Heterogeneities in Polymer Structural and Dynamic Properties in Graphene and Graphene Oxide Nanocomposites: Molecular Dynamics Simulations

The effect of graphene (G) and graphene oxide (GO), used as the nanofiller in polymer nanocomposites (NC), on the structural and dynamic properties of polymer chains, has been studied by means of molecular dynamics (MD) simulations. Two polymers, i.e., poly(propylene) and poly(vinyl alcohol), are employed as matrices to cover a wider range of polymer–filler interactions. The local structural properties, e.g., density profile, average R _g, and end‐to‐end distance as well as dynamic properties, e.g., estimated translational and orientational relaxation times, of polymer chains are studied. In addition, the interaction energies are estimated between polymers and nanofillers for different hybrid systems using MD pullout simulations. Strong heterogeneities in polymer structural and dynamic properties have been observed such that chains are more oriented and exhibit slower dynamics in the vicinity of the nanofillers (G and GO) as compared to bulk. It is also found that the orientation of polymer chains at the interface is more influenced by the nanofiller in such a way that the more oriented polymer chains are observed in G‐based NC for both polymers. However, the immobilization of polymer chains at the interface proves to be very much dependent on the polymer–filler interactions.

     

Effect of Vacancy Defects on the Young's Modulus and Fracture Strength of Graphene: A Molecular Dynamics Study

The Young's modulus of graphene with various rectangular and circular vacancy defects is investigated by molecular dynamics simulation. By comparing with the results calculated from an effective spring model, it is demonstrated that the Young's modulus of graphene is largely correlated to the size of vacancy defects perpendicular to the stretching direction. And a linear reduction of Young's modulus with the increasing concentration of mono‐atomic‐vacancy defects (i.e., the slope of ?0.03) is also observed. The fracture behavior of graphene, including the fracture strength, crack initiation and propagation are then studied by the molecular dynamics simulation, the effective spring model, and the quantized fracture mechanics. The blunting effect of vacancy edges is demonstrated, and the characterized crack tip radius of 4.44 Å is observed.     

氧化石墨烯/PMMA和表面官能化的石墨烯/PMMA复合材料的制备及其力学性能的研究

使用简单的溶液共混的方法制备了氧化石墨烯/聚甲基丙烯酸甲酯(GO/PMMA)和表面官能化的石墨烯/聚甲基丙烯酸甲酯复合材料.通过透射电镜(TEM),扫描电镜(SEM)和原子力显微镜(AFM)观察了石墨烯及复合材料的表观形貌.通过拉伸实验表征了其力学性能,研究发现随着石墨烯的加入,其拉伸强度和断裂伸长率都有所改善,而且表面官能化的石墨烯的复合材料的改善效果要优于氧化石墨烯.     

On the Mechanical Properties of Popgraphene-Based Nanotubes: a Reactive Molecular Dynamics Study

Carbon-based tubular materials have sparked a great interest in future electronics and optoelectronics device applications. In this work, we computationally studied the mechanical properties of nanotubes generated from popgraphene (PopNTs). Popgraphene is a 2D carbon allotrope composed of 5-8-5 rings. We carried out fully atomistic reactive (ReaxFF) molecular dynamics for PopNTs of different chiralities ( and ) and/or diameters and at different temperatures (from 300 up to 1200 K). Results showed that the tubes are thermally stable (at least up to 1200 K). All tubes presented stress/strain curves with a quasi-linear behavior followed by an abrupt drop of stress values. Interestingly, armchair-like PopNTs ( ) can stand a higher strain load before fracturing when contrasted to the zigzag-like ones ( ). Moreover, it was obtained that Young's modulus (Y_Mod) (750–900 GPa) and ultimate strength (σ_US) (120–150 GPa) values are similar to the ones reported for conventional armchair and zigzag carbon nanotubes. Y_Mod values obtained for PopNTs are not significantly temperature-dependent. While the σ_US values for the showed a quasi-linear dependence with the temperature, the exhibited no clear trends.     

Predictors of Cavitation in Glassy Polymers under Tensile Strain: A Coarse‐Grained Molecular Dynamics Investigation

The nucleation of cavities in a homogeneous polymer under tensile strain is studied in a coarse‐grained MD simulation. To establish a causal relation between local microstructure and the onset of cavitation, a detailed analysis of some local properties is presented. In contrast to common assumptions, the nucleation of a cavity is neither correlated to a local loss of density nor to stress at the atomic scale or the chain‐end density in the nondeformed state. Instead, a cavity in glassy polymers nucleates in regions that display a low bulk elastic modulus. Even if the localization of a cavity is not directly predictable from the initial configuration, the elastically weak zones identified in the initial state emerge as favorite spots for cavity formation.

