Modeling and Simulation of Polymer Nanocomposites

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Physics and Theory".

Deadline for manuscript submissions: closed (15 December 2021) | Viewed by 30301

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Materials Research and Technology, Luxembourg Institute of Science and Technology, L-4362 Esch-sur-Alzette, Luxembourg
Interests: computational chemistry; batteries; organic solutions; polymer electrolytes; nanocomposites
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Guest Editor
Polymer Physics, Department of Materials, ETH Zurich, Leopold-Ruzicka-Weg 4, CH-8093 Zurich, Switzerland
Interests: polymer physics; computational physics; applied mathematics; stochastic differential equations; coarse-graining; biophysics
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

In the past three decades, polymer nanocomposites, where spherical plate-like or anisotropic nanofillers (with dimensions of 1 to 150 nm) are distributed into polymer matrices, have received a tremendous attention from academia and industry since they can have dramatically improved properties (mechanical, electrical, optical, rheological) in comparison to polymer melts or blends. Although there is a plethora of experimental investigations for such kinds of properties, there is strong motivation to explore the nanoscopic behavior and fundamental polymer physics of such materials. It is well known that nanocomposite behavior depends on the filler characteristics such as size, surface area, and shape, loading, polymer-filler interaction, polymer conformations, and morphology. Recognizing the importance of theory and simulations in understanding nanoscopic behavior in polymer nanocomposites, this Special Issue of Polymers invites contributions addressing several areas of polymer nanocomposites, such as polymer nanofiller interfaces, polymer conformation and dynamics under confinement, mobility (diffusion) in nanocomposites, ionomer nanocomposites, matrix-free polymer grafted nanoparticles, properties modeling, theory development, algorithms, and coarse graining implementations to speed up simulations. 

Dr. Argyrios Karatrantos
Prof. Dr. Martin Kröger
Guest Editors

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Keywords

  • interfaces
  • polymer conformation
  • mobility (diffusion)
  • properties modeling
  • confinement
  • miscibility
  • theory
  • simulation (atomistic, coarse-grained, slip-springs models)

Published Papers (10 papers)

