Effect of Nanoparticles Surface Bonding and Aspect Ratio on Mechanical Properties of Highly Cross-Linked Epoxy Nanocomposites: Mesoscopic Simulations.

The paper aims to study the mechanical properties of epoxy resin filled with clay nanoparticles (NPs), depending on their shapes and content on the surface of a modifying agent capable of forming covalent bonds with a polymer. The cylindrical clay nanoparticles with equal volume and different aspects ratios (disks, barrel, and stick) are addressed. The NPs' bonding ratio with the polymer (RGC) is determined by the fraction of reactive groups and conversion time and varies from RGC = 0 (non-bonded nanoparticles) to RGC = 0.65 (more than half of the surface groups are linked with the polymer matrix). The performed simulations show the so-called load-bearing chains (LBCs) of chemically cross-linked monomers and modified nanoparticles to determine the mechanical properties of the simulated composites. The introduction of nanoparticles leads to the breaking of such chains, and the chemical cross-linking of NPs with the polymer matrix restores the LBCs and strengthens the composite. At small values of RGC, the largest value of the elastic modulus is found for systems filled with nanoparticles having the smallest surface area, and at high values of RGC, on the contrary, the systems containing disk-shaped particles with the largest surface area have a larger elastic modulus than the others. All calculations are performed within the framework of a mesoscopic model based on accurate mapping of the atomistic structures of the polymer matrix and nanoparticles into coarse-grained representations, which, if necessary, allow reverse data mapping and quantitative assessment of the state of the filled epoxy resin. On the other hand, the obtained data can be used to design the functional materials with specified mechanical properties based on other practically significant polymer matrices and nanofillers.

Additive-induced ordered structures formed by PC71BM fullerene derivatives.

We report the results of an experimental and theoretical study of structure formation in mixtures of phenyl-C71-butyric acid methyl ester (PC71BM) with high boiling octane based solvent additives 1,8-octanedithiol (ODT), 1,8-dibromooctane, and 1,8-diiodooctane obtained by evaporation of a host-solvent (chlorobenzene). Experimental studies by DSC, SAXS and WAXS methods found evidence of crystallization of fullerenes in the presence of the high boiling additives in the mixtures. A molecular dynamics simulation of a PC71BM/ODT mixture revealed the self-assembly of fullerenes into sponge-like network structures.

Thermoset Polymer Matrix Structure and Properties: Coarse-Grained Simulations.

The formation of a thermoset polymer network is a complex process with great variability. In this study, we used dissipative particle dynamics and graph theory tools to investigate the curing process and network topology of a phthalonitrile thermoset to reveal the influence of initiator and plasticizer concentration on its properties. We also propose a novel way to characterize the network topology on the basis of two independent characteristics: simple cycle length (which is mainly affected by the initiator amount) and the number of simple cycles passing through a single covalent bond (which is determined primarily by plasticizer concentration). These values can be treated in the more familiar terms of network "mesh size" and "sponginess", correspondingly. The combination of these two topological parameters allows one to characterize any given network in an implicit but precise way and predict the resulting network properties, including the mechanical modulus. We believe that the same approach could be useful for other polymer networks as well, including rubbers and gels.

Dynamic and Static Mechanical Properties of Crosslinked Polymer Matrices: Multiscale Simulations and Experiments.

We studied the static and dynamic mechanical properties of crosslinked polymer matrices using multiscale simulations and experiments. We continued to develop the multiscale methodology for generating atomistic polymer networks, and applied it to the case of phthalonitrile resin. The mechanical properties of the resulting networks were analyzed using atomistic molecular dynamics (MD) and dissipative particle dynamics (DPD). The Young's and storage moduli increased with conversion, due both to the appearance of a network of covalent bonds, and to freezing of degrees of freedom and lowering of the glass transition temperature during crosslinking. The simulations' data showed good quantitative agreement with experimental dynamic mechanical analysis measurements at temperatures below the glass transition. The data obtained in MD and DPD simulations at elevated temperatures were conformable. This makes it possible to use the suggested approach for the prediction of mechanical properties of a broad range of polymer matrices, including ones with high structural heterogeneity.

Simulation of heterogeneous end-coupling reactions in polydisperse polymer blends.

The influence of polydispersity on the interfacial kinetics of end-coupling and microstructure formation in the melt of immiscible polymers was studied using dissipative particle dynamics simulations. The irreversible reaction started at a flat interface between two layers, each of which contained polymer chains of two different lengths with functionalized or unreactive end groups. As in the case of fully functionalized monodisperse reactants [A. V. Berezkin and Y. V. Kudryavtsev, Macromolecules 44, 112 (2011)], four kinetic regimes were observed: linear (mean field coupling at the initial interface), saturation (decreasing the reaction rate due to the copolymer brush formation or reactant depletion near the interface), autocatalytic (loss of the initial interface stability and formation of a lamellar microstructure), and terminal (microstructure ripening under diffusion control). The interfacial instability is caused by overcrowding the interface with the reaction product, and it can be kinetically suppressed by increasing chain length of the reactants. Main effects of polydispersity are as follows: (i) the overall end-coupling rate is dominated by the shortest reactive chains; (ii) the copolymer concentration at the interface causing its instability can be not the same as in the lamellas formed afterwards; (iii) mean length of the copolymer product considerably changes with conversion passing through a minimum when a microstructure is just formed.