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氮化硼纳米片的绿色制备及在导热复合材料中的应用

石贤斌 张帅 陈超 聂向导 班露露 赵亚星 刘仁 桑欣欣

石贤斌, 张帅, 陈超, 等. 氮化硼纳米片的绿色制备及在导热复合材料中的应用[J]. 复合材料学报, 2023, 40(8): 4563-4572
引用本文: 石贤斌, 张帅, 陈超, 等. 氮化硼纳米片的绿色制备及在导热复合材料中的应用[J]. 复合材料学报, 2023, 40(8): 4563-4572
SHI Xianbin, ZHANG Shuai, CHEN Chao, NIE Xiangdao, BAN Lulu, ZHAO Yaxing, LIU Ren, SANG Xinxin. Green Preparation of Boron Nitride Nanosheets and Their Application in Thermal Conductivity Composites[J]. Acta Materiae Compositae Sinica, 2023, 40(8): 4563-4572.
Citation: SHI Xianbin, ZHANG Shuai, CHEN Chao, NIE Xiangdao, BAN Lulu, ZHAO Yaxing, LIU Ren, SANG Xinxin. Green Preparation of Boron Nitride Nanosheets and Their Application in Thermal Conductivity Composites[J]. Acta Materiae Compositae Sinica, 2023, 40(8): 4563-4572.

氮化硼纳米片的绿色制备及在导热复合材料中的应用

基金项目: 国家自然科学基金 (National Natural Science Foundation of China, 21803025);江苏省科技支撑计划 (Science and Technology Support Program of Jiangsu Province, BE2022087)
详细信息
    通讯作者:

    张帅,博士,高级工程师,研究方向为高性能复合材料

    桑欣欣,博士,副教授,硕士生导师,研究方向为高分子纳米复合材料 E-mail: sangxx@jiangnan.edu.cn

  • 中图分类号: TB332

Green Preparation of Boron Nitride Nanosheets and Their Application in Thermal Conductivity Composites

  • 摘要:   目的  聚合物基导热复合材料优异的可加工性、耐腐蚀性和电绝缘性使其在热管理领域广泛应用。然而,聚合物材料导热系数低,通常需添加大量的导热填料提高其导热性能,易导致聚合物自身的流动性和力学强度等性能劣变。通过构建有效的导热网络能够在减少填料用量的同时提升材料导热性能。六方氮化硼(h-BN)是一种常用的导热填料,将h-BN剥离制备成氮化硼纳米片(BNNS),不仅可以大幅度提升其热导率,且大的横纵比及比表面积有利于其在聚合物基体中形成热传导通路。但传统制备BNNS的方法主要采用有机溶剂辅助液相剥离,存在剥离效率低、环境污染大等问题。因此,发展BNNS的绿色、高效制备方法,通过构建导热网络,实现BNNS填充的聚合物复合材料在较低填料填充时达到较高的导热系数,具有重要意义。  方法  本文以氯化胆碱(ChCl)与植酸(PA)组成低共熔溶剂,采用液相超声的方法,对六方氮化硼进行插层剥离,通过调节溶剂组成调控BNNS的剥离效果,研究不同溶剂组成时所得BNNS分散液的产率及稳定性。通过SEM、TEM、AFM表征剥离所得BNNS的形貌,利用XRD、XPS分析BNNS的结构和组成。将剥离所得BNNS与AlO共同用作导热填料,采用溶液共混-热压的方法与PVDF进行复合。采用SEM观察复合材料的微观结构;利用激光导热仪测试复合材料热扩散系数,进一步计算复合材料的导热系数;通过自制的散热装置测试复合材料的散热性能,系统研究了材料结构与性能之间的关系。  结果  采用氯化胆碱与植酸形成的低共熔溶剂为绿色溶剂辅助剥离六方氮化硼,当氯化胆碱与植酸摩尔比为4:1时,可制备得到横向尺寸1-5 μm,厚度3-5 nm的BNNS,剥离效率高达47.9 %。XRD测试结果表明,剥离后BNNS具有良好的结晶结构,且其002晶面衍射峰向低角度偏移,且半峰宽变宽,层间距变大,该绿色溶剂体系成功实现了h-BN的插层剥离;XPS结果显示,BNNS表面在B元素周围发生了功能化,功能化的BNNS有助于其在聚合物基体中的良好分散。以制备的高质量BNNS为导热填料,与AlO填料协同,通过溶液共混-热压制备PVDF复合材料。复合材料的断面SEM照片显示,热压作用下,基体内BNNS形成明显的取向结构,BNNS薄片之间由AlO连接,形成类似豌豆荚结构。热导率测试及散热性能结果表明,当添加30 wt% AlO与20 wt% BNNS时,复合材料的面内热导率达到11.54 W/(m·K),垂直热导率达到5.70 W/(m·K),作为热界面材料较纯的PVDF散热性能提升约23%。  结论  利用氯化胆碱与植酸形成的低共熔溶剂代替传统有机溶剂,可以实现BNNS的绿色、高效制备,为制备大径厚比的BNNS导热填料提供了一种新方法。利用AlO与BNNS双填料的协同作用,通过构建豌豆荚结构,形成有效的导热网络,通过“导热填料-网络结构”协同提高复合材料的导热性能,制备得到导热性能优异的PVDF基复合材料,作为热界面材料能有效降低电子器件的表面温度。本研究为制备高导热界面材料提供了新颖、简单的途径。

     

  • 图  1  Al2O3-BNNS/PVDF复合材料制备示意图

    Figure  1.  Schematic diagram of the preparation of Al2O3-BNNS/PVDF composite

    图  2  不同ChCl-PA摩尔比时h-BN剥离效果: (a)和(b)分别为BNNS分散液放置3天前后的数码照片,(c) 不同氯化胆碱-植酸摩尔比时的剥离效率,(d) 不同氯化胆碱-植酸摩尔比时溶剂体系的表面张力。

    Figure  2.  The exfoliation of h-BN with different ChCl-PA molar ratio: Digital photographs of BNNS dispersion before (a) and after (b) standing for 3 days; (c) Yields of BNNS and (d) surface tension of the solvents with different ChCl-PA molar ratio.

