Effect of black phosphorous nanosheet on the flame retardance and mechanical property of polypropylene
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摘要: 利用球磨法制备了纳米黑磷(BP)与羟基锡酸锌(ZHS)复合的纳米复合阻燃剂ZHS-BP，将ZHS-BP通过熔融共混方式添加到聚丙烯(PP)中，研究了复合材料的热稳定性、燃烧性能和力学性能。结果表明BP和ZHS的加入都可以提高PP的热解残炭。仅添加2wt% BP可以使PP材料的极限氧指数由19.7%提高至23.8%，同时，BP的添加可以有效降低PP材料燃烧时的热释放速率峰值(PHRR)和总热释放量(THR)，对比纯PP分别降低32.52%和17.80%。但是，BP的添加会导致PP有毒烟气释放的增加，通过引入ZHS作为抑烟剂，制备了ZHS-BP/PP复合材料，其烟气平均比消光面积 (av-SEA) 和CO释放较BP/PP分别降低了15.42%和29.76%。材料的力学性能测试表明，加入单一的BP或ZHS会降低PP的力学性能，而ZHS-BP复合体系的加入可以有效提高复合材料的力学性能。与BP/PP相比，ZHS-BP/PP复合材料的拉伸强度和断裂拉伸率分别提高了12.51%和4.04%。Abstract: Ball-milling the mixture of black phosphorous (BP) and zinc hydroxyl stannate (ZHS) was carried out to prepare ZHS-BP nanocomposite, which was then introduced into polypropylene (PP) matrix as flame retardant via melt blending. The thermal stability, combustion and mechanical properties of the PP based composites were investigated. Results show that the addition of BP and ZHS could increase the carbon residue of PP, and only 2wt% BP increases the limiting oxygen index (LOI) of the BP/PP composite from 19.7% (for pure PP) to 23.8%. Moreover, BP can effectively reduce the peak heat release rate (PHRR) and total heat release (THR) of BP/PP composite, the values of which are decreased by 32.52% and 17.80% respectively compared with that of pure PP. However, the release of toxic gases from PP combustion is increased obviously as BP is added, ZHS was then introduced as the assistant agent to suppress the smoke release. As a result, the average specific extinction area (av-SEA) and CO emission of ZHS-BP/PP are decreased by 15.42% and 29.76% respectively compared with BP/PP. Mechanical properties test shows that merely adding BP or ZHS has negative effect on the mechanical properties of the composites. However, the addition of ZHS-BP nanocomposite effectively improves the mechanical properties. Compared with BP/PP, the tensile strength and breaking tensile ratio of ZHS-BP/PP composites are increased by 12.51% and 4.04%, respectively.
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Key words:
- polypropylene /
- nanomaterials /
- black phosphorus /
- zinc hydroxy stannate /
- flame retardancy /
- mechanical property
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图 1 BP-bulk(块状晶体)、BP、ZHS-BP、ZHS的XRD图谱
Figure 1. XRD patterns of BP-bulk, BP, ZHS-BP and ZHS
图 2 BP的TEM图像(a)和HRTEM图像(b)、ZHS-BP的TEM图像((c)、(d))和SAED图像(e)以及BP的AFM图像((f)、(g))
Figure 2. TEM image (a) and HRTEM image (b) of BP, TEM image ((c), (d)) and SAED patterns of ZHS-BP (e) as well as AFM image of BP ((f), (g))
图 3 BP(a)和ZHS-BP(b)高分辨率P 2p、BP(c)和ZHS-BP(d)高分辨率O 1s、ZHS和ZHS-BP高分辨率Sn 3d(e)以及高分辨率Zn 2p(f)
Figure 3. High-resolution P 2p of BP (a) and ZHS-BP (b), high-resolution O 1s of BP (c) and ZHS-BP (d), high-resolution Sn 3d (e) and high-resolution Zn 2p (f) of ZHS and ZHS-BP
图 5 PP、2%ZHS/PP、2%BP/PP、1%ZHS-1%BP/PP、0.5%ZHS-0.5%BP/PP和1.5%ZHS-1.5%BP/PP复合材料的TG曲线
Figure 5. TG curves of PP, 2%ZHS/PP, 2%BP/PP, 1%ZHS-1%BP/PP, 0.5%ZHS-0.5%BP/PP and 1.5%ZHS-1.5%BP/PP composites
图 6 PP、2%ZHS/PP、2%BP/PP、1%ZHS-1%BP/PP、0.5%ZHS-0.5%BP/PP和1.5%ZHS-1.5%BP/PP复合材料的锥形量热曲线：(a)热释放速率曲线；(b)总热释放量曲线；(c) CO释放率曲线；(d) CO2释放率曲线
