、环保的特点，又保持了泡沫减震、吸音的优点。但其侧链含有大量的碳氢基团，遇到高温或明火会迅速燃烧并蔓延；并且在高性能领域的SiFs长期依赖于进口。因此，提高SiFs的阻燃抑烟性能、扩大其应用范围刻不容缓。近年来，锆基金属有机框架（UiO-66）因其合成过程相对简单且具有较高的比表面积、热稳定性和力学稳定性被广泛作为高分子材料的阻燃添加剂。然而，其合成产量少，成本高。因此需要与其他阻燃剂复配使用，实现降低其添加量的同时提高材料阻燃性能。随着“双碳”目标的提出，工业固废的综合应用逐渐被国内外学者广泛关注。钢渣（SS）内含有大量的CaO、Al₂O₃、Fe₂O₃等金属氧化物，具有巨大的阻燃潜力。为此，本研究合成了三种不同官能团修饰的锆基金属有机框架（UiO-66-x）和改性钢渣（mSS）并将其引入SiFs体系，通过氧指数、烟密度、垂直燃烧、锥形量热及力学测试对SiFs复合材料的阻燃抑烟性能进行了研究。最后，通过对残炭的微观形态、官能团、元素组成、石墨化程度等分析揭示了其阻燃抑烟机理。主要研究结果如下：

（1）制备了三种UiO-66-x和mSS阻燃剂。通过溶剂热合成法分别制备了三种不同官能团修饰的UiO-66（UiO-66-NH₂、UiO-66-NO₂、UiO-66-(OH)₂）；通过磷酸、KH550硅烷偶联剂共混制备了mSS。通过一系列表征手段对所制备的阻燃添加剂的形貌、结构及组成进行了表征测试。最后，将阻燃剂按照一定比例添加至SiFs体系制备了SiFs复合材料。

（2）探究了UiO-66-x/SiFs、SS/SiFs和mSS/SiFs复合材料阻燃抑烟及力学性能。UiO-66-NH₂在改善SiFs复合材料力学性能的同时表现出良好的阻燃作用。添加2wt% UiO-66-NH₂的SiFs的热释放速率峰值（PHRR）和总产热量（THR）分别比纯SiFs降低了30.90%和40.52%；断裂伸长率比纯SiFs提高了11.43%。mSS显示出了比SS更优异的阻燃抑烟性能。添加3wt% mSS的SiFs的THR和最大烟密度（MSD）分别较纯SiFs降低了34.47%和81.67%，抗压强度提升了38.30%。

（3）探究了UiO-66-NH₂和mSS对SiFs复合材料的协同阻燃作用。综合探究结果表明，当UiO-66-NH₂和mSS的质量比为1.5:3时SiFs复合材料的综合性能最优。在该复配比下，SiFs复合材料的PHRR、MSD和总产烟量分别比纯SiFs降低了26.27%、67.61%和38.91%，并且较4.5% UiO-66-NH₂/SiFs和4.5% mSS/SiFs的力学性能也均有提升。因此，可以在减少UiO-66-NH₂添加量的同时，提高SiFs复合材料的阻燃抑烟及力学性能。

（4）揭示了UiO-66-NH₂/mSS对SiFs的协同阻燃抑烟机理。利用XPS、拉曼光谱、FTIR、SEM和热重分析对SiFs复合材料的元素组成、石墨化程度、官能团、微观形貌及热稳定性进行了分析。探究得出，UiO-66-NH₂/mSS/SiFs在燃烧过程中，UiO-66-NH₂热分解产生NH₂、H₂O、CO₂等难燃气体有效稀释SiFs基体内可燃气体浓度，mSS内磷元素终止自由基链式反应。此外，UiO-66-NH₂形成的ZrO₂和mSS中的金属氧化物保护基体的同时促进SiFs形成致密的炭层，阻止热量的传递。