     

Thermal,Mechanical and Dielectric Properties of Polyimide Composite Films by In-Situ Reduction of Fluorinated Graphene

Materials with outstanding mechanical properties and excellent dielectric properties are increasingly favored in the microelectronics industry. The application of polyimide (PI) in the field of microelectronics is limited because of the fact that PI with excellent mechanical properties does not have special features in the dielectric properties. In this work, PI composite films with high dielectric properties and excellent mechanical properties are fabricated by in-situ reduction of fluorinated graphene (FG) in polyamide acid (PAA) composites. The dielectric permittivity of pure PI is 3.47 and the maximum energy storage density is 0.664 J/cm³ at 100 Hz, while the dielectric permittivity of the PI composite films reaches 235.74 under the same conditions, a 68-times increase compared to the pure PI, and the maximum energy storage density is 5.651, a 9-times increase compared to the pure PI films. This method not only solves the problem of the aggregation of the filler particles in the PI matrix and maintains the intrinsic excellent mechanical properties of the PI, but also significantly improves the dielectric properties of the PI.     

Molecular Mechanisms on the Selectivity Enhancement of Ascorbic Acid,Dopamine, and Uric Acid by Serine Oligomers Decoration on Graphene Oxide: A Molecular Dynamics Study

The selectivity in the simultaneous detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA) has been an open problem in the biosensing field. Many surface modification methods were carried out for glassy carbon electrodes (GCE), including the use of graphene oxide and amino acids as a selective layer. In this work, molecular dynamics (MD) simulations were performed to investigate the role of serine oligomers on the selectivity of the AA, DA, and UA analytes. Our models consisted of a graphene oxide (GO) sheet under a solvent environment. Serine tetramers were added into the simulation box and were adsorbed on the GO surface. Then, the adsorption of each analyte on the mixed surface was monitored from MD trajectories. It was found that the adsorption of AA was preferred by serine oligomers due to the largest number of hydrogen-bond forming functional groups of AA, causing a 10-fold increase of hydrogen bonds by the tetraserine adsorption layer. UA was the least preferred due to its highest aromaticity. Finally, the role of hydrogen bonds on the electron transfer selectivity of biosensors was discussed with some previous studies. AA radicals received electrons from serine through hydrogen bonds that promoted oxidation reaction and caused the negative shifts and separation of the oxidation potential in experiments, as DA and UA were less affected by serine. Agreement of the in vitro and in silico results could lead to other in silico designs of selective layers to detect other types of analyte molecules.     

壳聚糖/氧化石墨烯纳米复合材料的形态和力学性能研究

通过溶液共混法成功制备了氧化石墨烯/壳聚糖纳米复合材料. 透射电镜(TEM)结果表明, 氧化石墨烯纳米粒子在壳聚糖基体中分散良好. 拉伸实验结果表明, 随氧化石墨烯含量的增加, 氧化石墨烯/壳聚糖纳米复合材料的杨氏模量和拉伸强度均显著改善, 加入4 wt%的氧化石墨烯能够使纳米复合材料的杨氏模量和拉伸强度分别提高123%和117%|但另一方面, 却也在一定程度上使复合材料的断裂伸长率或韧性下降.     

氧化石墨烯分离膜机械性能调控

氧化石墨烯(Graphene oxide,GO)片层组装制备的分离膜,具有可调控的纳米通道和独特的分离性能,是一种很有前景的分离材料,但较差的机械性能制约了其实际应用.将活性分子、阳离子等粒子引入到GO膜的片层间,利用其与GO形成的稳定键合可提高GO膜的机械性能.本文综述了国内外在GO膜机械性能调控方面的研究进展.依据...     

End Capping Alters the Structural Characteristics and Mechanical Properties of Transthyretin (105–115) Amyloid Protofibrils

Pathological amyloid proteins are associated with degenerative and neurodegenerative diseases. These amyloid proteins develop as oligomer, fibrillar, and plaque forms, due to the denatured and unstable status of the amyloid monomers. Specifically, the development of fibrillar amyloid proteins has been investigated through several experimental studies. To understand the generation of amyloid fibrils, environmental factors such as point mutations, pH, and polymorphic characteristics have been considered. Recently, amyloid fibril studies related to end‐capping effects have been conducted to understand amyloid fibril development. However, atomic‐level studies to determine the stability and mechanical properties of amyloid fibrils based on end capping have not been undertaken. In this study, we show that end capping alters the structural characteristics and conformations of transthyretin (TTR) amyloid fibrils by using molecular dynamics (MD) simulations. Variation in the structural conformations and characteristics of the TTR fibrils through end capping are observed, due to the resulting electrostatic energies and hydrophobicity characteristics. Moreover, the end capping changes the mechanical properties of TTR fibrils. Our results shed light on amyloid fibril formation under end‐capping conditions.     