Figure 6. Cone calorimetric test curves of PP, 2%ZHS/PP, 2%BP/PP, 1%ZHS-1%BP/PP, 0.5%ZHS-0.5%BP/PP and 1.5%ZHS-1.5%BP/PP composites: (a) Heat release rate (HRR) curves; (b) Total heat release (THR) curves; (c) CO release rate curves; (d) CO2 release rate curves
图 7 PP、2%ZHS/PP、1%ZHS-1%BP/PP、2%BP/PP复合材料的极限氧指数(LOI)
Figure 7. Limiting oxygen index (LOI) of PP, 2%ZHS/PP, 1%ZHS-1%BP/PP and 2%BP/PP composites
图 8 2%ZHS/PP ((a)、(a'))、2%BP/PP ((b)、(b'))、1%ZHS-1%BP/PP ((c)、(c'))在锥形量热测试后残炭照片和SEM图像
Figure 8. Carbon residue and SEM images of 2%ZHS/PP ((a), (a')), 2%BP/PP ((b), (b')) and 1%ZHS-1%BP/PP ((c), (c')) composite after cone calorimetry
图 9 2%BP/PP P2p (a)、1%ZHS-1%BP P2p (b)、1%ZHS-1%BP/PP O1s (c)残炭XPS图谱
Figure 9. XPS spectra of carbon residue of 2%BP/PP P2p (a), 1%ZHS-1%BP/PP P2p (b) and 1%ZHS-1%BP/PP O1s (c)
图 10 2%ZHS/PP (a)、2%BP/PP (b)、1%ZHS-1%BP/PP(c)残炭拉曼图谱
Figure 10. Raman patterns of carbon residue of 2%ZHS/PP (a), 2%BP/PP (b) and 1%ZHS-1%BP/PP (c)
图 11 PP、2%ZHS/PP、2%BP/PP、1%ZHS-1%BP/PP复合材料拉伸性能(a)、应力-应变曲线(b)
Figure 11. Tensile properties (a), stress-strain curves (b) of PP, 2%ZHS/PP, 2%BP/PP and 1%ZHS-1%BP/PP composites
图 12 PP(a)、2%ZHS/PP(b)、2%BP/PP(c)、1%ZHS-1%BP/PP(d)断裂表面SEM图像
Figure 12. SEM images of fractured surfaces of PP (a), 2%ZHS/PP (b), 2%BP/PP (c) and 1%ZHS-1%BP/PP (d)
表 1 羟基锡酸锌-纳米黑磷/聚丙烯(ZHS-BP/PP)复合材料的物料配比
Table 1. Formulations of zinc hydroxyl stannate-black phosphorous/polypropylene (ZHS-BP/PP) composite materials
wt% Sample PP ZHS BP PP 100 0 0 2%ZHS/PP 98 2 0 2%BP/PP 98 0 2 1%ZHS-1%BP/PP 98 1 1 0.5%ZHS-0.5%BP/PP 99 0.5 0.5 1.5%ZHS-1.5%BP/PP 97 1.5 1.5 
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表 2 PP、2%ZHS/PP、2%BP/PP、1%ZHS-1%BP/PP、0.5%ZHS-0.5%BP/PP和1.5%ZHS-1.5%BP/PP复合材料在N2中的TGA及DSC数据
Table 2. TGA and DSC data of of PP, 2%ZHS/PP, 2%BP/PP, 1%ZHS-1%BP/PP, 0.5%ZHS-0.5%BP/PP and 1.5%ZHS-1.5%BP/PP composites in N2
Simple T5%/℃ Tmax/℃ Y800/% YG/% Tg/℃ PP 398.5 440.7 0.15 0.15 −5.95 2%ZHS/PP 376.3 452.7 4.15 2.51 −6.63 2%BP/PP 399.4 459.9 3.77 3.57 −6.28 1%ZHS-1%BP/PP 428.9 458.6 3.08 2.17 −7.57 0.5%ZHS-0.5%BP/PP 419.0 447.2 1.42 0.97 −13.52 1.5%ZHS-1.5%BP/PP 420.9 456.9 4.26 2.90 −11.26 Notes: T5%—Temperature at 5% mass loss; Tmax—Temperature at maximum mass loss rate; Y800—Char yield at 800℃; YG—Normalized of char yield；Tg—Glass transition temperature.
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表 3 PP、2%ZHS/PP、2%BP/PP、1%ZHS-1%BP/PP、0.5%ZHS-0.5%BP/PP和1.5%ZHS-1.5%BP/PP复合材料锥形量热测试结果
Table 3. Cone calorimeter test results of PP, 2%ZHS/PP, 2%BP/PP, 1%ZHS-1%BP/PP, 0.5%ZHS-0.5%BP/PP and 1.5%ZHS-1.5%BP/PP composites
Simple TTI/s PHRR/(kW·m−2) THR/(MJ·m−2) Avg EHC/(MJ·kg−1) Av-SEA/(m2·kg−1) CO/(kg·kg−1) PP 38 1242.9 81.9 36.6 261.7 0.057 2%ZHS/PP 28 1057.6 77.3 36.0 292.1 0.055 2%BP/PP 21 838.7 67.6 31.6 517.2 0.168 1%ZHS-1%BP/PP 24 967.2 72.7 33.9 437.4 0.118 0.5%ZHS-0.5%BP/PP 26 956.7 80.7 35.3 350.4 0.102 1.5%ZHS-1.5%BP/PP 22 808.9 74.4 33.6 435.8 0.151 Notes: TTI—Ignition time; PHRR—Peak heat release rate; THR—Total value of heat release; Avg EHC—Average effective heat of combustion; Av-SEA—Average specific extinction area; CO—Carbon monoxide production.
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