Atomic scale characterization of interfacial properties of polymer/metal composites
-
摘要: 聚合物/金属界面性能显著影响由金属和聚合物形成的复合材料的力学性能。结合热力学理论分析和分子动力学模拟，系统计算了几种典型聚合物(聚乙烯 (PE)、聚丙烯 (PP)、聚苯乙烯 (PS))和金属(Al、Ni、Cu、Fe)形成界面的断裂能及界面强度。聚合物/金属界面的界面应力随着界面位移的增加先增加，达到强度后进入界面损伤阶段，界面应力减小，直到界面完全断裂，应力降低为0。不同聚合物/金属界面的强度大小变化趋势与界面断裂能一致，界面断裂能模拟与理论计算结果基本一致。聚合物/金属界面断裂能与金属表面能强弱有关，由于金属的表面能随着Ni、Fe、Cu、Al的顺序逐渐减小，相应形成的聚合物/金属界面的断裂能也按照聚合物/Ni、聚合物/Fe、聚合物/Cu、聚合物/Al的顺序逐渐减小；同种金属情况下，PE/金属和PP/金属的界面强度相近，且均小于PS/金属的界面强度。进一步，界面的损伤通过聚合物的自由体积演化进行了表征。研究结果为聚合物/金属复合材料的选材、设计及应用提供了依据。Abstract: The interfacial properties of polymer/metal significantly affect the mechanical properties of composites formed by metal and polymer. Combined with thermodynamic theoretical analysis and molecular dynamics simulation, the interface fracture energy and interface strength of the interface formed by several typical polymers (Polypropylene (PP), polyethylene (PE), polystyrene (PS)) and metals (Al, Ni, Cu, Fe) were systematically calculated. With the increase of interface displacement, the interface stress of polymer/metal interface first increases, then reaches the strength and enters the interface damage stage, and the interface stress decreases until the interface is completely broken, and the stress decreases to zero. The strength change trend of different polymer/metal interfaces is consistent with the interface fracture energy, and the simulation results of interface fracture energy are basically consistent with the theoretical calculation results. The interface fracture energy of polymer/metal interface is related to the surface energy of metal. As the surface energy of metal decreases with the order of Ni, Fe, Cu and Al, the interface fracture energy of polymer/metal interface also decreases with the order of polymer/Ni, polymer/Fe, polymer/Cu and polymer/Al. Under the same metal condition, the interface strength of PE/metal and PP/metal is similar, and both are smaller than that of PS/metal. Furthermore, the interface damage was characterized by the free volume evolution of the polymer. The research results provide a basis for material selection, design and application of polymer/metal composites.
-
图 1 聚乙烯 (PE)/Al界面模型示意图：(a) 整体视图；(b) 前视图；(c) 单条PE链
Figure 1. Schematic illustration of polyethylene (PE)/Al interface model: (a) Front view; (b) Overall view; (c) Single PE chain
图 2 界面应力-位移曲线：(a) PE/Al、PE/Cu、PE/Fe和PE/Ni；(b) PP/Al、PP/Cu、PP/Fe和PP/Ni；(c) PS/Al、PS/Cu、PS/Fe和PS/Ni；(d) 聚合物/金属界面强度比较
Figure 2. Interfacial stress-interfacial displacement curves: (a) PE/Al, PE/Cu, PE/Fe and PE/Ni; (b) PP/Al, PP/Cu, PP/Fe and PP/Ni; (c) PS/Al, PS/Cu, PS/Fe and PS/Ni; (d) Interface strength of polymer/metal interface models
图 3 聚合物/金属的界面断裂能
Figure 3. Interface fracture energy of polymer/metal interface models
图 4 PE/Al界面模型的界面应力-加载位移曲线及界面分离结构
Figure 4. Interfacial stress-loading displacement curve of PE/Al interface model and interface structure evolution during tension fracture
图 5 PE/Al界面模型的自由体积分数-加载位移曲线
Figure 5. Free volume fraction-loading displacement curve of PE/Al interface model
表 1 聚合物和金属的热力学参数
Table 1. Thermodynamic parameters of polymers and metals
Material h/nm Sv/(J·mol−1·K−1) H/(kJ·mol−1) V/(cm3·mol−1) γ/(J·m−2) Ni 0.27 10.12 17.47 6.59 1.19 Cu 0.27 9.58 13.00 7.10 0.76 Fe 0.28 8.23 14.90 7.10 0.78 Al 0.25 11.43 10.67 10.00 0.49 PP 1.16 19.86 8.70 215.00 0.15 PE 0.81 11.26 4.11 94.70 0.06 PS 1.53 19.49 10.00 594.00 0.08 Notes: PP—Polypropylene; PE—Polyethylene; PS—Polystyrene; h—Equilibrium distance between atoms; Sv—Vibrational part of melting entropy; H—Melting enthalpy; V—Molar volume; γ—Free energy of metal and polymer. 