Silicone rubber foam (SiFs) is a polymeric elastic material derived from foamed silicone rubber, combining the insulation and environmental benefits of silicone rubber with the shock absorption and sound absorption advantages of foam. However, its side chains contain a large number of hydrocarbon groups, making it prone to rapid combustion and flame spread when exposed to high temperatures or open flames. Additionally, high-performance SiFs have long relied on imports. Therefore, it is urgent to improve the flame retardant and smoke suppressant properties of SiFs and expand their application scope. In recent years, zirconium-based metal-organic frameworks (UiO-66) have been widely utilized as flame-retardant additives for polymeric materials due to their relatively simple synthesis process, high specific surface area, as well as excellent thermal and mechanical stability. However, their low production yield and high cost limit large-scale applications. Consequently, it is necessary to employ them in combination with other flame retardants to reduce the required dosage while simultaneously enhancing the flame-retardant performance of the materials. With the introduction of the “Dual Carbon” goals (carbon peak and carbon neutrality), the comprehensive utilization of industrial solid waste has been attracting increasing attention from researchers worldwide. Steel slag (SS) contains a large amount of metal oxides such as CaO, Al₂O₃, Fe₂O₃, etc., which have great potential for flame retardancy. Therefore, this study synthesized three zirconium-based metal-organic frameworks (UiO-66-x) with different functional groups and modified steel slag (mSS), which were then incorporated into the SiFs system. The flame retardancy and smoke suppression properties of the SiFs composites were systematically investigated through LOI, smoke density, vertical burning, cone calorimetry, and mechanical tests. Finally, the flame retardant and smoke suppression mechanisms were elucidated by analyzing the residual char's microstructure, functional groups, elemental composition, etc. The main findings are as follows:

(1) Three types of UiO-66-x and mSS flame retardants were prepared. UiO-66 (UiO-66-NH₂, UiO-66-NO₂, UiO-66-(OH)₂) with different functional group modifications were prepared by solvothermal synthesis, and mSS was prepared by blending phosphoric acid and KH550 silane coupling agent. SiFs composites were prepared by adding the flame retardants to SiFs system in a certain ratio. The morphology, structure and composition of the prepared flame retardant additives were characterized and tested by a series of characterization means, and the results showed that the desired flame retardants were successfully synthesized.

(2) The flame retardant, smoke suppression and mechanical properties of UiO-66-x/SiFs, SS/SiFs and mSS/SiFs composites were investigated. UiO-66-NH₂ showed good flame retardancy while improving the mechanical properties of SiFs composites. The peak heat release rate (PHRR) and total heat production (THR) of 2% UiO-66-NH₂/SiFs were reduced by 30.90% and 40.52%, respectively, compared with that of pure SiFs; the elongation at break was increased by 11.43% compared with that of pure SiFs. The mSS showed superior flame retardant and smoke suppression properties than SS. The THR and maximum smoke density (MSD) of 3% mSS/SiFs were reduced by 34.47% and 81.67%, respectively, and the compressive strength was improved by 38.30% compared with that of pure SiFs.

(3) The synergistic flame retardant effects of UiO-66-NH₂ and mSS on SiFs composites were explored. The comprehensive exploration results show that the integrated performance of SiFs composites was optimal when the mass ratio of UiO-66-NH₂ and mSS was 1.5:3. Under this compounding ratio, the PHRR, TSP and MSD of SiFs composites were reduced by 26.27%, 38.91% and 67.61%, respectively, compared with pure SiFs, and the mechanical properties were also improved over both 4.5% UiO-66-NH₂/SiFs and 4.5% mSS/SiFs. Therefore, it is possible to improve the flame retardant smoke suppression and mechanical properties of SiFs composites while reducing the amount of UiO-66-NH₂ added.

(4) Synergistic flame retardant and smoke inhibition mechanism of UiO-66-NH₂/mSS on SiFs was revealed. The elemental composition, graphitization degree, functional groups, microstructure, and thermal stability of SiFs composites were systematically characterized using XPS, Raman spectroscopy, FTIR, SEM, and thermogravimetric analysis. The investigation revealed that during the combustion process of UiO-66-NH₂/mSS/SiFs, the thermal decomposition of UiO-66-NH₂ produces refractory gases such as NH₂, H₂O and CO₂ to effectively dilute the concentration of combustible gases in the matrix of SiFs, and the elemental phosphorus in mSS terminates the free radical chain reaction. In addition, the metal oxides in ZrO₂ and mSS formed by UiO-66-NH₂ protect the substrate while promoting the formation of a dense charcoal layer in SiFs to prevent heat transfer.

