纳米高岭土/环氧树脂复合材料的制备及其分子动力学模拟

doi:10.16085/j.issn.1000-6613.2024-1541

摘要/Abstract

摘要：

为了研究纳米高岭土的掺量对环氧树脂热性能和力学性能的影响，以环氧树脂为基体并配以固化剂，以不同掺量下的纳米高岭土为填料构建了复合环氧树脂体系，分别考察了复合材料的玻璃化转变温度、弹性模量、剪切模量、泊松比、硬度等指标并计算了自由体积分数和相互作用能。结果表明：实验条件下当纳米高岭土掺量（质量分数）为10%时，环氧复合材料的玻璃化转变温度达到最大值120.06℃、硬度达到最大值6H，杨氏模量为6.655GPa，剪切模量为2.594GPa，泊松比为0.283，热稳定性能和力学性能均达到了最佳。通过分子动力学模拟，当复合材料的交联度为90%时，模型在平衡状态下的能量波动较小并处于平衡状态，此状态下计算得到的玻璃化转变温度和力学性能在纳米高岭土掺量10%时为最优，与实验值基本吻合。纳米高岭土自身有着优异的热力学性质的同时，其适量掺入可有效降低自由体积分数，与环氧树脂之间良好的界面能相互作用对于提升高岭土/环氧树脂纳米复合材料的热稳定性能和力学性能有着十分重要的作用，为环氧纳米复合材料的微观角度研究提供了理论基础。

关键词: 纳米高岭土, 环氧树脂, 玻璃化转变温度, 力学性能, 分子动力学模拟

Abstract:

To investigate the impact of nano kaolin content on the thermal and mechanical properties of epoxy resin, a composite epoxy resin system was developed using epoxy resin as the matrix and curing agent, and the composite epoxy resin system was constructed with nano kaolin as filler in different dosage. The glass transition temperature, elastic modulus, shear modulus, Poisson's ratio and hardness of the composites were examined, and the free volume fraction and interaction energy were quantified. Additionally, the free volume fraction and interaction energy were computed. The findings revealed that under experimental conditions, a nano kaolin mass fraction of 10% resulted in the nano kaolin/epoxy resin composite exhibited optimal properties: a glass transition temperature of 120.06℃, a hardness rating of 6H, a Young's modulus of 6.655GPa, a shear modulus of 2.594GPa and a Poisson's ratio of 0.283. This content led to the best thermal stability and mechanical properties. Molecular dynamics simulations further indicated that when the composite's crosslinking degree reached 90%, the model displayed minimal energy fluctuations in equilibrium. The glass transition temperature and mechanical properties calculated under these conditions were the best at a nano kaolin mass fraction of 10%, aligning well with the experimental results. Nano kaolin, known for its exceptional thermodynamic properties, could effectively reduce the free volume fraction when incorporated appropriately. The favorable interfacial energy interaction between nano kaolin and epoxy resin was pivotal in enhancing the thermal and mechanical characteristics of kaolin/epoxy resin nanocomposites. This research offered a foundational theory for the microscopic investigation of epoxy nanocomposites.

Key words: nano kaolin, epoxy resin, glass transition temperature, mechanical properties, molecular dynamics simulation

中图分类号:

TD985

张雨涵, 赵雪淞, 吴秀琳, 张婷, 杨龙凤. 纳米高岭土/环氧树脂复合材料的制备及其分子动力学模拟[J]. 化工进展, 2025, 44(11): 6477-6487.

ZHANG Yuhan, ZHAO Xuesong, WU Xiulin, ZHANG Ting, YANG Longfeng. Preparation and molecular dynamics simulation of nano kaolin/epoxy resin composites[J]. Chemical Industry and Engineering Progress, 2025, 44(11): 6477-6487.

