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兼具阻燃和导热性能的环氧树脂复合材料:石墨烯纳米片杂化三聚氰胺磷酸盐的作用

贾锡宁 王严 石慧 屈红强 郝建薇

贾锡宁, 王严, 石慧, 等. 兼具阻燃和导热性能的环氧树脂复合材料:石墨烯纳米片杂化三聚氰胺磷酸盐的作用[J]. 复合材料学报, 2023, 40(待排刊): 1-11
引用本文: 贾锡宁, 王严, 石慧, 等. 兼具阻燃和导热性能的环氧树脂复合材料:石墨烯纳米片杂化三聚氰胺磷酸盐的作用[J]. 复合材料学报, 2023, 40(待排刊): 1-11
Xining JIA, Yan WANG, Hui SHI, Hongqiang QU, Jianwei HAO. Epoxy resin composites with flame retardancy and thermal conductivity: effect of graphene nanoplatelets hybridized with melamine phosphate[J]. Acta Materiae Compositae Sinica.
Citation: Xining JIA, Yan WANG, Hui SHI, Hongqiang QU, Jianwei HAO. Epoxy resin composites with flame retardancy and thermal conductivity: effect of graphene nanoplatelets hybridized with melamine phosphate[J]. Acta Materiae Compositae Sinica.

兼具阻燃和导热性能的环氧树脂复合材料:石墨烯纳米片杂化三聚氰胺磷酸盐的作用

基金项目: 国家自然科学基金(批准号:21474008);河北省京津冀协同创新建设项目(批准号:20541401 D)
详细信息
    通讯作者:

    屈红强,博士,教授,博士生导师,研究方向为石墨烯无机杂化阻燃剂的制备及应用 E-mail: hqqu@163.com

    郝建薇,博士,教授,博士生导师,研究方向为聚合物阻燃、绿色阻燃剂的制备及应用 E-mail: hjw@bit.edu.cn

  • 中图分类号: TB332;TQ323.5

Epoxy resin composites with flame retardancy and thermal conductivity: effect of graphene nanoplatelets hybridized with melamine phosphate

  • 摘要: 研发制备低成本、少缺陷及高效率的石墨烯纳米片杂化阻燃剂对实现复合材料多功能性具有重要意义。以三聚氰胺为助剥离剂将微粉石墨(GRA)经机械球磨后与磷酸液相反应得到一种阻燃导热的石墨烯纳米片杂化三聚氰胺磷酸盐(GMP),在表征GMP形貌、结构、组成和热稳定性的基础上,研究了添加GMP环氧树脂(EP)复合材料的阻燃、热分解和导热性能。GMP的热失重分析结果表明,与三聚氰胺磷酸盐(MP)相比,初始分解温度提升了29.3℃,与环氧树脂的热分解温度更为匹配,有助于提高阻燃效率。氧指数仪、锥形量热仪和导热性能研究表明,GMP添加30wt%时,EP复合材料的极限氧指数达到了30.4%,UL 94垂直燃烧达到V-0级,峰值热释放速率(PHRR)和峰值烟释放速率(PSPR)分别下降69%和74.0%;导热系数提升至2.10 W·m−1·K−1, 相对于EP提升了708%。这是因为GMP中石墨烯纳米片(GNPs)与MP的相互作用促进了EP形成了致密的膨胀炭层,有效提高了EP复合材料的阻燃性;随着GMP添加量的增加,GNPs和石墨微片传热通道的形成改善了EP复合材料的导热性。本研究为解决EP复合材料因热沉积引发火灾危险的问题提供了兼具阻燃和导热性能的石墨烯纳米片杂化阻燃剂的设计和制备思路。

     

  • 图  1  石墨烯纳米片杂化三聚氰胺磷酸盐(GMP)制备路线示意图

    Figure  1.  Schematic diagram of preparation route of graphene nanoplatelets hybrid melamine phosphate (GMP)

    图  2  GNPs的TEM(a, b)、AFM(c)图像和截面分析(d)

    Figure  2.  TEM(a, b), AFM(c) images and section analysis(d) of the GNPs

    图  4  GRA和MN-GNPs的Raman光谱(a);GRA、MN、MP、MN-GNPs和GMP的XRD谱图(b);GRA、MP、MN-GNPs和GMP的FTIR谱图(c);MN-GNPs(d)和GMP(e)的XPS N1 s谱图

    Figure  4.  Raman spectra of GRA and MN-GNPs (a); XRD patterns of GRA MN, MP, MN-GNPs and GMP (b); FTIR spectra of GRA MP, MN-GNPS and GMP (c); XPS N1 s Spectra of MN-GNPs(d) and GMP(e)

    图  3  MP(a)和GMP(b)的SEM图像

    Figure  3.  SEM images of MP(a) and GMP(b)

    图  5  氮气气氛下GRA、MP和GMP的TGA(a)和DTG(b)曲线

    Figure  5.  TGA(a) and DTG(b) curves of GRA, MP and GMP under N2 atmosphere

    图  6  复合材料的HRR(a)、THR(b)、SPR(c)和TSP(d)曲线

    Figure  6.  The curves of HRR(a), THR(b), SPR(c) and TSP(d) for composites

    图  7  EP(a)和GMP20/EP (b)残炭的数码照片和插入的SEM图像

    Figure  7.  Digital photos and inserted SEM images of EP(a) and GMP20/EP(b) char residues

    图  8  氮气气氛下复合材料的TG(a)和DTG(b)曲线

    Figure  8.  TG(a) and DTG(b) curves of composites under N2 atmosphere

    图  9  复合材料导热系数与阻燃剂添加量的关系

    Figure  9.  The relation between thermal conductivity and flame retardants contents of composites