Silicone rubber foam (SiFs) is a polymeric elastic material derived from foamed silicone rubber, combining the insulation and environmental benefits of silicone rubber with the shock absorption and sound absorption advantages of foam. However, its side chains contain a large number of hydrocarbon groups, making it prone to rapid combustion and flame spread when exposed to high temperatures or open flames. Additionally, high-performance SiFs have long relied on imports. Therefore, it is urgent to improve the flame retardant and smoke suppressant properties of SiFs and expand their application scope. In recent years, zirconium-based metal-organic frameworks (UiO-66) have been widely utilized as flame-retardant additives for polymeric materials due to their relatively simple synthesis process, high specific surface area, as well as excellent thermal and mechanical stability. However, their low production yield and high cost limit large-scale applications. Consequently, it is necessary to employ them in combination with other flame retardants to reduce the required dosage while simultaneously enhancing the flame-retardant performance of the materials. With the introduction of the “Dual Carbon” goals (carbon peak and carbon neutrality), the comprehensive utilization of industrial solid waste has been attracting increasing attention from researchers worldwide. Steel slag (SS) contains a large amount of metal oxides such as CaO, Al₂O₃, Fe₂O₃, etc., which have great potential for flame retardancy. Therefore, this study synthesized three zirconium-based metal-organic frameworks (UiO-66-x) with different functional groups and modified steel slag (mSS), which were then incorporated into the SiFs system. The flame retardancy and smoke suppression properties of the SiFs composites were systematically investigated through LOI, smoke density, vertical burning, cone calorimetry, and mechanical tests. Finally, the flame retardant and smoke suppression mechanisms were elucidated by analyzing the residual char's microstructure, functional groups, elemental composition, etc. The main findings are as follows:

(1) Three types of UiO-66-x and mSS flame retardants were prepared. UiO-66 (UiO-66-NH₂, UiO-66-NO₂, UiO-66-(OH)₂) with different functional group modifications were prepared by solvothermal synthesis, and mSS was prepared by blending phosphoric acid and KH550 silane coupling agent. SiFs composites were prepared by adding the flame retardants to SiFs system in a certain ratio. The morphology, structure and composition of the prepared flame retardant additives were characterized and tested by a series of characterization means, and the results showed that the desired flame retardants were successfully synthesized.

(2) The flame retardant, smoke suppression and mechanical properties of UiO-66-x/SiFs, SS/SiFs and mSS/SiFs composites were investigated. UiO-66-NH₂ showed good flame retardancy while improving the mechanical properties of SiFs composites. The peak heat release rate (PHRR) and total heat production (THR) of 2% UiO-66-NH₂/SiFs were reduced by 30.90% and 40.52%, respectively, compared with that of pure SiFs; the elongation at break was increased by 11.43% compared with that of pure SiFs. The mSS showed superior flame retardant and smoke suppression properties than SS. The THR and maximum smoke density (MSD) of 3% mSS/SiFs were reduced by 34.47% and 81.67%, respectively, and the compressive strength was improved by 38.30% compared with that of pure SiFs.

(3) The synergistic flame retardant effects of UiO-66-NH₂ and mSS on SiFs composites were explored. The comprehensive exploration results show that the integrated performance of SiFs composites was optimal when the mass ratio of UiO-66-NH₂ and mSS was 1.5:3. Under this compounding ratio, the PHRR, TSP and MSD of SiFs composites were reduced by 26.27%, 38.91% and 67.61%, respectively, compared with pure SiFs, and the mechanical properties were also improved over both 4.5% UiO-66-NH₂/SiFs and 4.5% mSS/SiFs. Therefore, it is possible to improve the flame retardant smoke suppression and mechanical properties of SiFs composites while reducing the amount of UiO-66-NH₂ added.

(4) Synergistic flame retardant and smoke inhibition mechanism of UiO-66-NH₂/mSS on SiFs was revealed. The elemental composition, graphitization degree, functional groups, microstructure, and thermal stability of SiFs composites were systematically characterized using XPS, Raman spectroscopy, FTIR, SEM, and thermogravimetric analysis. The investigation revealed that during the combustion process of UiO-66-NH₂/mSS/SiFs, the thermal decomposition of UiO-66-NH₂ produces refractory gases such as NH₂, H₂O and CO₂ to effectively dilute the concentration of combustible gases in the matrix of SiFs, and the elemental phosphorus in mSS terminates the free radical chain reaction. In addition, the metal oxides in ZrO₂ and mSS formed by UiO-66-NH₂ protect the substrate while promoting the formation of a dense charcoal layer in SiFs to prevent heat transfer.

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