图/表 13

图1 纳米高岭土、不同掺量纳米高岭土制备的环氧复合材料SEM图

图2 不同掺量纳米高岭土复合环氧材料的TG曲线

图3 不同掺量纳米高岭土复合材料的玻璃化转变温度曲线

表1 不同掺量纳米高岭土/环氧树脂复合材料的力学性能计算值及标准差

纳米高岭土掺量/%	杨氏模量/GPa	剪切模量/GPa	泊松比
标准差	0.989	0.499	0.171
0	4.059	1.458	0.392
5	4.531	1.741	0.301
10	6.655	2.594	0.283
15	4.801	1.590	0.511
20	4.502	1.448	0.555
25	3.932	1.135	0.732

图4 不同掺量纳米高岭土/环氧树脂复合材料的硬度测试结果

图5 分子结构模型

图6 不同掺量下的纳米高岭土/环氧树脂复合材料的分子动力学模型

图7 动力学平衡过程中不同能量的变化趋势（1kcal=4.1868kJ）

图8 优化后的环氧复合材料交联模型

图9 不同纳米高岭土掺量下环氧复合材料的玻璃化转变温度

表2 不同掺量纳米高岭土/环氧树脂复合材料的力学性能模拟计算值及标准差

纳米高岭土掺量/%	杨氏模量/GPa	剪切模量/GPa	泊松比
标准差	1.077	0.470	0.185
0	4.273	1.527	0.367
5	4.720	1.832	0.288
10	6.933	2.535	0.209
15	4.899	1.638	0.496
20	4.641	1.592	0.546
25	3.814	1.113	0.714

图10 不同掺量纳米高岭土/环氧树脂复合材料模型的自由体积占比及自由体积计算结果

表3 纳米高岭土与环氧树脂间相互作用能计算结果

纳米高岭土掺量/%	相互作用能/kcal·mol^-1
0	-65.71
5	-312.75
10	-320.42
15	-318.78
20	-287.75
25	-269.73

