Search results for "dynamics."

Structure of Polymer-Grafted Nanoparticle Melts.

2020

The structure of neat melts of polymer-grafted nanoparticles (GNPs) is studied via coarse-grained molecular dynamics simulations. We systematically vary the degree of polymerization and grafting density at fixed nanoparticle (NP) radius and study in detail the shape and size of the GNP coronas. For sufficiently high grafting density, chain sections close to the NP core are extended and form a dry layer. Further away from the NP, there is an interpenetration layer, where the polymer coronas of neighboring GNPs overlap and the chain sections have almost unperturbed conformations. To better understand this partitioning, we develop a two-layer model, representing the grafted polymer around an N…

Role of the Intercrystalline Tie Chains Network in the Mechanical Response of Semicrystalline Polymers

2017

We examine the microscopic origin of the tensile response in semicrystalline polymers by performing large-scale molecular dynamics simulations of various chain lengths. We investigate the microscopic rearrangements of the polymers during tensile deformation and show that the intercrystalline chain connections known as tie chains contribute significantly to the elastic and plastic response. These results suggest that the mechanical behavior of semicrystalline polymers is controlled by two interpenetrated networks of entanglements and tie chains.

Statistical properties of linear-hyperbranched graft copolymers prepared via "hypergrafting" of AB(m) monomers from linear B-functional core chains: …

2015

The reaction of ABm monomers (m = 2, 3) with a multifunctional Bf-type polymer chain ("hypergrafting") is studied by coarse-grained molecular dynamics simulations. The ABm monomers are hypergrafted using the slow monomer addition strategy. Fully dendronized, i.e., perfectly branched polymers are also simulated for comparison. The degree of branching of the molecules obtained with the "hypergrafting" process critically depends on the rate with which monomers attach to inner monomers compared to terminal monomers. This ratio is more favorable if the ABm monomers have lower reactivity, since the free monomers then have time to diffuse inside the chain. Configurational chain properties are also…

1993

4-(4-Carboxyphenyl)-3,5-dioxo-1,2,4-triazolidin-1-yl moieties resulting from 4-(3,5-dioxo-1,2,4-triazolin-4-yl)benzoic acid (U4A) randomly attached to 1,4-polybutadiene form supramolecular aggregates which act as effective junction zones in new thermoplastic elastomers. Deuteron nuclear magnetic resonance (2H NMR) spectroscopy was used to investigate the molecular dynamics of the polymer backbone and the junction zones in selectively labelled samples. The spectra show motional heterogeneity along the polymer chain as well as in the supramolecular domains. Polybutadiene segments which are adjacent to these polar clusters are restricted in their mobility, even at temperatures 100 K above the …

Effects of pressure and of thermal history on the structural phase transition of KCN

1992

The cubic-noncubic structural phase transition of a KCN single crystal is studied as a function of thermal history and of hydrostatic pressure up to 2 kbar. The standard sequence of phases is cubic-monoclinic-orthorhombic on cooling and orthorhombic-cubic on heating. The monoclinic phase is also absent in first cooling runs at low pressures (p≦250 bar). The width of the monoclinic field inp, T phase diagram is increased in second cooling runs. The effects are discussed in terms of a martensitic transformation behavior and random strain fields.

Crystallization Behaviour at High Cooling Rates of Two Polypropylenes

1993

Phase distribution of quenched samples of two isotactic polypropylenes, having different molecular weight distributions, was evaluated by a deconvolution procedure of WAXD spectra. The dependence on cooling rate of the two resins shows the low molecular weights rich polymer is characterized by a faster kinetics with an α-monoclinic to mesomorphic transition taking place at higher cooling rates.

Combined main chain/side chain polymers. A new class of liquid crystalline polymers with unusual structural, thermodynamic and dynamic properties

1990

Abstract Combined main chain/side chain polymers carry rigid rod-like mesogenic units both in the side chain and along the chain backbone. The properties of such combined systems are expected to be controlled by the competition of the interactions between the mesogenic units in the side and main chains as well as the tendency of the chain backbones to maximize their entropy. The thermodynamic, structural and dynamic properties of such combined main chain/side chain liquid-crystalline polymers were investigated for various chain architectures. The combined systems were found to display properties corresponding in many cases to a favourable superposition of properties characteristic of both m…

Elastic Properties of Liquid Crystal Elastomer Balloons

2001

We introduce a method to measure elastic properties of smectic liquid crystalline elastomers. Freely suspended smectic polymer films containing photoreactive groups are inflated to spherical bubbles and crosslinked by UV light irradiation. After crosslinking, the balloon volume is varied and elastic properties of the material are determined from the relation between radius and inner excess pressure. The influence of the network topology on the elastic behaviour is discussed.

Disentangling the Role of Chain Conformation on the Mechanics of Polymer Tethered Particle Materials

2019

[Image: see text] The linear elastic properties of isotropic materials of polymer tethered nanoparticles (NPs) are evaluated using noncontact Brillouin light spectroscopy. While the mechanical properties of dense brush materials follow predicted trends with NP composition, a surprising increase in elastic moduli is observed in the case of sparsely grafted particle systems at approximately equal NP filling ratio. Complementary molecular dynamics simulations reveal that the stiffening is caused by the coil-like conformations of the grafted chains, which lead to stronger polymer–polymer interactions compared to densely grafted NPs with short chains. Our results point to novel opportunities to …

Structured Nanoparticles from the Self-Assembly of Polymer Blends through Rapid Solvent Exchange

2017

Molecular dynamics simulations were performed to study systematically the rapid mixing of a polymer blend in solution with a miscible nonsolvent. In agreement with experiments, we observe that polymers self-assemble into complex nanoparticles, such as Janus and core-shell particles, when the good solvent is displaced by the poor solvent. The emerging structures can be predicted on the basis of the surface tensions between the polymers as well as between the polymers and the surrounding liquid. Furthermore, the size of the nanoparticles can be independently tuned through the mixing rate and the polymer concentration in the feed stream; meanwhile, the composition of the nanoparticles can be c…