    图  10  相关报道的兼具阻燃导热复合材料导热系数和LOI的对比[6, 33-40]

    Figure  10.  Comparison of thermal conductivity and LOI of composites with flame retardant thermal conductivity was reported[6, 33-40]

    图  11  GMP30/EP(a, b, h)、MP30/EP(c, d, i)、MP-GRA30/EP(e, f, j)和EP(g, k)复合材料断裂表面的SEM图像及导热机制

    Figure  11.  SEM images of fractured surfaces and heat conductive mechanism of GMP30/EP(a, b, h), MP30/EP(c, d, i), MP-GRA30/EP(e, f, j) and EP(g, k) composites

    表  2  复合材料的配方及阻燃性能

    Table  2.   Formulation and flame retardancy of composites

    SampleE-51/wt%DDM/wt%MP/wt%GMP/wt%GRA/wt%P/wt%LOI/%EFFUL 94
    (3 mm)
    EP 80.0 20.0 0 0 0 0 24.5 NR
    GMP20/EP 64.0 16.0 0 20.0 0 2.3 27.1 1.13 V-1
    GMP25/EP 60.0 15.0 0 25.0 0 2.9 28.4 1.34 V-1
    GMP30/EP 56.0 14.0 0 30.0 0 3.5 30.4 1.68 V-0
    MP20/EP 64.0 16.0 20.0 0 0 2.8 26.8 0.82 V-1
    MP25/EP 60.0 15.0 25.0 0 0 3.5 28.5 1.14 V-0
    MP30/EP 56.0 14.0 30.0 0 0 4.2 31.0 1.55 V-0
    MP-GRA20/EP 64.0 16.0 16.8 0 3.2 2.3 26.9 1.04 V-1
    MP-GRA25/EP 60.0 15.0 21.1 0 3.9 2.9 28.1 1.24 V-1
    MP-GRA30/EP 56.0 14.0 25.3 0 4.7 3.5 30.1 1.19 V-0
    Notes: E-51−Epoxy monomer; DDM−4, 4-Diaminodiphenylmethane; MP−Melamine phosphate; GMP−Graphene nanoplatelets hybrid melamine phosphate; P−Phosphorus content in composite materials; EFF is defined as flame retardancy efficiency and represents the LOI increment produced by each 1 wt% of phosphorus in the composites.
    下载: 导出CSV

    表  1  MN-GNPs、MP和GMP的表面元素组成

    Table  1.   Surface elemental compositions of MN-GNPs, MP and GMP

    SampleC/wt%N/wt%O/wt%P/wt%N/P
    MN-GNPs66.128.75.2
    MP27.631.925.515.12.1
    GMP59.218.414.28.32.2
    下载: 导出CSV

    表  4  复合材料TG和DTG数据

    Table  4.   TG and DTG data of composites materials under N2 atmosphere

    SampleT5%/℃ΔT5%/℃Tmax/℃CR700℃/%ΔCR700℃/%
    Exp.Cal.Exp.Cal.
    EP 368.1 382.9 20.1
    GMP 292.6 396.4 42.0
    MP 263.3 391.2 28.1
    GMP20/EP 328.5 353.0 −24.5 364.0 29.7 24.2 5.5
    GMP30/EP 337.8 345.4 -8.0 363.3 38.2 26.5 11.7
    MP20/EP 332.8 347.1 −14.3 363.8 30.7 21.5 9.2
    MP30/EP 329.5 336.7 −7.2 363.3 33.5 22.3 11.2
    Notes: Exp.−The test results; Cal.−Calculated results; T5%− Temperature with weight loss of 5%; Tmax− The maximum decomposition temperature; CR700℃−Char residues at 700℃; ΔT5%= T5%Exp.T5%Cal.; ΔCR700℃= CR700℃Exp.− CR700℃Cal.
    下载: 导出CSV

    表  3  复合材料锥形量热仪测试数据

    Table  3.   Combustion parameters of composites from cone test

    SampleTTI/sPHRR/(kW·m−2)THR/(MJ·m−2)PSPR/(m2·s−1)TSP/(m2·kg−1)CR/%
    EP 40 954.8 90.0 0.454 41.9 5.0
    GMP20/EP 37 339.5 70.2 0.144 26.1 23.6
    GMP30/EP 42 297.4 62.7 0.118 19.5 31.3
    MP20/EP 37 285.3 77.1 0.127 22.9 24.8
    MP30/EP 37 247.7 68.6 0.116 18.7 29.6
    Notes: TTI−Time to Ignition; PHRR−Peak heat release rate; THR−Total heat release; PSPR−Peak smoke produce rate; TSP−Total smoke production; CR−Char residues.
    下载: 导出CSV

    表  5  复合材料的热扩散系数α、比热容Cp、密度ρ及导热系数λ

    Table  5.   Thermal diffusivity α, specific heat capacity Cp, density ρ and thermal conductivity λ of composites

    SampleGNPs/wt%GRA/wt%α/(mm2·s−1)Cp/( J·g−1·K−1)ρ/(g·cm−3)λ/(W·m−1·K−1)
    EP000.1631.4281.1030.26
    GMP30/EP≥0.5≤4.20.5882.5371.4092.10
    MP30/EP000.1972.4831.2740.62
    MP-GRA30/EP04.70.2531.6951.3050.56
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-02-21
  • 录用日期:  2022-04-10
  • 修回日期:  2022-03-27
  • 网络出版日期:  2022-04-26

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