Influence of Homogenizing Methodology on Mechanical and Tribological Performance of Powder Metallurgy Processed Titanium Composites Reinforced by Graphene Nanoplatelets

In the present work, 0.25 wt%GNP-Ti composites were prepared through powder metallurgy route by adopting three types of mixing modes to investigate the extent of mixing on the mechanical and tribological properties. Dry ball milling, wet ball milling, and rotator mixing were independently employed to homogenize the composite constituents. Three types of composite powders obtained were subsequently sintered into composite pellets by cold compaction followed by vacuum sintering. Morphological investigation of composite powders performed by SEM revealed better homogenization of GNPs in Ti matrix for dry ball milled composite powder, whereas wet ball milled and rotator mixed composite powders showed aggregation and bundling of GNPs. Micro Vickers hardness of composites produced via dry ball milling is 4.56% and 15.7% higher than wet ball milled and rotator mixed samples, respectively. Wear test performed by pin-on-disk tribometer showed higher wear loss for wet ball milled and rotator mixed composites in comparison to dry ball milled.     

Hybrid Gels Assembled from Fmoc–Amino Acid and Graphene Oxide with Controllable Properties

A supramolecular gel is obtained from the self‐assembly of an ultralow‐molecular‐weight gelator (N‐fluorenyl‐9‐methoxycarbonyl glutamic acid) in good and poor solvents. The gelators can self‐assemble into a lamellar structure, which can further form twisted fibers and nanotubes in the gel phase. Rheological studies show that the gels are robust and rigid, and are able to rapidly self‐recover to a gel after being destroyed by shear force. Fluorescence experiments reveal the aggregation‐induced emission effects of the gel system; the fluorescence intensity is significantly enhanced by gel formation. Graphene oxide (GO) is introduced into the system efficiently to give a hybrid material, and the interaction between gelators–GO sheets is studied. Rheological and fluorescent studies imply that the mechanical properties and the fluorescent emission of the hybrid materials can be fine‐tuned by controlling the addition of GO.     

Mechanical Properties of Gel-Derived Materials

The mechanical behaviour of xerogels and aerogels is generally described in terms of brittle and elastic materials, like glasses or ceramics. The main difference compared to silica glass is the order of magnitude of the elastic and rupture moduli which are 10⁴ times lower. However, if this analogy is pertinent when gels are under a tension stress (bending test) they exhibit a more complicated response when the structure is submitted to a compressive stress. The network is linearly elastic under small strains, then exhibits yield followed by densification and plastic hardening. As a consequence of the plastic shrinkage it is possible to densify and stiffen the gel at room temperature. These opposite behaviours (elastic and plastic) are surprisingly related to the same two kinds of gel features: the silanol content and the pore volume. Both elastic modulus and plastic shrinkage depend strongly on the volume fraction of pores and on the condensation reaction between silanols. On the mechanical point of view (rupture modulus and toughness), it is shown that pores and silanols play also an important role. Pores can be considered as flaws in the terms of fracture mechanics and the flaw size, calculated from rupture strength and toughness is related to the pore size distribution. Different kinds of gels structure (fractal or not fractal) have been synthesized by a control of the different steps of transformation such as sintering and plastic compaction. The relationships between structural and the elastic properties are discussed in terms of the percolation theory and fractal structure.     

Theoretical and Experimental Determination of Thermomechanical Properties of Epoxy-SiO2 Nanocomposites

Improvements in the thermomechanical properties of epoxy upon inclusion of well-dispersed SiO₂ nanoparticles have been demonstrated both experimentally and through molecular dynamics simulations. The SiO₂ was represented by two different dispersion models: dispersed individual molecules and as spherical nanoparticles. The calculated thermodynamic and thermomechanical properties were consistent with experimental results. Radial distribution functions highlight the interactions of different parts of the polymer chains with the SiO₂ between 3 and 5 nm into the epoxy, depending on the particle size. The findings from both models were verified against experimental results, such as the glass transition temperature and tensile elastic mechanical properties, and proved suitable for predicting thermomechanical and physicochemical properties of epoxy-SiO₂ nanocomposites.     

