Enhancement of fire insulation performance for aramid non-woven fabric via chitosan/M(OH)(OCH3) (M=Co, Ni)/sodium hexametaphosphate nano-composite coating
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摘要: 随着火灾场景的复杂化和火灾危险性的增加，市场迫切需要高性能耐火隔热纤维以更好保护消防救援人员。本工作利用层层自组装技术，将食品级六偏磷酸钠及复合二维纳米材料M(OH)(OCH3) (M=Co, Ni)的生物质壳聚糖交替涂覆于芳纶纤维无纺布(ANF)表面，制备了新型ANF纳米复合材料。结果表明，涂覆15层样品(CMP/ANF-Ⅲ)在空气中升温至800 ℃，残炭率由1.59%(纯ANF)提高至20.55%，热稳定性显著改善。CMP/ANF-Ⅲ的热释放速率峰值(PHRR)、总热释放速率(THR)较ANF分别降低48.90%、58.57%，阻燃性能显著提高。在垂直燃烧测试中，CMP/ANF-Ⅲ的损毁长度降低至2.4 cm(纯ANF 9.0 cm)。在耐火隔热测试中，纯ANF 12 s被烧穿，而CMP/ANF-Ⅲ在120 s仍保持完整，同时背面温度大幅降低至335 ℃(纯ANF超过500 ℃)。残炭分析表明，CMP/ANF-Ⅲ燃烧后生成致密的炭层，其能有效阻挡火焰的蔓延及与基体之间的热对流，提高无纺布阻燃隔热性能。气相产物分析表明，CMP/ANF-Ⅲ较低温度下即可释放出CO2、H2O、NH3等不燃性气体，起到气相阻燃作用。本工作研制的ANF纳米复合材料为新一代高效耐火防护服装的研发提供支持。Abstract: With the complexity of fire scenarios and the increasing risk of fire, there was an urgent need for high-performance fire-resistant insulation fibers to be better developed in the market to protect firefighting and rescue personnel. In this work, we used layer-by-layer self-assembly technique to alternately coat food-grade sodium hexametaphosphate and biomass chitosan mixed with two-dimensional nanomaterials M(OH)(OCH3) (M=Co, Ni) on the surface of aramid nonwoven fabric (ANF), and prepared novel ANF composite materials. The results show that after heating from room temperature to 800 ℃ in air, the char yield of the 15BL coated sample (CMP/ANF-Ⅲ) increases from 1.59% (pure ANF) to 20.55%, significantly enhancing its thermal stability. CMP/ANF-Ⅲ exhibits lower peak heat release rate (PHRR) and total heat release (THR), which are 48.90% and 58.57% lower than ANF, demonstrating a significantly improvement in flame retardancy. In the vertical flame test, the damaged length of CMP/ANF-Ⅲ reduces to 2.4 cm (while that of the pure ANF is 9.0 cm). In the fire resistance and insulation test, pure ANF burns through in 12 s, while CMP/ANF-Ⅲ remains unharmed for 120 s, and the backside temperature greatly drops to 335 ℃ (while the pure ANF is over 500 ℃). The analysis of residual char reveals that CMP/ANF-III generates a dense char layer after combustion, effectively blocking the spread of flame and thermal convection with the matrix, thereby improving the flame retardancy and thermal insulation properties of non-woven fabric. Gas phase product analysis shows that CMP/ANF-III can release non-combustible gases such as CO2, H2O, NH3, etc. at lower temperatures, performing a gas phase flame retardant function. The ANF nanocomposite material developed in this work supports the development of a new generation of highly efficient fire-resistant and thermal protective clothing.
