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导热高分子聚合物研究进展

刘裕芮 许艳菲

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导热高分子聚合物研究进展

刘裕芮, 许艳菲

Research progress of polymers with high thermal conductivity

Liu Yu-Rui, Xu Yan-Fei
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  • 传统高分子聚合物是良好的电绝缘体和热绝缘体. 高分子聚合物具备质量轻、耐腐蚀、可加工、可穿戴、电绝缘、低成本等优异特性. 高分子聚合物被广泛应用于各种器件. 由于高分子材料的热导率比较低(0.1—0.5 W·m–1·K–1), 热管理(散热)面临严峻的挑战. 理论及实验工作表明, 先进高分子材料可以具有比传统传热材料(金属和陶瓷)更高热导率. Fermi-Pasta-Ulam (FPU)理论结果发现低维度原子链具有非常高的热导率. 广泛使用的聚乙烯热绝缘体可以被转变为热导体: 拉伸聚乙烯纳米纤维的热导率大约为104 W·m–1·K–1, 拉伸的聚乙烯薄膜热导率大约为62 W·m–1·K–1. 首先, 本文通过理论和实验结果总结导热高分子材料的传热机理研究进展, 并讨论了导热高分子聚合物的制备策略; 然后, 讨论了在传热机制及宏量制备方面, 高分子聚合物研究领域所面临的新挑战; 最后, 对导热高分子的热管理应用前景进行了展望. 例如, 导热高分子聚合物在耐腐蚀散热片、低成本太阳能热水收集器、可穿戴智能冷却服饰、电子绝缘却高导热的电子封装材料等领域具有不可替代的热管理应用前景.
    Developing thermally conductive polymers is of fundamental interest and technological importance. Common polymers have low thermal conductivities on the order of 0.1 W·m–1·K–1 and thus are regarded as thermal insulators. Compared with the traditional heat conductors (metals and ceramics), polymers have unparalleled combined properties such as light weight, corrosion resistance, electrical insulation and low cost. Turning polymer insulators into heat conductors will provide new opportunities for future thermal management applications. Polymers may replace many metals and ceramics, serving as lightweight heat dissipators in electronics, refrigerators, and electrical vehicles.In this review and perspectives, we discuss the research progress of thermal transport mechanisms in polymers and reveal the relations between thermal conductivity and polymer structural parameters such as bond strength, crystallinity, crystallite size, chain orientation, radius of gyration, and molecular weight. We discuss the advanced strategies for developing thermally conductive polymers by both bottom-up and top-down approaches. We highlight how thermally conductive polymers provide new opportunities for thermal management applications. Finally, we emphasize the future challenges to and opportunities for designing and synthesizing polymers with metal-like thermal conductivity and exploring the thermal transport physics in polymers. We believe that the thermally conductive polymers with their unparalleled combination of characteristics (light weight, electrical insulation, easy processability, corrosion resistance, etc.) promise to possess many existing and unforeseen thermal management applications.
      通信作者: 许艳菲, yanfeixu@umass.edu
    • 基金项目: 美国阿莫赫斯特马萨诸塞大学教师启动基金资助的课题.
      Corresponding author: Xu Yan-Fei, yanfeixu@umass.edu
    • Funds: Project supported by the Faculty Startup Fund Support from University of Massachusetts Amherst, USA
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  • 图 1  微纳尺度及原子尺度下的高分子结构. 高分子链端、无定型链、链缠结、杂质等缺陷都可能成为热载流子散射点, 导致高分子聚合物高分子的热导率比较低 (约0.1 W·m–1·K–1)[24]

    Fig. 1.  Polymer structures at micro-nano scale and atomic scale. Defects such as chain ends, amorphous chains, chain entanglement, impurities in polymers act as heat carrier scattering sites and hinder efficient thermal transport, result in relatively low thermal conductivity (about 0.1 W·m–1·K–1)[24].

