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纳米黑磷阻燃聚丙烯及对力学性能的影响

李永翔 尹思浩 谢于辉 梅玉立 谢德龙 梅毅

李永翔, 尹思浩, 谢于辉, 等. 纳米黑磷阻燃聚丙烯及对力学性能的影响[J]. 复合材料学报, 2022, 39(7): 3178-3190. doi: 10.13801/j.cnki.fhclxb.20210804.004
引用本文: 李永翔, 尹思浩, 谢于辉, 等. 纳米黑磷阻燃聚丙烯及对力学性能的影响[J]. 复合材料学报, 2022, 39(7): 3178-3190. doi: 10.13801/j.cnki.fhclxb.20210804.004
LI Yongxiang, YIN Sihao, XIE Yuhui, et al. Effect of black phosphorous nanosheet on the flame retardance and mechanical property of polypropylene[J]. Acta Materiae Compositae Sinica, 2022, 39(7): 3178-3190. doi: 10.13801/j.cnki.fhclxb.20210804.004
Citation: LI Yongxiang, YIN Sihao, XIE Yuhui, et al. Effect of black phosphorous nanosheet on the flame retardance and mechanical property of polypropylene[J]. Acta Materiae Compositae Sinica, 2022, 39(7): 3178-3190. doi: 10.13801/j.cnki.fhclxb.20210804.004

纳米黑磷阻燃聚丙烯及对力学性能的影响

doi: 10.13801/j.cnki.fhclxb.20210804.004
基金项目: 云南省基础研究计划青年项目(202101AU070012);云南省教育厅科学研究基金项目(2021J0050)
详细信息
    通讯作者:

    谢德龙,博士,教授,博士生导师,研究方向为高分子阻燃和涂料应用 E-mail:cedlxie@kust.edu.cn

    梅毅,博士,教授,博士生导师,研究方向为磷化工节能与新材料 E-mail:meiyi_412@sina.com

  • 中图分类号: TB332

Effect of black phosphorous nanosheet on the flame retardance and mechanical property of polypropylene

  • 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%。

     

  • 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  4  BP、ZHS、ZHS-BP的TG曲线

    Figure  4.  TG curves of BP, 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%

    SamplePPZHSBP
    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
    下载: 导出CSV

    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

    SimpleT5%/℃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.
    下载: 导出CSV

    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

    SimpleTTI/sPHRR/(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.
    下载: 导出CSV
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  • 收稿日期:  2021-06-03
  • 修回日期:  2021-07-11
  • 录用日期:  2021-07-24
  • 网络出版日期:  2021-08-05
  • 刊出日期:  2022-07-30

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