Revealing the Role of Chain Conformations on the Origin of the Mechanical Reinforcement in Glassy Polymer Nanocomposites.

Understanding the mechanism of mechanical reinforcement in glassy polymer nanocomposites is of paramount importance for their tailored design. Here, we present a detailed investigation, via atomistic simulation, of the coupling between density, structure, and conformations of polymer chains with respect to their role in mechanical reinforcement. Probing the properties at the molecular level reveals that the effective mass density as well as the rigidity of the matrix region changes with filler volume fraction, while that of the interphase remains constant. The origin of the mechanical reinforcement is attributed to the heterogeneous chain conformations in the vicinity of the nanoparticles, involving a 2-fold mechanism. In the low-loading regime, the reinforcement comes mainly from a thin, single-molecule, 2D-like layer of adsorbed polymer segments on the nanoparticle, whereas in the high-loading regime, the reinforcement is dominated by the coupling between train and bridge conformations; the latter involves segments connecting neighboring nanoparticles.

Probing the Linear-to-Plastic Transition in Polymer Nanocomposites via Atomistic Simulations: The Role of Interphases.

Polymer nanocomposites have found ubiquitous use across diverse industries, attributable to their distinctive properties and enhanced mechanical performance compared to conventional materials. Elucidating the elastic-to-plastic transition in polymer nanocomposites under diverse mechanical loads is paramount for the bespoke design of materials with desired mechanical attributes. In the current work, the elastic-to-plastic transition is probed in model systems of polyethylene oxide (PEO) and silica, SiO2, nanoparticles, through detailed atomistic molecular dynamics simulations. This comprehensive, multi-scale analysis unveils pivotal markers of the elastic-to-plastic transition, highlighting the quintessential role of microstructural and regional heterogeneities in density, strain, and stress fields, featuring the polymer-nanoparticle interphase region. At the atomic level, the behavior of polymer chains interacting with nanoparticle surfaces is traced, differentiating between free and adsorbed chains, and identifying the microscopic origins of the linear-to-plastic transition. The mechanical behavior of subregions are characterized within the PEO/SiO2 nanocomposites, focusing on the interphase and bulk-like polymer areas, probing stress heterogeneities and their decomposition into various force contributions. At the inception of plasticity, a disruption is discerned in isotropy of the polymeric density field, the emergence of low-density regions, and microscopic voids/cavities within the polymer matrix concomitant with a transition of adsorbed chains to free. The yield strain also emerges as an inflection point in the local versus global strain diagram, demarcating the elastic limit, and the plastic regime shows pronounced strain heterogeneities. The decomposition of the atomic Virial stress into bonded and non-bonded interactions indicates that the rigidity of the material is primarily governed by non-bonded interactions, significantly influenced by the volume fraction of the nanoparticle. These findings emphasize the importance of the microstructural and micromechanical environment at the polymer-nanoparticle interface on the linear-to-plastic transition, which is of great importance in the design of nanocomposite materials with advanced mechanical properties.

Distribution of Mechanical Properties in Poly(ethylene oxide)/silica Nanocomposites via Atomistic Simulations: From the Glassy to the Liquid State.

Polymer nanocomposites exhibit a heterogeneous mechanical behavior that is strongly dependent on the interaction between the polymer matrix and the nanofiller. Here, we provide a detailed investigation of the mechanical response of model polymer nanocomposites under deformation, across a range of temperatures, from the glassy regime to the liquid one, via atomistic molecular dynamics simulations. We study the poly(ethylene oxide) matrix with silica nanoparticles (PEO/SiO2) as a model polymer nanocomposite system with attractive polymer/nanofiller interactions. Probing the properties of polymer chains at the molecular level reveals that the effective mass density of the matrix and interphase regions changes during deformation. This decrease in density is much more pronounced in the glassy state. We focus on factors that govern the mechanical response of PEO/SiO2 systems by investigating the distribution of the (local) mechanical properties, focusing on the polymer/nanofiller interphase and matrix regions. As expected when heating the system, a decrease in Young's modulus is observed, accompanied by an increase in Poisson's ratio. The observed differences regarding the rigidity between the interphase and the matrix region decrease as the temperature rises; at temperatures well above the glass-transition temperature, the rigidity of the interphase approaches the matrix one. To describe the nonlinear viscoelastic behavior of polymer chains, the elastic modulus of the PEO/SiO2 systems is further calculated as a function of the strain for the entire nanocomposite, as well as the interphase and matrix regions. The elastic modulus drops dramatically with increasing strain for both the matrix and the interphase, especially in the small-deformation regime. We also shed light on characteristic structural and dynamic attributes during deformation. Specifically, we examine the rearrangement behavior as well as the segmental and center-of-mass dynamics of polymer chains during deformation by probing the mobility of polymer chains in both axial and radial motions under deformation. The behavior of the polymer motion in the axial direction is dominated by the deformation, particularly at the interphase, whereas a more pronounced effect of the temperature is observed in the radial directions for both the interphase and matrix regions.