    图 2  室温下聚乙烯(PE)的热导率实验数据[21,38,39,43-50,58,83,87,94-97]及模拟值[35,54,98]; 室温下聚噻吩(PT)的热导率实验数据[39,40,99,100]及模拟值[56]

    Fig. 2.  Thermal conductivities of polyethylene at room temperature in experimental measurements[21,38,39,43-50,58,83,87,94-97]and simulations[35,54,98]. Thermal conductivities of polythiophene at room temperature in experimental measurements[39,40,99,100]and simulations[56].

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出版历程
  • 收稿日期:  2021-10-09
  • 修回日期:  2021-11-12
  • 上网日期:  2022-01-15
  • 刊出日期:  2022-01-20

导热高分子聚合物研究进展

  • 1. 马萨诸塞大学阿莫赫斯特分校机械与工业工程系, 阿莫赫斯特 01003
  • 2. 马萨诸塞大学阿莫赫斯特分校化学工程系, 阿莫赫斯特 01003
  • 通信作者: 许艳菲, yanfeixu@umass.edu
    基金项目: 美国阿莫赫斯特马萨诸塞大学教师启动基金资助的课题.

摘要: 传统高分子聚合物是良好的电绝缘体和热绝缘体. 高分子聚合物具备质量轻、耐腐蚀、可加工、可穿戴、电绝缘、低成本等优异特性. 高分子聚合物被广泛应用于各种器件. 由于高分子材料的热导率比较低(0.1—0.5 W·m–1·K–1), 热管理(散热)面临严峻的挑战. 理论及实验工作表明, 先进高分子材料可以具有比传统传热材料(金属和陶瓷)更高热导率. Fermi-Pasta-Ulam (FPU)理论结果发现低维度原子链具有非常高的热导率. 广泛使用的聚乙烯热绝缘体可以被转变为热导体: 拉伸聚乙烯纳米纤维的热导率大约为104 W·m–1·K–1, 拉伸的聚乙烯薄膜热导率大约为62 W·m–1·K–1. 首先, 本文通过理论和实验结果总结导热高分子材料的传热机理研究进展, 并讨论了导热高分子聚合物的制备策略; 然后, 讨论了在传热机制及宏量制备方面, 高分子聚合物研究领域所面临的新挑战; 最后, 对导热高分子的热管理应用前景进行了展望. 例如, 导热高分子聚合物在耐腐蚀散热片、低成本太阳能热水收集器、可穿戴智能冷却服饰、电子绝缘却高导热的电子封装材料等领域具有不可替代的热管理应用前景.

English Abstract

    • 高能量密度、高功率密度、高集成化器件需要优良的热管理[1-4]. 过热导致器件性能和安全性能下降[5]. 比如, 电动汽车的电池[6,7]、5G 网络基础设施[8]、LED照明[9]、电脑CPU[10]等器件面临着高热通量(高热流密度)和温度分布不均匀的挑战[11], 过热可能导致器件性能和寿命降低, 甚至有起火和爆炸危险[12]. 导热材料在器件散热管理领域至关重要[13-22]. 所有已知材料在室温下的热导率都分布在10–2—103 W·m–1·K–1数量级[5,13,23]. 相比于传统导热材料金属和陶瓷, 高分子聚合物因其质量轻、耐腐蚀、电绝缘、可塑性、低成本等的优异特性, 被广泛用于系统封装, 如芯片贴装[3,24]. 但是, 普通高分子聚合物是良好的热绝缘体, 其热导率约在0.1—0.5 W·m–1·K–1 [24-27], 导热性能不佳. 将绝热或低导热高分子聚合物转变成先进的导热聚合物将为解决散热问题提供新思路[11,24-26,28-34].