参考文献 51

[1]	WANG Haohuan, HUANG Zhengyong, ZENG Xiaoliang, et al. Enhanced anticarbonization and electrical performance of epoxy resin via densified spherical boron nitride networks[J]. ACS Applied Electronic Materials, 2023, 5(7): 3726-3732.
[2]	LIU Tianhui, ZHAO Yuzeng, DENG Yining, et al. Preparation of fully epoxy resin microcapsules and their application in self-healing epoxy anti-corrosion coatings[J]. Progress in Organic Coatings, 2024, 188: 108247.
[3]	HUANG Jialiang, ZHU Yu, GUO Shijia, et al. Surface treatment of large-area epoxy resin by water-perforated metal plate electrodes dielectric barrier discharge: Hydrophobic modification and uniformity improvement[J]. Applied Surface Science, 2023, 639: 158166.
[4]	MAHIDASHTI Z, RAMEZANZADEH B, BAHLAKEH G. Screening the effect of chemical treatment of steel substrate by a composite cerium-lanthanum nanofilm on the adhesion and corrosion protection properties of a polyamide-cured epoxy coating; Experimental and molecular dynamic simulations[J]. Progress in Organic Coatings, 2018, 114: 188-200.
[5]	QI Hongfei, HEISE Svenja, ZHOU Juncen, et al. Electrophoretic deposition of bioadaptive drug delivery coatings on magnesium alloy for bone repair[J]. ACS Applied Materials & Interfaces, 2019, 11(8): 8625-8634.
[6]	YANG Yuyun, ZHOU Juncen, CHEN Qiang, et al. In vitro osteocompatibility and enhanced biocorrosion resistance of diammonium hydrogen phosphate-pretreated/poly(ether imide) coatings on magnesium for orthopedic application[J]. ACS Applied Materials & Interfaces, 2019, 11(33): 29667-29680.
[7]	KHODAIR Ziad T, KHADOM Anees A, JASIM Hassan A. Corrosion protection of mild steel in different aqueous media via epoxy/nanomaterial coating: Preparation, characterization and mathematical views[J]. Journal of Materials Research and Technology, 2019, 8(1): 424-435.
[8]	YUAN Shuai, ZHAO Xia, JIN Zuquan, et al. Fabrication of an environment-friendly epoxy coating with flexible superhydrophobicity and anti-corrosion performance[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 633: 127545.
[9]	ZHOU Chaogang, CHEN Qiya, ZHAO Jingjing, et al. Superhydrophobic epoxy resin coating with composite nanostructures for metal protection[J]. Materials Today Communications, 2024, 38: 107803.
[10]	KANWAL Rumasa, MAQSOOD Muhammad Faheem, RAZA Mohsin ALI, et al. Polypyrrole coated carbon fiber/magnetite/graphene oxide reinforced hybrid epoxy composites for high strength and electromagnetic interference shielding[J]. Materials Today Communications, 2024, 38: 107684.
[11]	MENG Tian, CHEN Jingwei, Jiaqiang E, et al. Molecular dynamics study on the dissolution characteristics and cluster formation of Li₂CO₃ in supercritical water[J]. Journal of Molecular Liquids, 2023, 392: 123454.
[12]	HU Haowei, LI Qin, LIU Shuang, et al. Molecular dynamics study on water vapor condensation and infiltration characteristics in nanopores with tunable wettability[J]. Applied Surface Science, 2019, 494: 249-258.
[13]	MA Qiang, QI Penghao, DONG Guangneng. An experimental and molecular dynamics study of the superlubricity enabled by hydration lubrication[J]. Applied Surface Science, 2021, 553: 149590.
[14]	KOCAAGA Banu, Seniha GUNER F, KURKCUOGLU Ozge. Molecular dynamics simulations can predict the optimum drug loading amount in pectin hydrogels for controlled release[J]. Materials Today Communications, 2022, 31: 103268.
[15]	ZHANG Zhenpeng, WANG Heyu, LI Zhonglei, et al. Molecule diffusion behaviours of waterproof sealants into silicone rubber insulation for submarine cable joint based on molecular dynamics simulations[J]. High Voltage, 2021, 6(2): 230-241.
[16]	SHENG Can, WU Gai, SUN Xiang, et al. Molecular dynamics investigation of the thermo-mechanical properties of the moisture invaded and cross-linked epoxy system[J]. Polymers, 2021, 14(1): 103.
[17]	FRANK Katherine, CHILDERS Christopher, DUTTA Dhanadeep, et al. Fluid uptake behavior of multifunctional epoxy blends[J]. Polymer, 2013, 54(1): 403-410.
