作者：周逸¹, 刘薇², 冯晓娟², 邱萍², 李会东³, 潘永杲¹

作者单位：1. 常州检验检测标准认证研究院，江苏 常州 213164;
2. 中国计量科学研究院，北京 100029;
3. 中国科学院上海硅酸盐研究所，上海 201899

关键词：石墨烯;聚丙烯;复合材料;导热系数;热扩散系数;比热容

摘要：

针对现有文献报道的石墨烯/PP复合材料导热系数测量结果差异较大，该文对相应测量方法、仪器、样品尺寸和测量结果等进行分析和评价。制备质量分数为5%至30%的石墨烯/PP复合材料块状和薄片状等样品，分别通过QTM500型、TC3000型和DRE-Ⅲ型3种瞬态导热系数测试仪对块状样品导热系数进行直接测量，并通过LFA467型激光闪光法导热仪、DSC3+型差示扫描量热仪和ZB603C型电子天平和密度组件分别对各质量分数石墨烯/PP复合材料样品的热扩散系数、比热容和密度进行测量后计算获得导热系数。结果表明：3种瞬态导热系数测试仪测量纯PP、5%和10%质量分数石墨烯/PP复合样块导热系数偏差在2.6%~8.7%范围内，大于各仪器声称测量偏差；直接测量法与间接测量法获得的导热系数偏差大于36%，且随石墨烯质量分数的增加而变大。因此，在测量复合材料导热系数时应选择适用尺寸和量程的直接测量法，导热系数等热物性参数的量值传递体系仍需进一步建立和完善来提高直接测量法的准确性和间接测量法的可靠性。

Measurement and analysis of thermal properties of graphene/polypropylene composites
ZHOU Yi¹, LIU Wei², FENG Xiaojuan², QIU Ping², LI Huidong³, PAN Yonggao¹
1. Changzhou Institute of Inspection Testing Standardization and Certification, Changzhou 213164, China;
2. National Institute of Metrology, Beijing 100029, China;
3. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
Abstract: In view of the large differences in the measurement results of thermal conductivity of graphene/PP composites reported in the references, the methods, instruments, size of samples and measurement results are analyzed and evaluated in this paper. Bulk and flake samples of graphene/PP composites with mass fraction of 5% to 30% were prepared. The thermal conductivity of bulk samples was directly measured by three transient thermal conductivity testers: QTM500, TC3000 and DRE-Ⅲ. The thermal diffusivity, specific heat capacity and density of graphene/PP composites were measured by LFA467 laser flash thermal conductivity meter, DSC3+ differential scanning calorimeter, ZB603C electronic balance and density module and the thermal conductivity was calculated. The results show that the thermal conductivity deviation of pure PP, 5% and 10% graphene/PP composite samples measured by three kinds of transient thermal conductivity tester is in the range of 2.6%-8.7%, which is greater than the claimed measurement deviation of each instrument. The deviation of thermal conductivity obtained by direct measurement method and indirect measurement method is more than 36%, and increases with the increase of graphene mass fraction. Therefore, the appropriate direct measurement method with size of samples and range of instrument should be selected when measuring the thermal conductivity of composite materials. The value transfer system of thermal properties such as thermal conductivity still need to be further established and improved to increase the accuracy of direct measurement method and the reliability of indirect measurement method.
Keywords: graphene;polypropylene;composites;thermal conductivity;thermal diffusivity;specific heat capacity
2022, 48(2):66-74  收稿日期: 2021-08-29;收到修改稿日期: 2021-11-05
基金项目: 国家重点研发计划项目资助（2016YFF0101707）
作者简介: 周逸(1995-),男,江苏常州市人,助理工程师,硕士,研究方向为材料热物性测量与热工计量检测技术研究
参考文献
[1] 周逸, 林鸿, 冯晓娟, 等. 石墨烯及其复合材料导热系数测量的研究进展[J]. 计量学报, 2020, 41(2): 159-169
[2] ZHANG P, ZENG J H ZHAI S P, et al. Thermal properties of graphene filled polymer composite thermal interface materials[J]. Macromolecular Materials and Engineering, 2017, 302(9): 1700068
[3] 孙小菊. 氨基化氧化石墨烯-水泥基复合材料的制备与研究[J]. 中国测试, 2020, 46(11): 158-162
[4] SONG N, CAO D L, LUO X, et al. Highly thermally conductive polypropylene/graphene composites for thermal management[J]. Composites Part A, 2020, 135: 105912
[5] 汪文, 丁宏亮, 张子宽, 等. 石墨烯微片/聚丙烯导热复合材料的制备与性能[J]. 复合材料学报, 2013, 30(6): 14-20
[6] 陈宇强, 肖小亭, 张婧婧, 等. 聚丙烯/石墨烯微片纳米复合材料的导电导热性能[J]. 塑料, 2016, 45(5): 57-59+121
[7] 张丽欣, 杨燕青, 周健, 等. 石墨烯/聚丙烯复合材料的制备与性能[J]. 现代塑料加工应用, 2018, 30(3): 9-12
[8] 陈桂生, 廖艳, 曾亚光, 等. 材料热物性测试的研究现状及发展需求[J]. 中国测试, 2010, 36(5): 5-8
[9] OLDHAM K B, LUCHSINGER E B. On the hot-wire method for the determination of thermal conductivities[J]. Transactions of the Faraday Society, 1968, 64: 1791-1797
[10] 贺永智, 徐旭, 潘江, 等. 基于TPS法液体导热系数的测量[J]. 中国测试, 2021, 47(5): 52-57
[11] 施祖锋, 王鲜, 聂彦, 等. Mn0.77–xZn0.19+xFe2.04O4铁氧体磁性能及热导率分析[J]. 磁性材料及器件, 2020, 51(6): 1-4
[12] 张琳, 杜斌, 鲁燕萍. 激光热导仪准确测量比热容的方法研究[J]. 真空电子技术, 2015(2): 41-45
[13] XUE J, TAYLOR R. An evaluation of specific heat measurement methods using the laser flash technique[J]. International Journal of Thermophysics, 1993, 14(2): 313-320
[14] 李佳, 王灿, 王海峰, 等. 中温固体比热容测量基准的研究进展[J]. 计量学报, 2016, 37(4): 384-389
[15] 韦刘洋, 刘定福, 梁基照. 聚丙烯/石墨烯片纳米复合材料阻燃及导热性能[J]. 工程塑料应用, 2016, 44(10): 98-101,115
[16] 周健, 李茂东, 杨燕青, 等. 石墨烯/聚丙烯复合材料力学性能、结晶行为与微观结构[J]. 江苏理工学院学报, 2019, 25(6): 1-7
[17] GUSTAFSSON S E. Transient plane source techniques for thermal conductivity and thermal diffusivity measurements of solid materials[J]. Review of Scientific Instruments, 1991, 62(3): 797-804
[18] 李宝林. 药用聚丙烯密度测量的不确定度评定[J]. 塑料包装, 2012, 22(4): 25-26+49
[19] 聚乙烯和聚丙烯树脂密度的测定常温浮定法: SN/T 1513—2005[S], 2005.