      值得注意的是, 常用低热导聚合物, 比如聚乙烯(约0.5 W·m–1·K–1)的C—C(碳-碳)单键骨架与金刚石的C—C键有着类似之处[4,15]. 金刚石是目前最好的导热材料之一, 其热导率可以高达约2000 W·m–1·K–1[15]. 分子动力学模拟结果进一步表明, 单链聚乙烯可具有非常高的热导率 (约350 W·m–1·K–1, 或在某些特定情况下热导率是无穷大)[35,36]. 该模拟结果与 Fermi 等[37]讨论的一维热导体non-ergodic特性一致. 导热高分子聚合物不断被研发出来[21,38-50]. 比如, Choy等[38]研发了导热聚乙烯, Shen等[21]研发了导热单根聚乙烯纳米纤维, 其热导率高达约104 W·m–1·K–1. Xu等[39]研发了高导热性聚乙烯薄膜新材料, 其热导率约为 62 W·m–1·K–1, 其热导率比金属(304-stainless steel 约为15 W·m–1·K–1)[51]和陶瓷高(aluminum oxide约为30  W·m–1·K–1)[52].

      随着对微米纳米尺度传热机制研究的不断深入[4,36,53], 研究人员对聚合物导热机制有了更深入的理解[22,24,25,34,54,55], 聚合物热导率与结构参数之间的关系得到了进一步的阐释. 研究人员报道了高热导率的高分子聚合物材料, 在很多关键热管理应用中前景广阔.

    • 传统高分子聚合物的无序结构(比如高分子链纠缠)及缺陷(比如高分子链末端、空隙、杂质, 见图1)等都会限制其热载流子的有效传输, 导致高分子聚合物高分子的热导率比较低(约0.1 W·m–1·K–1)[24]. 在过去的几十年里, 研究人员对高分子聚合物热传输机制, 尤其是对高分子聚合物的热导率与其不同尺度下结构参数(从原子级到纳米级和微米级)关系有了更深入的探索, 并进一步揭示了聚合物单体结构[56]、原子间相互作用力、分子内/分子间相互作用力[57]、高分子链刚度[31]、高分子链取向[39,58,59]、结晶度[60]、晶体尺寸效应[61]、高分子链链长[62,63]、高分子链形态结构[41,64-73]、交联密度[74,75]、高分子分子量[31]与热导率之间的关系.

      图  1  微纳尺度及原子尺度下的高分子结构. 高分子链端、无定型链、链缠结、杂质等缺陷都可能成为热载流子散射点, 导致高分子聚合物高分子的热导率比较低 (约0.1 W·m–1·K–1)[24]

      Figure 1.  Polymer structures at micro-nano scale and atomic scale. Defects such as chain ends, amorphous chains, chain entanglement, impurities in polymers act as heat carrier scattering sites and hinder efficient thermal transport, result in relatively low thermal conductivity (about 0.1 W·m–1·K–1)[24].

      按照原子-弹簧模型, 一维高分子单原子链被简化为质量为 m 的小球被弹性系数为 K 的无质量弹簧连接起来的弹性链[4,76,77]. 相邻原子间的相互作用力被看作是正比于相对位移的弹性恢复力, 原子的振动则可以用耦合谐振子表示. 这种一维谐波链中的声速 (vs) 可以通过(1)式估算[77]:

      $ {v}_{{\rm{s}}}\approx x\sqrt{\frac{K}{\overline{M}}}=\sqrt{\frac{2\overline{E}}{\overline{{M}_{{\rm{b}}}}}}\text{, } $