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Research

26 pages, 45707 KiB  
Article
Structure and Dynamics of Highly Attractive Polymer Nanocomposites in the Semi-Dilute Regime: The Role of Interfacial Domains and Bridging Chains
by Emmanuel N. Skountzos, Katerina S. Karadima and Vlasis G. Mavrantzas
Polymers 2021, 13(16), 2749; https://doi.org/10.3390/polym13162749 - 16 Aug 2021
Cited by 4 | Viewed by 2783
Abstract
Detailed molecular dynamics (MD) simulations are employed to study how the presence of adsorbed domains and nanoparticle bridging chains affect the structural, conformational, thermodynamic, and dynamic properties of attractive polymer nanocomposite melts in the semi-dilute regime. As a model system we have chosen [...] Read more.
Detailed molecular dynamics (MD) simulations are employed to study how the presence of adsorbed domains and nanoparticle bridging chains affect the structural, conformational, thermodynamic, and dynamic properties of attractive polymer nanocomposite melts in the semi-dilute regime. As a model system we have chosen an unentangled poly(ethylene glycol) (PEG) matrix containing amorphous spherical silica nanoparticles with different diameters and at different concentrations. Emphasis is placed on properties such as the polymer mass density profile around nanoparticles, the compressibility of the system, the mean squared end-to-end distance of PEG chains, their orientational and diffusive dynamics, the single chain form factor, and the scattering functions. Our analysis reveals a significant impact of the adsorbed, interfacial polymer on the microscopic dynamic and conformational properties of the nanocomposite, especially under conditions favoring higher surface-to-volume ratios (e.g., for small nanoparticle sizes at fixed nanoparticle loading, or for higher silica concentrations). Simultaneously, adsorbed polymer chains adopt graft-like conformations, a feature that allows them to considerably extend away from the nanoparticle surface to form bridges with other nanoparticles. These bridges drive the formation of a nanoparticle network whose strength (number of tie chains per nanoparticle) increases substantially with increasing concentration of the polymer matrix in nanoparticles, or with decreasing nanoparticle size at fixed nanoparticle concentration. The presence of hydroxyl groups at the ends of PEG chains plays a key role in the formation of the network. If hydroxyl groups are substituted by methoxy ones, the simulations reveal that the number of bridging chains per nanoparticle decreases dramatically, thus the network formed is less dense and less strong mechanically, and has a smaller impact on the properties of the nanocomposite. Our simulations predict further that the isothermal compressibility and thermal expansion coefficient of PEG-silica nanocomposites are significantly lower than those of pure PEG, with their values decreasing practically linear with increasing concentration of the nanocomposite in nanoparticles. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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20 pages, 6249 KiB  
Article
Finite Element Analysis of Gas Diffusion in Polymer Nanocomposite Systems Containing Rod-like Nanofillers
by Thouaiba Htira, Sarra Zid, Matthieu Zinet and Eliane Espuche
Polymers 2021, 13(16), 2615; https://doi.org/10.3390/polym13162615 - 06 Aug 2021
Cited by 2 | Viewed by 2425
Abstract
Polymer-based films with improved gas barrier properties are of great interest for a large range of applications, including packaging and coatings. The barrier effect is generally obtained via the addition of a sufficient amount of impermeable nanofillers within the polymer matrix. Due to [...] Read more.
Polymer-based films with improved gas barrier properties are of great interest for a large range of applications, including packaging and coatings. The barrier effect is generally obtained via the addition of a sufficient amount of impermeable nanofillers within the polymer matrix. Due to their low environmental footprint, bio-based nanocomposites such as poly(lactic acid)–cellulose nanocrystal (PLA–CNC) nanocomposites seem to be an interesting alternative to synthetic-polymer-based nanocomposites. The morphology of such systems consists of the dispersion of impermeable rod-like fillers of finite length in a more permeable matrix. The aim of this work is to analyze, through finite element modeling (FEM), the diffusion behavior of 3D systems representative of PLA–CNC nanocomposites, allowing the determination of the nanocomposites’ effective diffusivity. Parametric studies are carried out to evaluate the effects of various parameters, such as the filler volume fraction, aspect ratio, polydispersity, and agglomeration, on the improvement of the barrier properties. The role of the filler–matrix interfacial area (or interphase) is also investigated and is shown to be particularly critical to the overall barrier effect for highly diffusive interphases. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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18 pages, 515 KiB  
Article
Interactions between Sterically Stabilized Nanoparticles: The Effects of Brush Bidispersity and Chain Stiffness
by Sergei A. Egorov
