王越¹， 顾傲天²， 杨毅¹

1. 南京理工大学 环境与生物工程学院，江苏 南京 210094； 2. 泰州学院 化学化工与材料工程学院，江苏 泰州 225300

引用格式：

王越， 顾傲天， 杨毅. 氧化石墨烯强化环氧树脂及类玻璃高分子的结构性能［J］. 中国粉体技术， 2027， 33（1）： 1-17.

Wang Yue， Gu Aotian， Yang Yi. Structure and properties of graphene oxide-reinforced epoxy resins and vitrimers［J］. China Powder Science and Technology， 2027， 33（1）： 1-17.

DOI：10.13732/j.issn.1008-5548.2027.01.003

收稿日期： 2026-05-27， 修回日期： 2026-08-27， 上线日期： 2026-09-15。

基金项目： 国家自然科学基金项目，编号：52470120。

第一作者： 王越（2002—），男，硕士生，研究方向为纳米材料。E-mail：wy1586147@163.com。

通信作者： 杨毅（1973—），男，研究员，博士，博士生导师，江苏省“333工程”、江苏省“六大人才高峰”人才，研究方向为环境功能材料。E-mail：yangyi@njust.edu.cn。

摘要： 【目的】 揭示氧化石墨烯（graphene oxide，GO）形貌与动态共价网络之间的协同增强机制。 【方法】 以化学组成相近但长径比显著不同的商业化长径比小的氧化石墨烯（low-aspect-ratio graphene oxide，GOc）与实验室合成的长径比大的氧化石墨烯（high-aspect-ratio graphene oxide，GOH）为纳米填料，系统考察GO形貌对环氧树脂和类玻璃高分子纳米复合材料结构、热学、电学、力学及应力松弛性能的影响。 【结果】 结构与成分表征表明，类玻璃高分子固化剂中硫原子与GO表面含氧官能团之间的物理极性亲和作用使GO在类玻璃高分子基体中的分散均匀性显著优于环氧树脂基体；GO的引入导致2种基体的玻璃化转变温度因自由体积增加而略有降低，但所有复合材料均保持了低电导率特性；力学性能测试表明，GOc在2种基体中的增强效果均优于GOH，其中GOc使类玻璃高分子和环氧树脂的储能模量分别提升约30%和5%，这与GOc平整厚实的片层形貌所赋予的低团聚特性及高效载荷传递能力密切相关；应力松弛测试进一步证实，GOc-类玻璃高分子复合材料在80、120 ℃下均表现出最快的松弛速率，揭示GOc优异分散性与类玻璃高分子动态共价网络之间的协同增强效应。 【结论】 调控GO形貌是优化动态聚合物纳米复合材料力学与松弛性能的有效策略，为开发可持续高性能热固性纳米复合材料提供实验依据。

关键词： 氧化石墨烯； 类玻璃高分子； 应力松弛； 储能模量； 动态共价网络

Abstract

Objective Epoxy resin （EP） is widely used in aerospace， automotive， electronic packaging， and laminated composite applications due to its mechanical strength， chemical resistance， dimensional stability， and electrical insulation. However， its permanently cross-linked network makes it intrinsically brittle and prevents reshaping or recycling after curing. Covalent adaptable networks （CANs）， particularly epoxy-based vitrimers， overcome this limitation by enabling topological rearrangement through reversible bond exchange while maintaining the cross-link density. Graphene oxide （GO） is a widely adopted reinforcement for such networks. However， existing studies have focused almost exclusively on GO loading， and the role of GO sheet morphology in governing the reinforcement of dynamic covalent networks remains unclear. Therefore， this study aims to reveal the synergistic reinforcement mechanism between GO morphology and dynamic covalent networks， and to establish morphology engineering as a design parameter for sustainable， reprocessable， high-performance thermosets.