下载: 导出CSV
表 2 聚合物和金属间的界面自由能
$ {\gamma _{\text{P-M}}} $ Table 2. Interface energy
$ {\gamma _{\text{P-M}}} $ of polymer/metalJ·m−2 PP PE PS Ni 0.670 0.627 0.636 Cu 0.455 0.412 0.421 Fe 0.465 0.422 0.431 Al 0.320 0.277 0.286
下载: 导出CSV
表 3 聚合物和金属的表面能
Table 3. Surface energy of polymers and metals
Metal γm/(J·m−2) Polymer γp/(J·m−2) Ni 2.426 PP 0.027 Cu 2.166 PE 0.030 Fe 2.222 PS 0.030 Al 1.347 — — Notes: γp—Surface energy of polymer; γm—Surface energy of metal.
下载: 导出CSV
表 4 聚合物/金属的界面断裂能
$ \varGamma $ Table 4. Interface fracture energy
$ \varGamma $ of polymer/metalJ·m−2 PP PE PS Ni 1.783 1.830 1.820 Cu 1.738 1.785 1.775 Fe 1.784 1.831 1.821 Al 1.054 1.101 1.091
下载: 导出CSV
表 5 聚合物/金属界面模型的尺寸
Table 5. Size of polymer/metal interface models
Model PE/Al PE/Ni PE/Fe PE/Cu PP/Al PP/Ni Size/nm3 3.65×3.65×5.92 3.52×3.52×5.16 3.58×3.58×5.15 3.62×3.61×5.24 4.05×4.05×5.87 4.23×4.23×4.78 Model PP/Fe PP/Cu PS/Al PS/Ni PS/Fe PS/Cu Size/nm3 3.94×3.94×5.33 3.98×3.98×5.46 4.45×4.45×5.77 4.23×4.23×5.41 4.30×4.30×6.82 4.33×4.33×6.71
下载: 导出CSV
-
[1] LANDGREBEAB D, KRAUSELB V, RAUTENSTRAUCHB A, et al. Energy-efficiency in a hybrid process of sheet metal forming and polymer injection moulding[J]. Procedia CIRP,2016,40:109-114. doi: 10.1016/j.procir.2016.01.068 [2] 梅宝平, 钟轶峰, 黄子昂, 等. 金属芯压电纤维/聚合物复合材料压电-黏弹-塑性行为的细观力学模型[J]. 复合材料学报, 2018, 35(1):229-237. doi: 10.13801/j.cnki.fhclxb.20170412.007MEI Baoping, ZHONG Yifeng, HUANG Zi'ang, et al. Micromechanical model of piezoelectric viscoelastic-plastic behavior of metal core piezoelectric fiber/polymer composites[J]. Acta Materiae Compositae Sinica,2018,35(1):229-237(in Chinese). doi: 10.13801/j.cnki.fhclxb.20170412.007 [3] XIN Y M, ZHANG S L, LOU Y, et al. Determinative energy dissipation in liquid metal polymer composites for advanced electronic applications[J]. Advanced Materials Technologies,2020,5(5):2000018. doi: 10.1002/admt.202000018 [4] ZHOU Y C, WANG L, ZHANG H, et al. Enhanced high thermal conductivity and low permittivity of polyimide based composites by core-shell Ag@SiO2 nanoparticle fillers[J]. Applied Physics Letters,2012,101(1):012903. doi: 10.1063/1.4733324 [5] 夏振庭, 钟轶峰, 黄子昂, 等. 含金属芯压电压磁纤维/聚合物基复合材料时变、非线性和多物理场响应的细观力学模型[J]. 复合材料学报, 2017, 34(12):2747-2755.XIA Zhenting, ZHONG Yifeng, HUANG Zi'ang, et al. Micromechanics modeling of time-dependent, nonlinear and multiphysics response of metal core piezoelectric and piezomagnetic fibers reinforced polymer matrix composites[J]. Acta Materiae Compositae Sinica,2017,34(12):2747-2755(in Chinese). [6] LIANG L H, LIU H Y, LONG H, et al. Size-dependent damage and fracture of two-layer systems[J]. Engineering Fracture Mechanics,2018,199:635-646. doi: 10.1016/j.engfracmech.2018.06.040 [7] 杨诗润, 甘华华, 杨冰, 等. 聚合物复合材料界面技术的研究进展[J]. 现代塑料加工应用, 2015, 27(6):57-59. doi: 10.3969/j.issn.1004-3055.2015.06.016YANG Shirun, GAN Huahua, YANG Bing, et al. Research progress of interface technology of polymer composites[J]. Modern Plastics Processing and Application,2015,27(6):57-59(in Chinese). doi: 10.3969/j.issn.1004-3055.2015.06.016 [8] 尚福林, 北村隆行. 