石墨烯/六方氮化硼改性水性散热涂层的制备及性能研究

Preparation and properties of waterborne graphene/hexagonal boron nitride modified heat dissipation coating

摘要

[目的] 将石墨烯(GE)和六方氮化硼(h-BN)作为改性剂添加到水性有机硅改性环氧树脂氨基烤漆(EP)中，以制备一种GE/h-BN水性散热涂层，并探讨最佳h-BN含量条件下添加GE对涂层热导率、散热性能及热稳定性的影响。[方法] 通过热导率、散热温差和热重分析测试来确定涂层的散热和热稳定性效果，采用扫描电镜考察涂层的内部微观结构，并探讨了散热机制。[结果] 添加h-BN能提高涂层的散热效果和热稳定性，其最佳引入量约为24.0%(质量分数)。在此基础上，用不同含量的GE作进一步改性。试验结果证明，少量GE对涂层的散热性能有促进效果，过量则会导致涂层综合性能下降，GE的最佳引入量约为4.0%(质量分数)。[结论] 当GE含量过高时，其会与h-BN发生团聚，这是导致涂层性能下降的主要原因。明确涂层中GE和h-BN之间的共存关系有望进一步提升水性有机硅改性环氧树脂氨基烤漆的综合性能。

Abstract

[Objective] To prepare a waterborne heat-dissipation coating, graphene (GE) and hexagonal boron nitride (h-BN) was introduced as modifiers into a waterborne organosilicon-modified epoxy amino baking paint (EP). The effect of GE addition on the thermal conductivity, heat dissipation performance, and thermal stability of the coating under the optimal h-BN content was studied. [Method] The heat dissipation and thermal stability of coating were evaluated through thermal conductivity measurement, heat dissipation temperature difference testing, and thermogravimetric analysis. The internal microstructure of the coating was examined by scanning electron microscopy (SEM), and the heat dissipation mechanism was discussed. [Result] The addition of h-BN enhanced the heat dissipation efficiency and thermal stability of the coating, with an optimal content being approximately 24.0% by mass. On this basis, further modification was conducted using different dosages of GE. The experimental results showed that a small dosage of GE promoted the heat dissipation performance of the coating, while excessive dosage of GE led to a deterioration of other properties of the coating. The optimal GE dosage was approximately 4.0% by mass. [Conclusion] Excessive GE content causes aggregation with h-BN, which is the main reason for the degradation of coating performance. Clarifying the coexistence relationship between GE and h-BN in the coating is expected to further improve the comprehensive performance of the waterborne organosilicon-modified epoxy amino baking paint.

关键词

水性有机硅改性环氧树脂 / 石墨烯 / 六方氮化硼 / 复合涂层 / 散热 / 热导率

Key words

waterborne organosilicon-modified epoxy resin / graphene / hexagonal boron nitride / composite coating / heat dissipation / thermal conductivity

参考文献

[1] 任云鹏, 邢宝岩, 李世杰, 等. 石墨烯增效环氧导热涂层的制备及应用[J]. 涂料工业, 2024, 54(5): 66-70.

[2] REN Y P , XING B Y , LI S J , et al. Preparation and application of graphene enhanced epoxy thermal conductivity coating[J]. Paint & Coatings Industry, 2024, 54(5): 66-70.

[3] 车建. 石墨烯导热防腐涂层腐蚀促进活性的抑制研究[D]. 大连: 大连理工大学, 2022.

[4] CHE J. Inhibition of corrosion-promotion activity of graphene thermally conductive anti-corrosion coatings[D]. Dalian: Dalian University of Technology, 2022.

[5] 梁宇, 陈凯锋, 黄从树, 等. 石墨烯在功能涂料中的应用研究进展[J]. 装备环境工程, 2019, 16(8): 95-101.

[6] LIANG Y , CHEN K F , HUANG C S , et al. Application research progress of graphene functional coatings[J]. Equipment Environmental Engineering, 2019, 16(8): 95-101.

