GO表面原位生长CNTs改善聚丙烯导热复合材料分散与界面形态

doi:10.11949/0438-1157.20220835

化工学报 ›› 2022, Vol. 73 ›› Issue (11): 5150-5157.DOI: 10.11949/0438-1157.20220835

• 材料化学工程与纳米技术 • 上一篇下一篇

GO表面原位生长CNTs改善聚丙烯导热复合材料分散与界面形态

徐欢¹(), 柯律¹, 张生辉¹, 张子林¹, 韩广东², 崔金声², 唐道远³, 黄东辉³, 高杰峰⁴, 何新建⁵()

^1.中国矿业大学材料与物理学院，江苏徐州 221116
^2.浩珂科技有限公司，山东济宁 272100
^3.安徽森泰木塑集团股份有限公司，安徽广德 242299
^4.扬州大学化学化工学院，江苏扬州 225200
^5.中国矿业大学安全工程学院，江苏徐州 221116

收稿日期:2022-06-21 修回日期:2022-08-15 出版日期:2022-11-05 发布日期:2022-12-06
通讯作者: 何新建
作者简介:徐欢(1989—)，男，博士，副教授，hihuan@cumt.edu.cn
基金资助:
国家自然科学基金项目(52003292);江苏省自然科学基金项目(BK20200661);中国博士后科学基金项目(2020M681763);江苏省博士后科研资助计划项目(2021K578C);中央高校基本科研业务费专项资金(2021QN1115)

Upgrading dispersion and interfacial morphologies for thermally conductive polypropylene composites by in situ growth of carbon nanotubes at graphene oxide

Huan XU¹(), Lyu KE¹, Shenghui ZHANG¹, Zilin ZHANG¹, Guangdong HAN², Jinsheng CUI², Daoyuan TANG³, Donghui HUANG³, Jiefeng GAO⁴, Xinjian HE⁵()

^1.School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China
^2.Haoke Technology Co. , Ltd. , Jining 272100, Shandong, China
^3.Anhui Sentai WPC Group Share Co. , Ltd. , Guangde 242299, Anhui, China
^4.School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225200, Jiangsu, China
^5.School of Safety Engineering, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China

Received:2022-06-21 Revised:2022-08-15 Online:2022-11-05 Published:2022-12-06
Contact: Xinjian HE

摘要/Abstract

摘要：

二维结构氧化石墨烯(GO)纳米片在高分子导热复合材料领域有良好应用前景，但常受限于片层间相互作用过大导致的局部团聚，不利于力学性能和导热性能的提高。借助GO纳米片表面和边缘提供的大量活性位点以吸附铁基催化剂，进而通过微波辅助合成方法在GO表面原位生长碳纳米管(CNTs)的策略，在数分钟内合成具有三维多层次结构的纳米杂化体(GO-CNT)。通过常规熔融共混方法，可获得GO-CNT在聚丙烯(PP)基体中良好剥离与均匀分散形态，明显不同于GO/PP复合体系中严重的局部团聚现象。均匀分散的GO-CNT对PP复合材料的力学性能和导热性能提升效果显著：在3%(质量分数)含量下，复合材料的屈服强度和热导率分别达到了38.0 MPa和0.76 W/(m·K)，较纯PP增幅分别为20%和230%，明显优于传统GO改性复合材料。本研究为解决纳米片状填料在导热复合材料中的应用瓶颈提供了可行的结构设计策略和复合材料制备方法。

关键词: 氧化石墨烯, 碳纳米管, 原位纳米杂化, 热导率, 力学性能

Abstract:

Conventional 2D graphene oxide (GO) nanosheets have shown promise in the applications of thermally conductive polymer nanocomposites, which is unfortunately dwarfed by the local aggregation of GO due to the extensive interplanar interactions. Here, a microwave-assisted synthetic approach was proposed to enable in situ growth of carbon nanotubes (CNTs) at both the basal planes and the edges of GO templates, engendering a minute-level and straightforward route to create 3D hierarchical nanohybrids (GO-CNT). The nanohybrids and GO [1%, 2% and 3%(mass)] were incorporated into polypropylene (PP) using common extrusion compounding amenable to scale up. Unlike the prominent local aggregation of GO in PP composites, GO-CNT was properly exfoliated and dispersed regardless of the loadings. This contributed to multiple improvements in mechanical properties and thermal conductivity for GC/PP, as exemplified by the highest yield strength (38.0 MPa) and thermal conductivity [0.76 W/(m·K)] for GC3, displaying remarkable increase of 20% and 230% compared to those of pure PLA. This work affords elucidation of direct covalent functionalization of 2D nanosheets and property-by-morphology understanding in polymer composites, which may motivate further extension to other polymer composite systems.

Key words: graphene oxide, carbon nanotube, in situ nanohybridization, thermal conductivity, mechanical properties

中图分类号:

TB 332

徐欢, 柯律, 张生辉, 张子林, 韩广东, 崔金声, 唐道远, 黄东辉, 高杰峰, 何新建. GO表面原位生长CNTs改善聚丙烯导热复合材料分散与界面形态[J]. 化工学报, 2022, 73(11): 5150-5157.