界面裂纹萌生与扩展的分子动力学模拟[J]. 力学学报, 2007, 39(4):571-576. doi: 10.3321/j.issn:0459-1879.2007.04.021SHANG Fulin, KITAMURA Takayuki. Molecular dynamics simulation of interfacial crack initiation and propagation[J]. Chinese Journal of Theoretical and AppliedMechanics,2007,39(4):571-576(in Chinese). doi: 10.3321/j.issn:0459-1879.2007.04.021 [9] MELTONYAN A V, POGHOSYAN A H, SARGSYAN S H, et al. The features of poly(vinylimidazole) adsorption on gold surface: A molecular dynamics study[J]. Colloid and Polymer Science,2019,297:1345-1352. doi: 10.1007/s00396-019-04554-x [10] ROUT A, PANDEY P, OLIVEIRA E F, et al. Atomically locked interfaces of metal (aluminum) and polymer (polypropylene) using mechanical friction[J]. Polymer,2019,169:148-153. doi: 10.1016/j.polymer.2019.02.049 [11] LIU D L, ZHOU F, ZHOU H Z. The polymer-metal interactive behavior in polyphenylene sulfide/aluminium hetero interface in nano injection molding[J]. Composite Interfaces,2020,27(3):277-288. doi: 10.1080/09276440.2019.1626138 [12] SHIMIZU K, MIYATA T, NAGAO T, et al. Visualization of the tensile fracture behaviors at adhesive interfaces between brass and sulfur-containing rubber studied by transmission electron microscopy[J]. Polymer,2019,181:121789. doi: 10.1016/j.polymer.2019.121789 [13] LI X P, LIU F W, GONG N N, et al. Enhancing the joining strength of injection-molded polymer-metal hybrids by rapid heating and cooling[J]. Journal of Materials Processing Technology,2017,249:386-393. doi: 10.1016/j.jmatprotec.2017.06.034 [14] SU C H, CHEN H L, JU S P, et al. The mechanical behaviors of polyethylene/silver nanoparticle composites: An insight from molecular dynamics study[J]. Scientific Reports,2020,10(1):7600. doi: 10.1038/s41598-020-64566-4 [15] ZHOU M Y, XIONG X, DRUMMER D, et al. Interfacial interaction and joining property of direct injection-molded polymer-metal hybrid structures: A molecular dynamics simulation study[J]. Applied Surface Science,2019,478:680-689. doi: 10.1016/j.apsusc.2019.01.286 [16] KISIN S, BOŽOVIĆ VUKIĆ J, VAN DER VARST P G T, et al. Estimating the polymer-metal work of adhesion from molecular dynamics simulations[J]. Chemistry of Materials,2007,19(4):903-907. doi: 10.1021/cm0621702 [17] CHENG H C, HSU Y C, WU C H, et al. Molecular dynamics study of interfacial bonding strength of self-assembled monolayer-coated Au-epoxy and Au-Au systems[J]. Applied Surface Science,2011,257:8665-8674. doi: 10.1016/j.apsusc.2011.05.045 [18] HIRAHARA T, HIDAI H. Fiber implantation for interfacial joining of polymer to metal[J]. ACS Applied Polymer Materials,2020,2(8):3049-3053. doi: 10.1021/acsapm.0c00603 [19] WANG H, TAO J, JIN K. The effect of MWCNTs with different diameters on the interface properties of Ti/CFRP fiber metal laminates[J]. Composite Structures,2021,266:113818. doi: 10.1016/j.compstruct.2021.113818 [20] BANDARENKA H, BALUCANI M, CRESCENZI R, et al. Formation of composite nanostructures by corrosive deposition of copper into porous silicon[J]. Superlattices and Microstructures,2008,44(4-5):583-587. doi: 10.1016/j.spmi.2007.11.004 [21] 王帅, 姚寅, 杨亚政, 等. 