[7] 李金凤, 丁华, 陈名海, 等. 导热填料对碳纳米管水性辐射散热涂料性能的影响[J]. 上海涂料, 2019, 57 (1): 1-6.

[8] LI J F , DING H , CHEN M H , et al. The effect of heat conducting filler on the properties of waterborne carbon nanotubes radiation heat dissipation coatings[J]. Shanghai Coatings, 2019, 57 (1): 1-6.

[9] 柴全微. 高导热涂料的制备及在电机上的应用[J]. 现代涂料与涂装, 2018, 21(1): 6-9.

[10] CHAI Q W. Preparation of high thermal conductivity coatings and its application on motor[J]. Modern Paint & Finishing, 2018, 21(1): 6-9.

[11] 周开河, 曹文杰, 朱艳伟, 等. 一种变压器外壳用防腐导热涂层体系的制备及性能[J]. 电镀与涂饰, 2020, 39(20): 1444-1450.

[12] ZHOU K H , CAO W J , ZHU Y W , et al. Preparation and properties of an anticorrosion and heat conduction coating system for transformer shell[J]. Electroplating & Finishing, 2020, 39(20): 1444-1450.

[13] YAO Y M , SUN J J , ZENG X L , et al. Construction of 3D skeleton for polymer composites achieving a high thermal conductivity[J]. Small, 2018, 14(13): 1704044.

[14] ZHU P J , YAN Y N , ZHOU Y , et al. Thermal properties of graphene and graphene-based nanocomposites: a review[J]. ACS Applied Nano Materials, 2024, 7(8): 8445-8463.

[15] SHI X F , WANG K H , TIAN J , et al. Few-layer hydroxyl-functionalized boron nitride nanosheets for nanoscale thermal management[J]. ACS Applied Nano Materials, 2020, 3(3): 2310-2321.

[16] 邢伟义, 陈亮, 周慕天, 等. 氮化硼/石墨烯复合导热填料的制备及其环氧树脂复合材料阻燃导热绝缘性能的研究[J]. 中国科学: 化学, 2023, 53(2): 207-216.

[17] XING W Y , CHEN L , ZHOU M T , et al. Preparation of boron nitride/graphene composite thermal conductive filler and study on flame retardant, thermal conductivity and insulation properties of epoxy resin composites[J]. Scientia Sinica Chimica, 2023, 53(2): 207-216.

[18] 罗舒娟, 邓玉媛, 徐新宇, 等. 改性六方氮化硼/环氧树脂复合材料研究进展[J]. 化工新型材料, 2024, 52(7): 1-6.

[19] LUO S J , DENG Y Y , XU X Y , et al. Research progress on modified hexagonal boron nitride/epoxy resin composites[J]. New Chemical Materials, 2024, 52(7): 1-6.

[20] 高逸晖, 穆琪, 赵文忠, 等. 六方氮化硼改性防腐涂料对海洋环境服役翅片散热器散热性能影响研究[J]. 装备环境工程, 2025, 22(1): 125-132.

[21] GAO Y H , MU Q , ZHAO W Z , et al. Effects of boron nitride nanosheets modified anticorrosive coating on heat dissipation performance of fin heatsinks[J]. Equipment Environmental Engineering, 2025, 22(1): 125-132.

[22] 姜军. 石墨烯玻璃纤维的热稳定性研究[D]. 北京: 中国石油大学(北京), 2023.

[23] JIANG J. Thermal stability studies of graphene glass fiber fabric[D]. Beijing: China University of Petroleum (Beijing), 2023.

[24] 熊美. 硼−氮化合物新结构的理论与实验研究[D]. 秦皇岛: 燕山大学, 2017.

[25] XIONG M. Theoretical and experimental research of novel structures of boron-nitride compounds[D]. Qinhuangdao: Yanshan University, 2017.

[26] POURHASHEM S , RASHIDI A , VAEZI M R , et al. Excellent corrosion protection performance of epoxy composite coatings filled with amino-silane functionalized graphene oxide[J]. Surface & Coatings Technology, 2017, 317: 1-9.