      其中 x 是两个最近邻原子之间的距离; K 是最近邻原子之间的弹性常数; M是原子的平均质量; Mb是骨架原子的平均质量; $\overline{ {E}}$是骨架的平均键能($\overline{{E}}$ = Kx2/2). 研究表明, 声速可以用来估计高分子聚合物的高温下的最低热导率[78,79]. 含有更强的碳-碳共价键的一维度聚合物单晶, 骨架刚度大, 沿高分子链方向可以实现更有效的声子传输, 可以实现更高导热性[24,31,33,65]. 在分子模拟结果表明沿链方向热导率在单晶聚乙烯(PE, 约350 W·m–1·K–1)[35]和聚乙炔(PA, 约480 W·m–1·K–1)非常高[80]. 聚乙烯纳米纤维[21](约104 W·m–1·K–1)和聚乙烯薄膜[39](约62 W·m–1·K–1)中测得较高的热导率. 聚合物主链中碳碳共价键和其分子的有序性实现了高分子链方向. 目前许多导热高分聚合物纤维制备策略是通过机械拉伸方法对聚合物链取向的优化, 并实现其热导率(沿链长方向)的提高. 在二维尺度的导热聚合物薄膜开发等方面, 也证实了通过优化取向能实现更高的面内热导率[38,47,50]. 最近, Deng等[81,82]提出有机材料导热调控的新方式, 通过电场调控有机材料(尼龙和聚偏二氟乙烯)的热导率.

      高分子聚合物均方半径(radius of gyration)表征高分子分子链在空间的延伸程度. 具有更大的均方半径聚乙烯样品展示了更高的热导率[63]. 分子量(molecular weight, MW)是高分子聚合物性能表征的重要参数, 科研人员对聚合分子量与热导率与关系进行了深入的研究. 实验数据表明[63,83], 聚乙烯的热导率随着分子量的增加而增加, 比如具有低分子量的聚乙烯(Mw约为3.5×104), 其热导率约为1.2 W·m–1·K–1 [84]; 具有高分子量的聚乙烯(Mw约为3×106), 热导率约为是4.8 W·m–1·K–1 [84]. 高分子链末端可以被看作是缺陷并对热载流子的运输有散射作用. 在给定质量下, 分子量更高的聚乙烯具有较少的链端, 可导致链端对热载流子的散射减少[24]. 非共价键相互作用, 如氢键[41,85]、离子键[57], 堆积相互作用(π-π stacking)[84]、范德瓦耳斯力等[64,86]也对高分子聚合物的热导率起着至关重要的作用. 比如Kim等[41]与Xie等[85]报道了氢键可以使聚丙烯酸(PAA)和聚乙烯醇(PVA)复合材料表现出高热导率[41,85], Shanker等[57]报道了离子化的聚电解质具有高热导率, Xu等[84]报道了共轭聚噻吩材料具有高热导率. 最近Yu等[86]报道指出利用范德瓦耳斯力形成的限域效应能提高聚合物的热导率.

    • 根据其构建对象, 目前制备先进导热高分子材料的策略可以分为自上而下(top-down)和自下而上(bottom-up)两大类. 自上而下法从聚合物本身入手, 主要包括机械拉伸处理[21,38,39,43,47,58,87,88]、电纺法[11,89-91]、模板辅助法[31,45]等. 机械拉伸处理下, 聚合物热导率随着拉伸比升高, 这是由于拉伸后趋于笔直和有序的高分子骨架更有利于热传导效率的提高. 以聚乙烯纳米纤维为例, 2010年Shen 等[21]报道了一种机械拉伸处理后的纳米纤维热导率可约达 104 W·m–1·K–1. 这一热导率已经超过了包括铂、铁和镍在内的半数纯金属, 而块体聚乙烯的热导率通常只在0.1 W·m–1·K–1数量级. 这一高导热性的实现有赖于拉伸作用对聚合物纤维链取向的改善, 纤维质量进一步趋近于“理想的”聚乙烯单晶.

      除机械拉伸纤维外, 二维聚合物薄膜由于其独特的比表面积大的优势, 其在热交换等领域的应用潜力也吸引了研究人员的兴趣[59,92,93]. 例如, 导热聚合物薄膜可为下一代热交换器提供新的可能性. 自从Choy 等[43]首次报道高导热的聚乙烯薄膜以来(约14 W·m–1·K–1), 基于机械拉伸策略开发的聚合物薄膜研究已经取得了许多突破[38,47,50]. Xu 等[39]报道了一种高拉伸比下热导率约达到 62 W·m–1·K–1的聚乙烯薄膜, 拉伸作用下导热性的提高有赖于聚合物链取向的改善、分子链的伸展, 分子链有序性的提高, 以及结晶度和结晶尺寸等的提升.