Unraveling the Effect of Strain Rate and Temperature on the Heterogeneous Mechanical Behavior of Polymer Nanocomposites via Atomistic Simulations and Continuum Models.

Polymer nanocomposites are characterized by heterogeneous mechanical behavior and performance, which is mainly controlled by the interaction between the nanofiller and the polymer matrix. Optimizing their material performance in engineering applications requires understanding how both the temperature and strain rate of the applied deformation affect mechanical properties. This work investigates the effect of strain rate and temperature on the mechanical properties of poly(ethylene oxide)/silica (PEO/SiO2) nanocomposites, revealing their behavior in both the melt and glassy states, via atomistic molecular dynamics simulations and continuum models. In the glassy state, the results indicate that Young's modulus increases by up to 99.7% as the strain rate rises from 1.0 × 10-7 fs-1 to 1.0 × 10-4 fs-1, while Poisson's ratio decreases by up to 39.8% over the same range. These effects become even more pronounced in the melt state. Conversely, higher temperatures lead to an opposing trend. A local, per-atom analysis of stress and strain fields reveals broader variability in the local strain of the PEO/SiO2 nanocomposites as temperature increases and/or the deformation rate decreases. Both interphase and matrix regions lose rigidity at higher temperatures and lower strain rates, blurring their distinctiveness. The results of the atomistic simulations concerning the elastic modulus and Poisson's ratio are in good agreement with the predictions of the Richeton-Ji model. Additionally, these findings can be leveraged to design advanced polymer composites with tailored mechanical properties and could optimize structural components by enhancing their performance under diverse engineering conditions.

Mechanical Behavior of Polymer Nanocomposites via Atomistic Simulations: Conformational Heterogeneity and the Role of Strain Rate.

Polymer nanohybrids with a high fraction of nanofillers have been found to exhibit improved mechanical properties compared to the neat polymer homogeneous systems. Since polymer-based materials are characterized by a broad range of relaxation times, it is expected that their response under external load would depend on the actual rate of the applied deformation. In this work, we investigate the heterogeneous mechanical behavior in glassy poly(ethylene oxide)/silica nanoparticles (PEO/SiO2) nanocomposites via detailed atomistic molecular dynamics simulations. Our goal is to unravel the effect of strain rate on the mechanism of polymer nanocomposite reinforcement, within the glassy state, by directly probing the mechanical properties at the molecular level. By applying tensile deformations with various strain rates we clearly demonstrate that the value of the applied strain rate strongly affects the mechanical properties of the PEO/SiO2 model systems, inducing a transition from a rubber-like behavior, at low strain rate, to a more brittle one, at high strain rates. Then, we further investigate the mechanical heterogeneity in glassy PEO/SiO2 systems by probing directly the stress and strain fields for various conformations of adsorbed (trains, tails, loops, and bridges), and free polymer chains. Our data emphasize the importance of both train and bridge conformations on the mechanical reinforcement of the polymer nanocomposites. Last, we also probe the mobility of various chain conformations, under different applied strain rates, and their contribution to the overall mechanical behavior of the nanocomposite, during the deformation process.

A methodology for determining the local mechanical properties of model atomistic glassy polymeric nanostructured materials.

We propose a methodology for calculating the distribution of the mechanical properties in model atomistic polymer-based nanostructured systems. The use of atomistic simulations is key in unravelling the fundamental mechanical behavior of composite materials. Most simulations involving the mechanical properties of polymer nanocomposites (PNCs) concern their global (average) properties, which are typically extracted by applying macroscopic strain on the boundaries of the simulation box and calculating the total (global) stress by invoking the Virial formalism over all atoms within the simulation box; thus, extracting the pertinent mechanical properties from the corresponding stress-strain relation. However, in order to probe the distribution of mechanical properties within heterogeneous multi-component polymer-based systems, a detailed computation of stress and strain fields within specific sub-domains is necessary. For example, it is well known for multi-component nanostructured systems, such as PNCs, that the mechanical behavior of the polymer/nanofiller interphases, or interfaces, is crucial for determining the global mechanical properties of the composite materials. Here we propose a new methodology to probe the distribution of mechanical properties by directly computing the (local) stress and strain at the atomic level, and averaging over user-defined subdomains. The workflow of our computational method possesses the following features:•Calculating the stress and strain per atom (or per particle) for nanostructured microscopic (here atomistic) model configurations, under an imposed applied deformation.•Averaging the local, per-atom defined, stress and strain on user-defined subdomains within the nanostructured model system.•Predicting the mechanical properties within the specific subdomains, focusing on polymer/solid interphases.