Polymers 2021, 13(14), 2296; https://doi.org/10.3390/polym13142296 - 13 Jul 2021
Cited by 5 | Viewed by 1604
Abstract
Density Functional Theory is employed to study structural properties and interactions between solvent-free polymer-grafted nanoparticles. Both monodisperse and bidisperse polymer brushes with variable chain stiffness are considered. The three major control parameters are the grafting density, the grafted chain length, and its stiffness. [...] Read more.
Density Functional Theory is employed to study structural properties and interactions between solvent-free polymer-grafted nanoparticles. Both monodisperse and bidisperse polymer brushes with variable chain stiffness are considered. The three major control parameters are the grafting density, the grafted chain length, and its stiffness. The effect of these parameters on the brush-brush overlap and attractive interaction strength is analyzed. The Density Functional Theory results are compared with the available simulation data, and good quantitative agreement is found. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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20 pages, 8363 KiB  
Article
Wetting Simulations of High-Performance Polymer Resins on Carbon Surfaces as a Function of Temperature Using Molecular Dynamics
by Swapnil S. Bamane, Prashik S. Gaikwad, Matthew S. Radue, S. Gowtham and Gregory M. Odegard
Polymers 2021, 13(13), 2162; https://doi.org/10.3390/polym13132162 - 30 Jun 2021
Cited by 14 | Viewed by 2982
Abstract
Resin/reinforcement wetting is a key parameter in the manufacturing of carbon nanotube (CNT)-based composite materials. Determining the contact angle between combinations of liquid resin and reinforcement surfaces is a common method for quantifying wettability. As experimental measurement of contact angle can be difficult [...] Read more.
Resin/reinforcement wetting is a key parameter in the manufacturing of carbon nanotube (CNT)-based composite materials. Determining the contact angle between combinations of liquid resin and reinforcement surfaces is a common method for quantifying wettability. As experimental measurement of contact angle can be difficult when screening multiple high-performance resins with CNT materials such as CNT bundles or yarns, computational approaches are necessary to facilitate CNT composite material design. A molecular dynamics simulation method is developed to predict the contact angle of high-performance polymer resins on CNT surfaces dominated by aromatic carbon, aliphatic carbon, or a mixture thereof (amorphous carbon). Several resin systems are simulated and compared. The results indicate that the monomer chain length, chemical groups on the monomer, and simulation temperature have a significant impact on the predicted contact angle values on the CNT surface. Difunctional epoxy and cyanate ester resins show the overall highest levels of wettability, regardless of the aromatic/aliphatic nature of the CNT material surface. Tetrafunctional epoxy demonstrates excellent wettability on aliphatic-dominated surfaces at elevated temperatures. Bismaleimide and benzoxazine resins show intermediate levels of wetting, while typical molecular weights of polyether ether ketone demonstrate poor wetting on the CNT surfaces. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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29 pages, 11544 KiB  
Article
Multiscale Modeling of Epoxy-Based Nanocomposites Reinforced with Functionalized and Non-Functionalized Graphene Nanoplatelets
by Hashim Al Mahmud, Matthew S. Radue, Sorayot Chinkanjanarot and Gregory M. Odegard
Polymers 2021, 13(12), 1958; https://doi.org/10.3390/polym13121958 - 13 Jun 2021
Cited by 26 | Viewed by 3426
Abstract
The impact on the mechanical properties of an epoxy resin reinforced with pristine graphene nanoplatelets (GNP), highly concentrated graphene oxide (GO), and functionalized graphene oxide (FGO) has been investigated in this study. Molecular dynamics (MD) using a reactive force field (ReaxFF) has been [...] Read more.
The impact on the mechanical properties of an epoxy resin reinforced with pristine graphene nanoplatelets (GNP), highly concentrated graphene oxide (GO), and functionalized graphene oxide (FGO) has been investigated in this study. Molecular dynamics (MD) using a reactive force field (ReaxFF) has been employed in predicting the effective mechanical properties of the interphase region of the three nanocomposite materials at the nanoscale level. A systematic computational approach to simulate the reinforcing nanoplatelets and probe their influence on the mechanical properties of the epoxy matrix is established. The modeling results indicate a significant degradation of the in-plane elastic Young’s (decreased by ~89%) and shear (decreased by ~72.5%) moduli of the nanocomposite when introducing large amounts of oxygen and functional groups to the robust sp2 structure of the GNP. However, the wrinkled morphology of GO and FGO improves the nanoplatelet-matrix interlocking mechanism, which produces a significant improvement in the out-of-plane shear modulus (increased by 2 orders of magnitudes). The influence of the nanoplatelet content and aspect ratio on the mechanical response of the nanocomposites has also been determined in this study. Generally, the predicted mechanical response of the bulk nanocomposite materials demonstrates an improvement with increasing nanoplatelet content and aspect ratio. The results show good agreement with experimental data available from the literature. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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20 pages, 7106 KiB  