      聚合物喷射静电拉伸纺丝法简称电纺法, 也是一种常用制备导热高分子的方法. 通过在纺丝毛细管口和纤维收集装置之间施加强电场, 当静电力能够克服液滴表面张力时形成射流, 随着溶剂在纺丝过程中蒸发, 形成连续的纳米纤维. 由于这一成型过程中聚合物纤维的链取向得到改善, 其沿纤维方向的热导率能得到显著增强[11,89-91]. 2015年, Ma等[46]在45 kV的电压下制备的静电纺丝聚乙烯纳米纤维沿纤维轴向的热导率约为 9.3 W·m–1·K–1, 相当于块体聚乙烯的 (约0.4 W·m–1·K–1) 20 倍以上. 显微拉曼光谱的表征结果进一步证实了静电纺丝法对聚合物链取向和结晶度的影响与大幅提升的热导率之间的关系[46]. 此外, Zhang等[83]对聚合物电纺纤维的分子量与其热导率的研究发现, 随着聚乙烯纤维Mw从 35000 到3000000, 其热导率持续上升, 这一结果可以归因于高分子量的聚乙烯纤维中更高的结晶度.

      Cao等[45]使用改进的纳米多孔模板润湿技术制备出了热导率在室温下高达为约26.5 W·m–1·K–1的高密度聚乙烯(HDPE纳米阵列). 这一纳米阵列分子链的高度取向可能源于剪切速率、振动扰动、易位、纳米限制和结晶的综合作用. 这一研究为探索如何提高聚合物本征导热性提供了更多可行的方向.

      与自上而下法不同, 自下而上法从聚合物的结构单元(单体)入手, 通过聚合手段和条件调控高分子的导热性能, 主要包括模板辅助聚合法[40] (template- assisted electrochemical polymerization)和化学气相沉积法(chemical vapor deposition, CVD) 等[84]. 模板辅助聚合法是一种制备可控高分子纳米结构的有效策略, 基于这种方法制备的聚噻吩纳米纤维的热导率能够约达到 4.4 W·m–1·K–1, 相当于传统块体聚噻吩热导率的20倍以上[40]. 化学气相沉积法(CVD)广泛用于制备高纯度高性能薄膜的一类技术, 能够有效调控高分子的链结构和形貌, 目前基于化学气相沉积方法制备的聚噻吩薄膜达到了约2.2 W·m–1·K–1的热导率[84].

    • 科研人员用分子模拟和实验数据证明高分子聚合物可以是良好的热导体, 并对其传热机制进行了研究. 但是聚合物传热的理论模型与实验进展间存在较大的差距 (图2). 文献[54]中 1D, 2D 和 3D 样品热导率的模拟误差值为10次独立模拟结果平均值的标准偏差; 文献[21]中的误差值为多次测量平均值的标准偏差; 文献[87]包括了总接触热阻和测量纤维直径的误差; 文献[48]中误差值为20次重复测量平均值的标准偏差; 文献[95]中的误差值包括系统误差和热导率的标准偏差; 文献[46]中误差值包括纤维尺寸; 文献[39]中的误差值包括样品几何测量、辐射贡献和热分流测量误差; 包括来自数据处理的标准误差和整个样品的热导率变化. 文献[58]中的误差值包括数据处理标准误差和样品内的热导率变化. 很多理论热导率数值并未得到实验数据的证实, 高分子导热待传热机制需要进一步研究.