Methods Two GO grades with comparable surface chemistry and lateral dimensions but distinctly different aspect ratios were selected as nanofillers： a commercial low-aspect-ratio graphene oxide （GOc） and a laboratory-synthesized high-aspect-ratio graphene oxide （GOH） prepared using a modified Hummers method. The GO powders were characterized using Fourier transform infrared spectroscopy （FTIR）， Raman spectroscopy， scanning electron microscope （SEM）， and transmission electron microscope （TEM） to compare their oxygen-containing functional groups， defect density， lateral dimensions， sheet thickness， and degrees of exfoliation. Four nanocomposites containing 1 wt% filler were then fabricated. For the epoxy system， GO was ultrasonically dispersed in acetone for 30 min and then mixed with Araldite LY564 epoxy under mechanical stirring at 80 ℃ for 18 h. Subsequently， the mixture was combined with Aradur 2 954 hardener at a volume ratio of 100：35， degassed at 60 ℃ for 1 h， and cured at 80 ℃ for 1 h followed by 160 ℃ for 4 h. For the vitrimer system， 4-aminophenyl disulfide was used as the dynamic hardener. The mixture was degassed at 80 ℃ for 1 h and cured at 120 ℃ for 2.5 h， followed by curing at 150 ℃ for 2 h. Unfilled EP and vitrimer controls were prepared following identical procedures. Structure and filler dispersion were assessed by Raman spectroscopy and SEM imaging of cryo-fractured cross-sections. Interfacial chemistry was probed by XPS analysis of the C 1s， O 1s， and S 2p regions. Glass transition temperatures were determined using differential scanning calorimetry （DSC）. Stress relaxation was measured using the same dynamic mechanical thermal analysis （DMTA） instrument at 80 ℃ for 100 min and at 120 ℃ for 30 min. Electrical conductivity was obtained using impedance spectroscopy on silver-painted specimens.

Results and Discussion FTIR and Raman results confirmed that GOc and GOH contained equivalent hydroxyl， carbonyl， and carboxyl groups， as well as comparable I_D/I_G ratios， indicating similar oxidation levels. SEM showed that both grades exhibited lateral dimensions of 5-10 μm， predominantly 6-8 μm. TEM images clearly discriminated between the two morphologies. GOc consisted of flat， multilayer stacks with greater thickness， whereas GOH consisted of thinner， few-layer， strongly wrinkled sheets， indicating that the aspect-ratio difference originated from exfoliation rather than from chemistry. The D and G bands were retained in all four nanocomposites， confirming that GO was incorporated without structural degradation. XPS spectra of the composites showed no chemical shifts relative to the neat matrices， which demonstrated that no new covalent bonds were formed at 1 wt%. Thus， the improved dispersion observed in the vitrimer was attributed to physical polar affinity between the sulfur atoms of the disulfide hardener and the oxygen-containing groups on GO. SEM fractography supported this interpretation： GOc-vitrimer exhibited the most uniform dispersion and the most diffuse filler-matrix interface， while GOH-epoxy showed pronounced agglomerates， sharp interfaces， and voids that served as crack initiation sites. Incorporation of GO lowered T_g in both matrices， from 163 ℃ （DMTA） and 158 ℃ （DSC） for neat EP and from 143 ℃ and 138 ℃ for neat vitrimer. This decrease was attributed to weak filler-polymer interfacial bonding and the additional free volume introduced by GO. All samples remained electrically insulating， with conductivities on the order of 10⁻⁹ S·m⁻¹， because the oxygen-containing groups disrupted the delocalized π-electron system and no percolating network was formed. Mechanically， GOc increased the storage modulus of vitrimer and EP by approximately 30% and 5%， respectively， whereas GOH provided about 20% reinforcement in vitrimer and negligible reinforcement in EP， which was consistent with the lower agglomeration tendency and more efficient load transfer of the flat， thicker GOc sheets. Stress relaxation was markedly faster in vitrimer than in EP at both temperatures owing to disulfide exchange. Among all samples， GOc-vitrimer exhibited the fastest relaxation behavior， revealing a genuine synergy between well-dispersed GOc and the dynamic covalent network.

Conclusion GO morphology is a decisive parameter that governs the overall performance of polymer nanocomposites， while the matrix type further amplifies or suppresses the reinforcement through interfacial affinity and network dynamics. Low-aspect-ratio GOc outperforms high-aspect-ratio GOH in both matrices， and its combination with a disulfide-based vitrimer simultaneously optimizes mechanical stiffness and stress relaxation without compromising electrical insulation. Morphology engineering of GO therefore provides an experimental basis and a practical design route for high-performance， reprocessable， and sustainable thermosetting nanocomposites.

Keywords： graphene oxide； vitrimer； stress relaxation； storage modulus； dynamic covalent networks

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