双层金属纳米板界面能密度的尺寸效应[J]. 力学学报, 2017, 49(5):978-984. doi: 10.6052/0459-1879-17-142WANG Shuai, YAO Yin, YANG Yazheng, et al. Size effect of the interface energy density in bi-nano-scaled-metallic plates[J]. Chinese Journal of Theoretical and Applied Mechanics,2017,49(5):978-984(in Chinese). doi: 10.6052/0459-1879-17-142 [22] 李凯凯, 张建勋, 张威, 等. 冲击载荷下(纤维/聚合物)-金属层合板的大挠度动力响应[J]. 复合材料学报, 2020, 37(1):147-154.LI Kaikai, ZHANG Jianxun, ZHANG Wei, et al. Dynamic response of large deflection of (fiber/polymer)-metal laminates under impact load[J]. Acta Materiae Compositae Sinica,2020,37(1):147-154(in Chinese). [23] KU J H, JUNG I H, RHEE K Y, et al. Atmospheric pressure plasma treatment of polypropylene to improve the bonding strength of polypropylene/aluminum composites[J]. Composites Part B: Engineering,2013,45(1):1282-1287. doi: 10.1016/j.compositesb.2012.06.016 [24] LIANG L H, WEI H, LI X N, et al. Size-dependent interface adhesive energy and interface strength of nanostructured systems[J]. Surface & Coatings Technology,2013,236:525-530. doi: 10.1016/j.surfcoat.2013.10.045 [25] LIANG L H, YOU X M, MA H S. Interface energy and its influence on interface fracture between metal and ceramic thin films in nanoscale[J]. Journal of Applied Physics,2010,108(8):084317. doi: 10.1063/1.3501090 [26] WUNDERLICH B. Thermal analysis[M]. New York: Academic Press, 1990: 357. [27] VITOS L, RUBAN A, SKRIVER H L. The surface energy of metals[J]. Surface Science,1998,411(1-2):186-202. doi: 10.1016/S0039-6028(98)00363-X [28] 陈晓磊. 固体聚合物表面接触角的测量及表面能研究[D]. 长沙: 中南大学, 2012.CHEN Xiaolei. Measurement of surface contact angle and surface energy of solid polymers[D]. Changsha: Central South University, 2012(in Chinese). [29] CHANG Q, XIE J, MAO A, et al. Study on interface structure of Cu/Al clad plates by roll casting[J]. Metals,2018,8(10):770. doi: 10.3390/met8100770 [30] ZHENG T, WANG S, ZHOU L, et al. The disentanglement and shear properties of amorphous polyethylene during friction: Insights from molecular dynamics simulations[J]. Applied Surface Science,2022,580:152301. doi: 10.1016/j.apsusc.2021.152301 [31] DAUBER-OSGUTHORPE P, ROBERTS V A, OSGUTHORPE D J, et al. Structure and energetics of ligand binding to proteins: Escherichia coli dihydrofolate reductase-trimethoprim, a drug-receptor system[J]. Proteins,1988,4(1):31-47. doi: 10.1002/prot.340040106 [32] RAMAKRISHNAN S K, MARTIN M, CLOITRE T, et al. Design rules for metal binding biomolecules: Understanding of amino acid adsorption on platinum crystallographic facets from density functional calculations[J]. Physical Chemistry Chemical Physics,2015,17(6):4193-4198. doi: 10.1039/C4CP05112B [33] KANHAIYA K, KIM S, IM W, et al. Accurate simulation of surfaces and