    图  3  h-BN(a)与BNNS(b)的SEM图片; (c) BNNS的TEM图片; (d) BNNS的AFM图片与(e)BNNS厚度曲线; (f)h-BN与BNNS的XRD谱图。

    Figure  3.  (a) SEM image of h-BN; (b) SEM image of BNNS; (c) TEM image of BNNS; (d) AFM image of BNNS and (e) thickness lines of BNNS; (f) XRD patterns of h-BN and BNNS

    图  4  h-BN及BNNS的XPS谱图:(a) XPS全谱 (b) B1 s谱图

    Figure  4.  XPS patterns of h-BN and BNNS: (a) Full XPS patterns, (b) XPS spectrum of B1 s.

    图  5  PVDF基复合材料脆断面的SEM照片:(a) PVDF、(b) Al2O3、(c) Al2O3/PVDF、(d) Al2O3-BNNS5/PVDF、(e) Al2O3-BNNS10/PVDF、(f) Al2O3-BNNS15/PVDF、(g) Al2O3-BNNS20/PVDF以及(h) BNNS20/PVDF。

    Figure  5.  SEM images for the fracture surfaces of Al2O3-BNNS/PVDF composites: (a) PVDF, (b) Al2O3,(c) Al2O3/PVDF, (d) Al2O3-BNNS5/PVDF, (e) Al2O3-BNNS10/PVDF, (f) Al2O3-BNNS15/PVDF, (g) Al2O3-BNNS20/PVDF and (h) BNNS20/PVDF.

    图  6  Al2O3-BNNS/PVDF复合材料的面内(a)和垂直方向热导率(b)

    Figure  6.  Thermal conductivity of Al2O3-BNNS/PVDF composites: (a) In-plane and (b) out-of-plane.

    图  7  Al2O3-BNNS/PVDF复合材料红外热成像分析

    (a) Al2O3-BNNS/PVDF复合材料红外热成像,其中A~G分别为PVDF、Al2O3/PVDF、Al2O3-BNNS5/PVDF、Al2O3-BNNS10/PVDF、Al2O3-BNNS15/PVDF、Al2O3-BNNS20/PVDF以及BNNS20/PVDF。(b)复合材料表面温度随加热时间的变化,(c)自制散热装置图

    Figure  7.  Infrared thermal imaging analysis of Al2O3-BNNS/PVDFF composites, Surface temperature variation with heating time of Al2O3-BNNS/PVDF composites

    表  1  Al2O3-六方氮化硼纳米片(BNNS)/PVDF复合材料物料配比

    Table  1.   Formulation of Al2O3- hexagonal boron nitride nanosheets (BNNS)/PVDF composites

    SampleAl2O3/wt%BNNS/wt%PVDF/wt%
    Al2O3/PVDF30070
    Al2O3-BNNS5/PVDF30565
    Al2O3-BNNS10/PVDF301060
    Al2O3-BNNS15/PVDF301555
    Al2O3-BNNS20/PVDF302050
    BNNS20/PVDF02080
    下载: 导出CSV

    表  2  h-BN与BNNS的XPS元素含量分析

    Table  2.   Analysis of the XPS element content about h-BN and BNNS

    ElementC1 sN1 sB1 sO1 s
    At Conc./%BN14.3430.9752.522.16
    BNNS45.4019.4429.096.07
    下载: 导出CSV

    表  3  Al2O3-BNNS/PVDF复合材料比热、密度以及热扩散系数

    Table  3.   Heat capacity, density and thermal diffusivity of Al2O3-BNNS/PVDF composites

    SampleCp/(J·g−1·K−1)ρ/(g·cm−3)In-planeα/(mm2·s−1)Out-of-planeα/(mm2·s−1)
    PVDF1.3421.8000.0910.091
    Al2O3/PVDF1.0992.1072.6390.925
    Al2O3−BNNS5/PVDF1.0602.1283.0541.289
    Al2O3−BNNS10/PVDF1.0132.1514.0751.387
    Al2O3−BNNS15/PVDF0.9782.1744.7582.424
    Al2O3−BNNS20/PVDF1.0352.1975.0732.507
    BNNS20/PVDF0.9901.8693.9200.194
    Notes: Cp, ρ, In-plane α and Out-of-plane α are the heat capacity, density, In-plane thermal diffusivity and Out-of-plane thermal diffusivity of the composites.
    下载: 导出CSV

    表  4  BN填充PVDF导热复合材料热导率比较

    Table  4.   Comparison for the thermal conductivity of PVDF based composites in literature

    MatrialBN LoadingOther filler LoadingIn-plane TC/(W·m−1·K−1)Reference
    BN-f-SiC/PVDF20wt% BN26wt% f-SiC1.41[25]
    BNNS/PVDF4wt% BNNS/4.69[26]
    GNP-BN/PVDF30wt% BN2.5wt% GNP0.72[27]
    BN-CNT/PVDF30wt% BN2.5wt% CNT2.18[28]
    Al2O3−BNNS/PVDF20wt% BNNS30wt% Al2O311.54This work
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-09-02
  • 修回日期:  2022-10-08
  • 录用日期:  2022-10-16
  • 网络出版日期:  2022-11-05
  • 刊出日期:  2023-08-15

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