Huan XU, Lyu KE, Shenghui ZHANG, Zilin ZHANG, Guangdong HAN, Jinsheng CUI, Daoyuan TANG, Donghui HUANG, Jiefeng GAO, Xinjian HE. Upgrading dispersion and interfacial morphologies for thermally conductive polypropylene composites by in situ growth of carbon nanotubes at graphene oxide[J]. CIESC Journal, 2022, 73(11): 5150-5157.

图/表 6

图1 微波辅助合成方法制备纳米杂化体GO-CNT流程示意图

Fig.1 Schematic illustration for the fabrication of GO-CNT nanohybrids by MAS approach

图2 纳米杂化体GO-CNT结构演变过程

Fig.2 Structural evolution during the synthesis GO-CNT nanohybrids

图3 复合材料中碳纳米结构表征

Fig.3 Structural identification for nanocomposites

图4 SEM观察复合材料GO2和GC2中分散形态与界面结合情况

Fig.4 SEM images showing the dispersion and interfacial morphologies for GO2 and GC2

图5 复合材料拉伸性能与断裂机制

Fig.5 Tensile properties and fracture mechanisms of nanocomposites

图6 复合材料的导热性能

Fig.6 Thermal conductivity of nanocomposites

参考文献 34

1	Tan X, Yuan Q L, Qiu M T, et al. Rational design of graphene/polymer composites with excellent electromagnetic interference shielding effectiveness and high thermal conductivity: a mini review[J]. Journal of Materials Science & Technology, 2022, 117: 238-250.
2	陈海斌, 陈瑞, 刘美琪, 等. 基于外力诱导取向的高导热聚合物基复合材料研究进展[J]. 复合材料学报, 2022, 39(4): 1486-1497.
	Chen H B, Chen R, Liu M Q, et al. Research progress of force-induced oriented highly thermally conductive polymer composites[J]. Acta Materiae Compositae Sinica, 2022, 39(4): 1486-1497.
3	Chen X J, Su Y H, Reay D, et al. Recent research developments in polymer heat exchangers—a review[J]. Renewable and Sustainable Energy Reviews, 2016, 60: 1367-1386.
4	Zhang Y H, Wang W, Zhang F, et al. Micro-diamond assisted bidirectional tuning of thermal conductivity in multifunctional graphene nanoplatelets/nanofibrillated cellulose films[J]. Carbon, 2022, 189: 265-275.
5	Zhou S S, Xu T L, Jin L Y, et al. Ultraflexible polyamide-imide films with simultaneously improved thermal conductive and mechanical properties: design of assembled well-oriented boron nitride nanosheets[J]. Composites Science and Technology, 2022, 219: 109259.
6	Sun D X, Gu T, Mao Y T, et al. Fabricating high-thermal-conductivity, high-strength, and high-toughness polylactic acid-based blend composites via constructing multioriented microstructures[J]. Biomacromolecules, 2022, 23(4): 1789-1802.
7	Zhang C, Liu T. A review on hybridization modification of graphene and its polymer nanocomposites[J]. Chinese Science Bulletin, 2012, 57(23): 3010-3021.
8	Liu X X, Huang Y Z, Huang Z X. Compatibilizing and functionalizing polypropylene/polyethylene by in-situ exfoliating hexagonal boron nitride at interface[J]. Composites Science and Technology, 2022, 221: 109354.
9	Mu X, Wu X F, Zhang T, et al. Thermal transport in graphene oxide—from ballistic extreme to amorphous limit[J]. Scientific Reports, 2014, 4: 3909.
10	Zhang H J, Fonseca A F, Cho K. Tailoring thermal transport property of graphene through oxygen functionalization[J]. The Journal of Physical Chemistry C, 2014, 118(3): 1436-1442.
11	Liu L Q, Gao Y, Liu Q, et al. High mechanical performance of layered graphene oxide/poly(vinyl alcohol) nanocomposite films[J]. Small, 2013, 9(14): 2466-2472.
12	Garcia P S, Oliveira Y, Valim F, et al. Tailoring the graphene oxide chemical structure and morphology as a key to polypropylene nanocomposite performance[J]. Polymer Composites, 2021, 42(11): 6213-6231.
13	Yu W, Xie H Q, Li F X, et al. Significant thermal conductivity enhancement in graphene oxide papers modified with alkaline earth metal ions[J]. Applied Physics Letters, 2013, 103(14): 141913.
14	Zhou Y, Li L, Chen Y, et al. Enhanced mechanical properties of epoxy nanocomposites based on graphite oxide with amine-rich surface[J]. RSC Advances, 2015, 5(119): 98472-98481.
15	Graziano A, Garcia C, Jaffer S, et al. Functionally tuned nanolayered graphene as reinforcement of polyethylene nanocomposites for lightweight transportation industry[J]. Carbon, 2020, 169: 99-110.
16	Sreenatha P R, Mandal S, Singh S, et al. Remarkable synergetic effect by in-situ covalent hybridization of carbon dots with graphene oxide and carboxylated acrylonitrile butadiene rubber[J]. Polymer, 2019, 175: 283-293.