[18]	LI Mingyue, MIN Zhaohui, WANG Qichang, et al. Effect of epoxy resin content and conversion rate on the compatibility and component distribution of epoxy asphalt: A MD simulation study[J]. Construction and Building Materials, 2022, 319: 126050.
[19]	SUN Yingying, CHEN Lin, CUI Liu, et al. Molecular dynamics simulation of cross-linked epoxy resin and its interaction energy with graphene under two typical force fields[J]. Computational Materials Science, 2018, 143: 240-247.
[20]	BI Maoqiang, TONG Zhonghe, XIE Chuanlin, et al. The improvement mechanism of styrene grafted nano-Al₂O₃ on the hydrophobicity of epoxy resin composites: Based on molecular dynamics and experimental research[J]. Materials Today Communications, 2024, 40: 109369.
[21]	HONG Zixiao, XU Yuxin, YE Daiqi, et al. One-step fabrication of a robust and transparent superhydrophobic self-cleaning coating using a hydrophobic binder at room temperature: A combined experimental and molecular dynamics simulation study[J]. Surface and Coatings Technology, 2023, 472: 129943.
[22]	POURHASHEM Sepideh, HADIZADEH Mohammad Hassan, JI Xiaohong, et al. Recognizing the function of different silane coupling agents on MXene adsorption/barrier behavior in solvent-borne epoxy coatings: Experimental studies, density functional theory, and molecular dynamics simulations[J]. Progress in Organic Coatings, 2024, 192: 108453.
[23]	LI Shuo, YE Wenting, SHI Yeran, et al. Atomistic simulation and experimental verification of tribological behavior of high entropy alloy/graphene composite coatings[J]. Surface and Coatings Technology, 2023, 467: 129683.
[24]	YU Huiping, TONG Zhihao, CHEN Pei, et al. Effects of different parameters on thermal and mechanical properties of aminated graphene/epoxy nanocomposites connected by covalent: A molecular dynamics study[J]. Current Applied Physics, 2020, 20(4): 510-518.
[25]	HADDEN C M, JENSEN B D, BANDYOPADHYAY A, et al. Molecular modeling of EPON-862/graphite composites: Interfacial characteristics for multiple crosslink densities[J]. Composites Science and Technology, 2013, 76: 92-99.
[26]	YANG Seunghwa, KWON Sunyong, LEE Man Young, et al. Molecular dynamics and micromechanics study of hygroelastic behavior in graphene oxide-epoxy nanocomposites[J]. Composites Part B: Engineering, 2019, 164: 425-436.
[27]	毕茂强, 彭豪, 文娅, 等. 纳米掺杂环氧树脂热力学性能的分子动力学模拟[J]. 电瓷避雷器, 2023(2): 142-149.
	BI Maoqiang, PENG Hao, WEN Ya, et al. Molecular dynamics simulation of the thermodynamic properties of nano-doped epoxy resins[J]. Insulators and Surge Arresters, 2023(2): 142-149.
[28]	ANAM Ashutosh, GAMIT Nilam, PRAJAPATI Vimalkumar, et al. An overview of kaolin and its potential application in thermosetting polymers[J]. Materials Today Communications, 2023, 36: 106827.
[29]	SU Linna, ZENG Xiaoliang, HE Hongping, et al. Preparation of functionalized kaolinite/epoxy resin nanocomposites with enhanced thermal properties[J]. Applied Clay Science, 2017, 148: 103-108.
[30]	ZHANG Yuhan, ZHAO Xuesong, SHANG Baoyue, et al. Characterization of nano-kaolin and its enhancement of the mechanical and corrosion resistance of epoxy coatings[J]. Materials Today Communications, 2024, 41: 110371.
[31]	SONG Yunfei, YU Guoyang, YIN Hedong, et al. Temperature dependence of elastic modulus of single crystal sapphire investigated by laser ultrasonic[J]. Acta Physica Sinica, 2012, 61(6): 064211.
[32]	王成江, 周文戟, 范正阳, 等. 六方氮化硼纳米掺杂增强环氧树脂热学和力学性能的分子动力学模拟[J]. 绝缘材料, 2021, 54(1): 78-83.
	WANG Chengjiang, ZHOU Wenji, FAN Zhengyang, et al. Molecular dynamics simulation on thermal and mechanical properties of h-BN nano-doping enhanced epoxy resin[J]. Insulating Materials, 2021, 54(1): 78-83.
[33]	TABORDA-BARRAZA M, PELISSER F, GLEIZE Philippe J P. Thermal-mechanical properties of metakaolin-based geopolymer containing silicon carbide microwhiskers[J]. Cement and Concrete Composites, 2021, 123: 104168.
[34]	ZIDI Zeineb, LTIFI Mounir, ZAFAR Idrees. Synthesis and attributes of nano-SiO₂ local metakaolin based-geopolymer[J]. Journal of Building Engineering, 2021, 33: 101586.