interfaces of ten FCC metals and steel using Lennard-Jones potentials[J]. npj Computational Materials,2021,7:17. doi: 10.1038/s41524-020-00478-1 [34] HEINZ H, VAIA R A, FARMER B L, et al. Accurate simulation of surfaces and interfaces of face-centered cubic metals using 12-6 and 9-6 Lennard-Jones potentials[J]. The Journal of Physical Chemistry C,2008,112(44):17281-17290. doi: 10.1021/jp801931d [35] TAM L H, LAU D. A molecular dynamics investigation on the cross-linking and physical properties of epoxy-based materials[J]. RSC Advances,2014,4(62):33074-33081. doi: 10.1039/C4RA04298K [36] VARSHNEY V, PATNAIK S S, ROY A K, et al. Heat transport in epoxy networks: A molecular dynamics study[J]. Polymer,2009,50(14):3378-3385. doi: 10.1016/j.polymer.2009.05.027 [37] AWASTHI A P, LAGOUDAS D C, HAMMERAND D C. Modeling of graphene-polymer interfacial mechanical behavior using molecular dynamics[J]. Modelling and Simulation in Materials Science and Engineering,2009,17:015002. doi: 10.1088/0965-0393/17/1/015002 [38] ZABIHI Z, ARAGHI H, RODRIGUEZ P E D S, et al. Vapor sensing and interface properties of reduced graphene oxidepoly(methyl methacrylate) nanocomposite[J]. Journal of Materials Science: Materials in Electronics,2019,30:2908-2919. doi: 10.1007/s10854-018-00567-4 [39] HANSON B, HOFMANN J, PASQUINELLI M A. Influence of copolyester composition on adhesion to soda-lime glass via molecular dynamics simulations[J]. ACS Applied Materials & Interfaces,2016,8(21):13583-13589. doi: 10.1021/acsami.6b01851 [40] ZHANG M, JIANG B, CHEN C, et al. The effect of temperature and strain rate on the interfacial behavior of glass fiber reinforced polypropylene composites: A molecular dynamics study[J]. Polymers,2019,11(11):1766. doi: 10.3390/polym11111766 [41] JONES J E. On the determination of molecular fields. II. From the equation of state of a gas[J]. Proceedings of the Royal Society of London. Series A,1924,106:463-477. [42] THOMPSON A P, AKTULGA H M, BERGER R, et al. LAMMPS—A flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales[J]. Computer Physics Communications,2022,271:108171. doi: 10.1016/j.cpc.2021.108171 [43] STUKOWSKI A. Visualization and analysis of atomistic simulation data with OVITO-the open visualization tool[J]. Modelling and Simulation in Materials Science and Engineering,2010,18(1):015012. doi: 10.1088/0965-0393/18/1/015012 [44] 张可, 姚重阳, 李栋宇, 等. 基于分子模拟的聚醚醚酮拉伸力学行为与改性[J]. 航空材料学报, 2022, 42(2):47-56. doi: 10.11868/j.issn.1005-5053.2021.000143ZHANG Ke, YAO Chongyang, LI Dongyu, et al. Tensile mechanical behavior and modification of polyether ether ketone based on molecular simulation[J]. Journal of Aeronautical Materials,2022,42(2):47-56(in Chinese). doi: 10.11868/j.issn.1005-5053.2021.000143 [45] STUKOWSKI A. Computational analysis methods in atomistic modeling of crystals[J]. JOM,2014,66:399-407. doi: 10.1007/s11837-013-0827-5 -
下载:
点击查看大图
图(5) / 表(5)
计量
- 文章访问数: 401
- HTML全文浏览量: 267
- PDF下载量: 39
- 被引次数: 0