      图  2  室温下聚乙烯(PE)的热导率实验数据[21,38,39,43-50,58,83,87,94-97]及模拟值[35,54,98]; 室温下聚噻吩(PT)的热导率实验数据[39,40,99,100]及模拟值[56]

      Figure 2.  Thermal conductivities of polyethylene at room temperature in experimental measurements[21,38,39,43-50,58,83,87,94-97]and simulations[35,54,98]. Thermal conductivities of polythiophene at room temperature in experimental measurements[39,40,99,100]and simulations[56].

      正如原子模拟结果所示, 结晶聚乙烯单链沿骨架方向有希望能达到很高的理论热导率[35], 这一结果在 Fermi 等[37]对一维热导体的非遍历特性讨论中也得到了支持. 不同理论模型对沿聚乙烯链方向热导率的预测分别高达约 350 W·m–1·K–1 [35]和 130 W·m–1·K–1 [54], 对聚乙烯薄膜和块体结晶聚乙烯的预测也达到了约70 W·m–1·K–1 和 45 W·m–1·K–1 [54]. 基于理论计算的可喜结果似乎昭示着聚合物导热及其应用的光明前景. 然而, 所有上述理论模型均基于聚合物为晶体这一假设. 实际上, 很难制备理想的块体聚合物单晶. 由于聚合物复杂的无序结构, 模拟结果[35,54,98]目前还不能用实验数据证明[21,38,39,43-50,58,83,87,94-97] (图2). 在结晶聚合物中, 沿链排列方向能实现高效的热传导[21,24,87,98]. 然而, 在无定形或半结晶态的聚合物中, 无序结构会阻碍热量的有效传递[24,25,32,33]. 例如聚合物链取向的随机性、大量存在的缺陷, 如空隙、杂质和链端等, 都会导致热载流子的散射, 从而使热导率进一步降低[29]. 迄今为止, 还没有确切的机制能够解释传热机制. 因此, 高分子聚合物的无序复杂结构给不同尺度下的传热机制研究带来了巨大的挑战. 比如, 高分子聚合物链的拓扑结构和热导率的定量影响并不明确; 高分子聚合物的链纠缠对热导率的定量影响并不明确.

      除了高导热性外, 材料的使用寿命和稳定性也是限制其得到大规模应用的一大因素. 为了适应特定的热管理应用需求, 导热聚合物还需要高热稳定性和高熔点. 此外, 大规模投入使用的聚合物热管理材料必然需要实现对工业制造成本的优化, 目前, 机械拉伸法下制备的超高拉伸比纳米纤维热导率已经取得了可喜的数据, 但是制造成本大大地限制了其应用潜能.

    • 本文简要回顾了导热高分子聚合物领域的最新发展. 讨论了聚合物中的传热机理, 分析了热导率与链结构之间的关系, 包括键强度、链取向、链刚度、分子量、结晶度等如何影响热导率, 介绍了制备导热高分子聚合物策略. 同时也提出了未来导热高导热聚合物高分子研究(传热机制及宏量制备等方面)面临的挑战. 导热聚合物具有其他材料无法替代的独特优势, 兼具质量轻、电绝缘性、耐腐蚀、高耐用性、可加工性、价格低和柔性, 将为未来的热管理应用提供新的可能. 例如, 导热和电绝缘聚合物将为电子封装(例如 LED 封装)提供新的可能性, 有效地解决 LED 电流过热问题可能导致 LED 发光效率低和寿命短的问题[25,101]; 导热和耐腐蚀的聚合物薄膜将有望在广泛的应用中取代金属热交换器[92,93]; 具有可控光学特性(比如具有良好的可见光反射率[102-104], 或者具有极优的辐射制冷性能[105])、疏水性[106]、透气性[107,108]、及可穿戴性[102,109,110]的导热聚合物将为可穿戴冷却产品提供新的机会. 随着对聚合物热传输机理的理解取得的不断突破及导热聚合物制备策略的进展, 我们相信, 导热高分子聚合物凭借其独特的特性组合, 在许多现有和不可预见的热管理领域中将大有可为.

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