Article
Molecular Dynamics of Janus Nanodimers Dispersed in Lamellar Phases of a Block Copolymer
by J. Javier Burgos-Mármol and Alessandro Patti
Polymers 2021, 13(9), 1524; https://doi.org/10.3390/polym13091524 - 09 May 2021
Cited by 5 | Viewed by 2671
Abstract
We investigate structural and dynamical properties of Janus nanodimers (NDs) dispersed in lamellar phases of a diblock copolymer. By performing molecular dynamics simulations, we show that an accurate tuning of the interactions between NDs and copolymer blocks can lead to a close control [...] Read more.
We investigate structural and dynamical properties of Janus nanodimers (NDs) dispersed in lamellar phases of a diblock copolymer. By performing molecular dynamics simulations, we show that an accurate tuning of the interactions between NDs and copolymer blocks can lead to a close control of NDs’ space distribution and orientation. In particular, NDs are preferentially found within the lamellae if enthalpy-driven forces offset their entropic counterpart. By contrast, when enthalpy-driven forces are not significant, the distribution of NDs, preferentially observed within the inter-lamellar spacing, is mostly driven by excluded-volume effects. Not only does the degree of affinity between host and guest species drive the NDs’ distribution in the polymer matrix, but it also determines their space orientation. In turn, these key structural properties influence the long-time dynamics and the ability of NDs to diffuse through the polymer matrix. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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32 pages, 8851 KiB  
Article
Potential of Mean Force between Bare or Grafted Silica/Polystyrene Surfaces from Self-Consistent Field Theory
by Aristotelis P. Sgouros, Constantinos J. Revelas, Apostolos T. Lakkas and Doros N. Theodorou
Polymers 2021, 13(8), 1197; https://doi.org/10.3390/polym13081197 - 07 Apr 2021
Cited by 10 | Viewed by 2559
Abstract
We investigate single and opposing silica plates, either bare of grafted, in contact with vacuum or melt phases, using self-consistent field theory. Solid–polymer and solid–solid nonbonded interactions are described by means of a Hamaker potential, in conjunction with a ramp potential. The cohesive [...] Read more.
We investigate single and opposing silica plates, either bare of grafted, in contact with vacuum or melt phases, using self-consistent field theory. Solid–polymer and solid–solid nonbonded interactions are described by means of a Hamaker potential, in conjunction with a ramp potential. The cohesive nonbonded interactions are described by the Sanchez-Lacombe or the Helfand free energy densities. We first build our thermodynamic reference by examining single surfaces, either bare or grafted, under various wetting conditions in terms of the corresponding contact angles, the macroscopic wetting functions (i.e., the work of cohesion, adhesion, spreading and immersion), the interfacial free energies and brush thickness. Subsequently, we derive the potential of mean force (PMF) of two approaching bare plates with melt between them, each time varying the wetting conditions. We then determine the PMF between two grafted silica plates separated by a molten polystyrene film. Allowing the grafting density and the molecular weight of grafted chains to vary between the two plates, we test how asymmetries existing in a real system could affect steric stabilization induced by the grafted chains. Additionally, we derive the PMF between two grafted surfaces in vacuum and determine how the equilibrium distance between the two grafted plates is influenced by their grafting density and the molecular weight of grafted chains. Finally, we provide design rules for the steric stabilization of opposing grafted surfaces (or fine nanoparticles) by taking account of the grafting density, the chain length of the grafted and matrix chains, and the asymmetry among the opposing surfaces. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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12 pages, 4915 KiB  
Article
Novel Hybrid Polymer Composites with Graphene and MXene Nano-Reinforcements: Computational Analysis
by Sigitas Kilikevičius, Saulė Kvietkaitė, Leon Mishnaevsky, Jr., Mária Omastová, Andrey Aniskevich and Daiva Zeleniakienė
Polymers 2021, 13(7), 1013; https://doi.org/10.3390/polym13071013 - 25 Mar 2021
Cited by 16 | Viewed by 3531
Abstract
This paper presents a computational analysis on the mechanical and damage behavior of novel hybrid polymer composites with graphene and MXene nano-reinforcements targeted for flexible electronics and advanced high-strength structural applications with additional functions, such as real-time monitoring of structural integrity. Geometrical models [...] Read more.