The classical molecular dynamics simulation of graphene on Ru(0001) using a fitted Tersoff interface potential

The accurate molecular dynamics simulation of weakly bound adhesive complexes, such as supported graphene (gr), is challenging because of the lack of an adequate interface potential. Instead of the widely used Lennard‐Jones potential for weak and long‐range interactions, we use a newly parameterized Tersoff potential for gr/Ru(0001) system. The new interfacial force field provides adequate moire superstructures in accordance with scanning tunneling microscopy images and with density functional theory (DFT) results. In particular, the corrugation of ξ ≈ 1.0 ± 0.2 Å is found that is somewhat smaller than found by DFT approaches (ξ ≈ 1.2 Å) and is close to scanning tunneling microscope measurements (ξ ≈ 0.8 ± 0.3 Å). The new potential could open the way toward large‐scale simulations of supported gr with adequate moire supercells in many fields of gr research. Moreover, the new interface potential might provide a new strategy in general for obtaining accurate interaction potentials for weakly bound adhesion in large‐scale systems in which atomic dynamics is inaccessible yet by accurate DFT calculations. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of the Nanotube Radius and the Volume Fraction on the Mechanical Properties of Carbon Nanotube-Reinforced Aluminum Metal Matrix Composites

By using the advantages of carbon nanotubes (CNTs), such as their excellent mechanical properties and low density, CNT-reinforced metal matrix composites (MMCs) are expected to overcome the limitations of conventional metal materials, i.e., their high density and low ductility. To understand the behavior of composite materials, it is necessary to observe the behavior at the molecular level and to understand the effect of various factors, such as the radius and content of CNTs. Therefore, in this study, the effect of the CNT radius and content on the mechanical properties of CNT-Al composites was observed using a series of molecular dynamics simulations, particularly focusing on MMCs with a high CNT content and large CNT diameter. The mechanical properties, such as the strength and stiffness, were increased with an increasing CNT radius. As the CNT content increased, the strength and stiffness increased; however, the fracture strain was not affected. The behavior of double-walled carbon nanotubes (DWNTs) and single-walled carbon nanotubes (SWNTs) was compared through the decomposition of the stress–strain curve and observations of the atomic stress field. The fracture strain increased significantly for SWNT-Al as the tensile force was applied in the axial direction of the armchair CNTs. In the case of DWNTs, an early failure was initiated at the inner CNTs. In addition, the change in the elastic modulus according to the CNT content was predicted using the modified rule of mixture. This study is expected to be useful for the design and development of high-performance MMCs reinforced by CNTs.     

湿法改性石墨烯在制备橡胶复合材料中的应用

橡胶由于其高弹性、良好的生物相容性、耐化学腐蚀及长期使用的稳定性等优点,在众多领域已有一百多年的应用历史。一般来说,在生胶硫化之前需要加入增强填料、润滑剂、偶联剂和促进剂等各类添加剂,以达到使用要求的性能。其中增强填料起到提高橡胶强度、提高橡胶耐磨耐热性、延长橡胶使用寿命的作用。相比于炭黑或者二氧化硅这些传统增强填料,新兴纳米材料石墨烯由于其优异的性能,只需极少量便可使橡胶的性能显著增强。然而,石墨烯片层之间的范德华力严重的阻碍了其在高分子机体内的分散,其在橡胶基体的分散性直接决定了石墨烯对于橡胶材料的增强效果。近年来,越来越多的研究开始关注通过在溶液中的湿法改性,包括物理或化学的方法来改性石墨烯,促进它与橡胶二者界面的相互作用,提高石墨烯在橡胶基体中的分散效果。本文总结了近几年湿法改性石墨烯在制备石墨烯/橡胶复合材料方面的研究进展。     

不同氧化程度氧化石墨烯的制备及湿敏性能研究

基于氧化石墨烯具有多种含氧官能团和极大的比表面积,研究了不同氧化程度氧化石墨烯的湿敏性能。采用改进的Hummers法制备不同氧化程度的氧化石墨,经过超声分散制备氧化石墨烯水相分散液后,制成氧化石墨烯薄膜湿敏元件。采用X射线衍射、原子力显微镜、红外光谱、拉曼光谱和X射线光电子能谱对实验样品的结构和谱学特性进行表征。结果表明:石墨经氧化后,底面间距增大为0.9 nm左右;随氧化剂用量的增加,氧化石墨中石墨的衍射峰逐渐消失,石墨相微晶尺寸逐渐减小,O/C原子比逐渐增大,氧化程度逐渐升高;氧化石墨烯在水相分散液中可达单层分散,单层氧化石墨烯厚度约为1.3 nm;氧化石墨烯表面接有-OH、C-O-C、C=O和COOH官能团,且官能团含量随氧化程度的升高而增大;氧化石墨烯薄膜元件在室温下对湿度的响应时间约3 s,灵敏度达99%;在11.3%-93.6%相对湿度范围内,元件的电阻随湿度升高显著减小,较高氧化程度的氧化石墨烯薄膜的电阻对数与相对湿度呈线性变化;氧化程度越高,元件灵敏度越高,响应时间越短。