17	Wu X, Mu F W, Zhao H Y. Recent progress in the synthesis of graphene/cnt composites and the energy-related applications[J]. Journal of Materials Science & Technology, 2020, 55: 16-34.
18	Mahadevaswamy M B, Aradhya R, Bhattacharya S, et al. Effect of hybrid carbon nanofillers at percolation on electrical and mechanical properties of glass fiber reinforced epoxy[J]. Journal of Applied Polymer Science, 2022, 139(26): e52439.
19	Li H Y, Yang L, Weng G S, et al. Toughening rubbers with a hybrid filler network of graphene and carbon nanotubes[J]. Journal of Materials Chemistry A, 2015, 3(44): 22385-22392.
20	Zheng Y, Li D, Ahmed Z, et al. Carbon nanotube-on-graphene heterostructures[J]. Journal of Electronic Materials, 2020, 49(11): 6806-6816.
21	Mi X Q, Zhong L Y, Wei F, et al. Fabrication of halloysite nanotubes/reduced graphene oxide hybrids for epoxy composites with improved thermal and mechanical properties[J]. Polymer Testing, 2019, 76: 473-480.
22	Kumar R, Alaferdov A V, Singh R K, et al. Self-assembled nanostructures of 3D hierarchical faceted-iron oxide containing vertical carbon nanotubes on reduced graphene oxide hybrids for enhanced electromagnetic interface shielding[J]. Composites Part B: Engineering, 2019, 168: 66-76.
23	Kumar R, Sahoo S, Tan W K, et al. Microwave-assisted thin reduced graphene oxide-cobalt oxide nanoparticles as hybrids for electrode materials in supercapacitor[J]. Journal of Energy Storage, 2021, 40: 102724.
24	Shang H, Ke L, Xu W X, et al. Microwave-assisted direct growth of carbon nanotubes at graphene oxide nanosheets to promote the stereocomplexation and performances of polylactides[J]. Industrial & Engineering Chemistry Research, 2022, 61(2): 1111-1121.
25	Xu H, Wu D, Yang X, et al. Thermostable and impermeable "nano-barrier walls" constructed by poly(lactic acid) stereocomplex crystal decorated graphene oxide nanosheets[J]. Macromolecules, 2015, 48(7): 2127-2137.
26	Xie L, Shan B, Sun X, et al. Natural fiber-anchored few-layer graphene oxide nanosheets for ultrastrong interfaces in poly(lactic acid)[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(4): 3279-3289.
27	Yang G J, Liu Z P, Weng S T, et al. Iron carbide allured lithium metal storage in carbon nanotube cavities[J]. Energy Storage Materials, 2021, 36: 459-465.
28	Schniepp H C, Li J, McAllister M J, et al. Functionalized single graphene sheets derived from splitting graphite oxide[J]. The Journal of Physical Chemistry B, 2006, 110(17): 8535-8539.
29	Bajpai R, Wagner H D. Fast growth of carbon nanotubes using a microwave oven[J]. Carbon, 2015, 82: 327-336.
30	Wang H, Wang Y F, Cao X W, et al. Vibrational properties of graphene and graphene layers[J]. Journal of Raman Spectroscopy, 2009, 40(12): 1791-1796.
31	Xu H, Adolfsson K H, Xie L, et al. Zero-dimensional and highly oxygenated graphene oxide for multifunctional poly(lactic acid) bionanocomposites[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(10): 5618-5631.
32	Xu H, Xie L, Wu D, et al. Immobilized graphene oxide nanosheets as thin but strong nanointerfaces in biocomposites[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(4): 2211-2222.
33	石兴达, 陈华艳, 戈亚南, 等. 低界面热阻改性氮化铝和多壁碳纳米管充填PVDF构建杂化三维网络及其导热性能强化[J]. 化工学报, 2022, 73(5): 2262-2269.
	Shi X D, Chen H Y, Ge Y A, et al. Construction of three-dimensional network by modified MWCNT and AlN fillings in PVDF to improve the thermal conductivity[J]. CIESC Journal, 2022, 73(5): 2262-2269.
34	蔡楚玥, 方晓明, 张正国, 等. CNTs阵列增强石蜡/硅橡胶复合相变垫片的散热性能研究[J]. 化工学报, 2022, 73(7): 2874-2884.
	Cai C Y, Fang X M, Zhang Z G, et al. Enhancing heat dissipation performance of paraffin/silicone rubber phase change thermal pad by introducing carbon nanotubes[J]. CIESC Journal, 2022, 73(7): 2874-2884.

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GO表面原位生长CNTs改善聚丙烯导热复合材料分散与界面形态

Upgrading dispersion and interfacial morphologies for thermally conductive polypropylene composites by in situ growth of carbon nanotubes at graphene oxide

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