This paper presents a computational analysis on the mechanical and damage behavior of novel hybrid polymer composites with graphene and MXene nano-reinforcements targeted for flexible electronics and advanced high-strength structural applications with additional functions, such as real-time monitoring of structural integrity. Geometrical models of three-dimensional representative volume elements of various configurations were generated, and a computational model based on the micromechanical finite element method was developed and solved using an explicit dynamic solver. The influence of the geometrical orientation, aspect ratio, and volume fractions of the inclusions, as well as the interface properties between the nano-reinforcements and the matrix on the mechanical behavior, was determined. The results of the presented research give initial insights about the mechanical and damage behavior of the proposed composites and provide insight for future design iterations of similar multifunctional materials. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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17 pages, 472 KiB  
Article
Heterogeneity Effects in Highly Cross-Linked Polymer Networks
by Gérald Munoz, Alain Dequidt, Nicolas Martzel, Ronald Blaak, Florent Goujon, Julien Devémy, Sébastien Garruchet, Benoit Latour, Etienne Munch and Patrice Malfreyt
Polymers 2021, 13(5), 757; https://doi.org/10.3390/polym13050757 - 28 Feb 2021
Cited by 3 | Viewed by 2381
Abstract
Despite their level of refinement, micro-mechanical, stretch-based and invariant-based models, still fail to capture and describe all aspects of the mechanical properties of polymer networks for which they were developed. This is for an important part caused by the way the microscopic inhomogeneities [...] Read more.
Despite their level of refinement, micro-mechanical, stretch-based and invariant-based models, still fail to capture and describe all aspects of the mechanical properties of polymer networks for which they were developed. This is for an important part caused by the way the microscopic inhomogeneities are treated. The Elastic Network Model (ENM) approach of reintroducing the spatial resolution by considering the network at the level of its topological constraints, is able to predict the macroscopic properties of polymer networks up to the point of failure. We here demonstrate the ability of ENM to highlight the effects of topology and structure on the mechanical properties of polymer networks for which the heterogeneity is characterised by spatial and topological order parameters. We quantify the macro- and microscopic effects on forces and stress caused by introducing and increasing the heterogeneity of the network. We find that significant differences in the mechanical responses arise between networks with a similar topology but different spatial structure at the time of the reticulation, whereas the dispersion of the cross-link valency has a negligible impact. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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28 pages, 8301 KiB  
Article
Interface and Interphase in Polymer Nanocomposites with Bare and Core-Shell Gold Nanoparticles
by Albert J. Power, Ioannis N. Remediakis and Vagelis Harmandaris
Polymers 2021, 13(4), 541; https://doi.org/10.3390/polym13040541 - 12 Feb 2021
Cited by 18 | Viewed by 3542
Abstract
Metal nanoparticles are used to modify/enhance the properties of a polymer matrix for a broad range of applications in bio-nanotechnology. Here, we study the properties of polymer/gold nanoparticle (NP) nanocomposites through atomistic molecular dynamics, MD, simulations. We probe the structural, conformational and dynamical [...] Read more.
Metal nanoparticles are used to modify/enhance the properties of a polymer matrix for a broad range of applications in bio-nanotechnology. Here, we study the properties of polymer/gold nanoparticle (NP) nanocomposites through atomistic molecular dynamics, MD, simulations. We probe the structural, conformational and dynamical properties of polymer chains at the vicinity of a gold (Au) NP and a functionalized (core/shell) Au NP, and compare them against the behavior of bulk polyethylene (PE). The bare Au NPs were constructed via a systematic methodology starting from ab-initio calculations and an atomistic Wulff construction algorithm resulting in the crystal shape with the minimum surface energy. For the functionalized NPs the interactions between gold atoms and chemically adsorbed functional groups change their shape. As a model polymer matrix we consider polyethylene of different molecular lengths, from the oligomer to unentangled Rouse like systems. The PE/Au interaction is parametrized via DFT calculations. By computing the different properties the concept of the interface, and the interphase as well, in polymer nanocomposites with metal NPs are critically examined. Results concerning polymer density profiles, bond order parameter, segmental and terminal dynamics show clearly that the size of the interface/interphase, depends on the actual property under study. In addition, the anchored polymeric chains change the behavior/properties, and especially the chain density profile and the dynamics, of the polymer chain at the vicinity of the Au NP. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymer Nanocomposites)
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