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Key words:
- nanocomposite /
- coating /
- aramid fiber /
- flame retardancy /
- thermal insulation
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图 1 芳纶纤维无纺布(ANF)纳米复合材料的制备
Figure 1. Preparation of aramid nonwoven fabric (ANF) nanocomposites
图 2 ANF、M(OH)(OCH3)、CMP/ANF-Ⅰ、CMP/ANF-Ⅱ、CMP/ANF-Ⅲ样品的XRD谱图
Figure 2. The XRD spectra of ANF、M(OH)(OCH3)、CMP/ANF-Ⅰ、CMP/ANF-Ⅱ和CMP/ANF-Ⅲ
图 3 (a) ANF、(b) CMP/ANF-Ⅰ、(c) CMP/ANF-Ⅱ、(d) CMP/ANF-Ⅲ样品表面SEM照片；(e) ANF、(f) CMP/ANF-Ⅰ、(g) CMP/ANF-Ⅱ、(h) CMP/ANF-Ⅲ样品截面SEM照片；(i) ANF、(j) CMP/ANF-Ⅰ、(k) CMP/ANF-Ⅱ、(l) CMP/ANF-Ⅲ样品截面低倍数SEM照片
Figure 3. SEM images of the surface of (a) ANF, (b) CMP/ANF-Ⅰ, (c) CMP/ANF-Ⅱ, (d) CMP/ANF-Ⅲ, SEM images of the cross-section of (e) ANF, (f) CMP/ANF-Ⅰ, (g) CMP/ANF-Ⅱ, (h) CMP/ANF-Ⅲ, low magnification SEM images of the cross-section of (i) ANF、(j) CMP/ANF-Ⅰ、(k) CMP/ANF-Ⅱ、(l) CMP/ANF-Ⅲ
图 4 (a) CMP/ANF-Ⅲ表面EDS能谱结果、(b) CMP/ANF-Ⅲ截面的EDS能谱结果
Figure 4. (a)SEM and its elemental analysis mapping of the surface of CMP/ANF-Ⅲ, (b)SEM and its elemental analysis mapping of the cross-section of CMP/ANF-Ⅲ
图 6 ANF和CMP/ANF-Ⅲ的热释放速率曲线
Figure 6. Heat release rate (HRR) curves of ANF and CMP/ANF-Ⅲ
图 7 (a) ANF、(b) CMP/ANF-Ⅰ、(c) CMP/ANF-Ⅱ、(d) CMP/ANF-Ⅲ样品垂直燃烧测试损毁长度图片
Figure 7. The damaged length of (a) ANF、(b) CMP/ANF-Ⅰ、(c) CMP/ANF-Ⅱ、(d) CMP/ANF-Ⅲ in vertical flame test
图 8 (a) ANF、(b) CP/ANF、(c) CMP/ANF-Ⅱ、(d) CMP/ANF-Ⅲ暴露于火焰的红外热成像图
Figure 8. Infrared thermal imaging images of (a) ANF, (b) CP/ANF, (c) CMP/ANF-Ⅱ, (d) CMP/ANF-Ⅲ exposed to flame
图 9 ANF纳米复合材料耐火隔热性能演示：(a) ANF、(b) CP/ANF、(c) CMP/ANF-Ⅲ
Figure 9. Demonstration of fire resistance and thermal insulation performance of (a) ANF, (b) CP/ANF, (c) CMP/ANF-Ⅲ
图 10 ANF、CP/ANF、CMP/ANF-Ⅲ样品燃烧后残炭的傅里叶红外光谱图
Figure 10. Infrared spectra of residual char of ANF, CP/ANF, CMP/ANF-Ⅲ
图 12 ANF、CP/ANF、CMP/ANF-Ⅲ样品燃烧后残炭的XRD谱图
Figure 12. The XRD spectra of residual char of ANF, CP/ANF, CMP/ANF-Ⅲ
图 13 ANF、CP/ANF、CMP/ANF-Ⅲ样品燃烧后残炭的扫描电镜图
Figure 13. SEM images of residual char of ANF, CP/ANF, CMP/ANF-Ⅲ after combustion
图 14 (a) ANF、(b) CMP/ANF-Ⅲ的3 D TG-IR曲线
Figure 14. 3 D TG-IR maps of (a) ANF、(b) CMP/ANF-Ⅲ
图 15 (a) ANF、(b) CMP/ANF-Ⅲ 不同温度下热解产物的红外图谱
Figure 15. IR spectra of pyrolysis products at different temperatures of(a) ANF、(b) CMP/ANF-Ⅲ
表 1 复合材料样品的基本参数
Table 1. Basic data of composites
Composite Thickness/
mmQuality/g Thickening
rate/%Weight gain
rate/%ANF 12.0 3.0 / / CMP/ANF-Ⅰ 13.1 5.5 9.2 84.3 CMP/ANF-Ⅱ 13.6 6.8 13.3 127.4 CMP/ANF-Ⅲ 14.0 8.1 16.7 169.9 
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表 2 TG和DTG结果中的重要参数
Table 2. TG and DTG results of composites
Composite T5%/
℃Tmax%/
℃Rmax/
(%·℃−1)Char residue/
wt%ANF 273 596 −0.94 1.59 CMP/ANF-Ⅰ 69 535 −0.63 14.85 CMP/ANF-Ⅱ 69 561 −0.61 17.42 CMP/ANF-Ⅲ 70 571 −0.55 20.55 Notes: T5%—temperature at 5% quality loss of composite; Tmax—temperature of the maximum quality loss of composite; Rmax—maximum mass loss rate of composite; Char residue—the residue mass of composite
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