[35]	SINGLA Rashmi, SENNA Mamoru, MISHRA T, et al. High strength metakaolin/epoxy hybrid geopolymers: Synthesis, characterization and mechanical properties[J]. Applied Clay Science, 2022, 221: 106459.
[36]	CHEN Shibo, WANG Xiaobo, ZHU Guiyu, et al. Developing multi-wall carbon nanotubes/fusion-bonded epoxy powder nanocomposite coatings with superior anti-corrosion and mechanical properties[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 628: 127309.
[37]	QU Jiajun, GAO Ke, HOU Gunayi, et al. Molecular dynamics simulation of glass transition and thermal stability of novel silicone elastomer and its nanocomposites[J]. Materials Today Communications, 2022, 33: 104517.
[38]	SONG Jingfu, ZHAO Gai, DING Qingjun, et al. Molecular dynamics study on the thermal, mechanical and tribological properties of PBI/PI composites[J]. Materials Today Communications, 2022, 30: 103077.
[39]	Saki OTA, MICHISHIO Koji, HARADA Miyuki. Development of T_g-less epoxy thermosets by introducing crosslinking points into rigid mesogenic moiety via Schiff base-derived self-polymerization[J]. Materials Today Communications, 2022, 31: 103501.
[40]	GEORGE Jesiya Susan, Poornima VIJAYAN P, VAHABI Henri, et al. Sustainable hybrid green nanofiller based on cellulose nanofiber for enhancing the properties of epoxy resin[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 694: 134082.
[41]	SHENG Lisha, WANG Yi, CHEN Zhenqian. Kinetic and thermodynamic property study of electrostatic-assisted porous liquids, nanofluids and nanoparticle organic hybrid materials by molecular dynamics simulation[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 674: 131898.
[42]	BISH D L, VON DREELE R B. Rietveld refinement of non-hydrogen atomic positions in kaolinite[J]. Clays and Clay Minerals, 1989, 37(4): 289-296.
[43]	HADIPEYKANI Majid, AGHADAVOUDI Farshid, TOGHRAIE Davood. A molecular dynamics simulation of the glass transition temperature and volumetric thermal expansion coefficient of thermoset polymer based epoxy nanocomposite reinforced by CNT: A statistical study[J]. Physica A: Statistical Mechanics and Its Applications, 2020, 546: 123995.
[44]	杨潞霞, 郭志婧, 郭丽媛, 等. 基于Perl语言的交联环氧树脂分子模型的构建和性能仿真[J]. 计算机与应用化学, 2017, 34(2): 172-176.
	YANG Luxia, GUO Zhijing, GUO Liyuan, et al. The construction of the model and properties simulation of crosslinking epoey resin based on Perl[J]. Computers and Applied Chemistry, 2017, 34(2): 172-176.
[45]	LI Yunlong, YANG Bin, YU Zitao, et al. A study on effects of Stone-Thrower-Wales defective carbon nanotubes on glass transition temperature of polymer composites using molecular dynamics simulations[J]. Computational Materials Science, 2021, 186: 110005.
[46]	HOUSKA J, ZEMAN P. Role of Al in Cu-Zr-Al thin film metallic glasses: Molecular dynamics and experimental study[J]. Computational Materials Science, 2023, 222: 112104.
[47]	HUANG Ming, ALVAREZ Nicolas J, PALMESE Giuseppe R, et al. The effect of network topology on material properties in vinyl-ester/styrene thermoset polymers using molecular dynamics simulations and time-temperature superposition[J]. Computational Materials Science, 2022, 207: 111264.
[48]	SALMAN M, VERESTEK W, SCHMAUDER S. Atomistic-scale modeling of nano-clay-filled shape memory polymers[J]. Computational Materials Science, 2021, 188: 110246.
[49]	ZHANG H J, SELLAIYAN S, SAKO K, et al. Effect of free-volume holes on static mechanical properties of epoxy resins studied by positron annihilation and PVT experiments[J]. Polymer, 2020, 190: 122225.
[50]	KUMAR H, SIDDARAMAIAH, KUMARASWAMY G N, et al. Free volume and the physico-mechanical behaviour of polyurethane/polyacrylonitrile interpenetrating polymer networks: Positron annihilation results[J]. Polymer International, 2005, 54(10): 1401-1407.
[51]	李建超. 杂化体增强及表面镶嵌微珠的ER复合涂层耐磨防腐性能与机理研究[D]. 北京: 北京科技大学, 2022.
	LI Jianchao. Wear and corrosion resistance properties and mechanism of ER composite coatings reinforced by hybrids and embedded with FACs[D]. Beijing: University of Science and Technology Beijing, 2022.