Molecular mechanisms of the chain diffusion between crystalline and amorphous fractions in polyethylene (original) (raw)
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Dynamics of twist point defects with stretching in a polymer crystal
Journal of Experimental and Theoretical Physics, 2000
A molecular-dynamics simulation of the behavior of a twist point defect with stretching in a chain of an equilibrium polymer crystal ("united" atoms approximation for polyethylene) is performed for immobile and mobile neighboring chains. It is shown that such a defect in a cold polymer crystal possesses soliton-type mobility. The upper limit of the spectrum of soliton velocities is found, and it is the same for both cases. The maximum possible velocity of defects is three times lower than the theoretical limit of the spectrum (which is equal to the velocity of "torsional" sound in an isolated chain). An explanation of the reason for this discrepancy is proposed: because of the interaction of two "degrees of freedom" of the defect (twisting and stretching) the energy of a nonlinear wave is dissipated in the linear modes of the system, which results in effective friction whose magnitude depends strongly on the velocity of the defect. The "boundary of the spectrum of soliton velocities" determines the transition between regimes of strong and weak braking of defects.
The Journal of Chemical Physics, 2001
Molecular dynamics simulations of unentangled linear polyethylene melts have been performed for systems composed of 10 chains of 100 united atoms over a pressure range of 1 to 5000 bar and a temperature range of 375 to 475 K. Transition rates, activation volumes, and activation energies are in good agreement with values from similar simulations quoted in literature for systems well above T g . Second-neighbor torsional angle coupling is observed to increase with increasing pressure and decreasing temperature. The lifetime of this coupling between conformational events is presented for the first time. Geometric autocorrelation functions are analyzed in terms of their distribution of relaxation times and reveal a process on the time scale of a few picoseconds and another on the time scale of a few nanoseconds. An intermediate process develops between these two time scales at high pressure and low temperature.
Macromolecules, 1990
Molecular dynamics is used to study the melting on the surface of a polyethylene-like crystal. The rate constant for melting of a crystalline molecule without and with one to four folds is determined at several different temperatures and molecular lengths. The results show a strong dependence of the transition rate on the number of folds. For a constant lamellar thickness, the transition rate decreases with increasing number of folds for temperatures near the equilibrium melting temperature, as expected from analogy with experimental melting temperatures. In contrast, the transition rate increases with increasing number of folds for temperaturesthat exceed the equilibrium melting temperature by more than 100 K. Two melting paths are suggested to explain the simulation data. One pathway involves a competition between melting and crystallization. This pathway leads to a decreasing transition rate as a function of increasing folding. The second pathway exhibits dominating melting. In this case, the rate of transition tends to increase with increasing number of folds. Diffusion coefficients of segments at different locations along the chain show that motion of the ends of a polymer chain or of the folds is faster than in the center of the stem. The overall effect of increasing temperature is to increase the diffusion coefficients.
The effects of interphase topology, entanglements, and chain dynamics on the mechanical response of semicrystalline polyethylene have been examined using atomistic simulations. In particular, the prevalence of the cavitation and melting/recrystallization mechanisms for yield and plastic flow were found to depend on both topological and dynamical properties of the molecular segments in the semicrystalline interphase. First, two different protocols were used during preparation of the interphase ensemble to modulate the distribution of (i) loops, bridges, and tails and (ii) entanglements within the noncrystalline domain. A protocol denoted "step-wise cooling" produced structures having a large fraction of long, entangled segments that yielded by the melting/recrystallization mechanism about 50% of the time. By contrast, the protocol denoted "instantaneous quench" produced structures that yielded by melting/recrystallization about 73% of the time. Second, two different united atom force fields, PYS and TraPPE-UA, that exhibit nearly identical topological characteristics of the noncrystalline domain but different mobilities were used to study the effect of chain dynamics on yield mechanisms. At the slower strain rate used in this work, yield and plastic flow proceeded exclusively via cavitation for the model using the TraPPE-UA force field, whereas both cavitation and melting/recrystallization were observed for the model using the PYS force field. The greater prevalence of melting/recrystallization in the latter case is attributed to faster chain-sliding dynamics in the crystalline domain. The dependences of the yield mechanism on topology and dynamics are found to be related.
Molecular dynamics simulations have been used to prepare semicrystalline samples of linear polyethylene (PE) using the anisotropic united atom (AUA4) model. The initial configurations of the simulations were obtained by controlled melting of the pure crystalline system and a unique re-connection method between chain segments in the intercrystalline regions. Systems containing two crystalline slabs and two large intercrystalline regions are built with different defects, introduced to mimic the structure of real PE systems, namely: bridging chains connecting two different crystalline slabs, reentrant chains emerging and re-entering into the same crystalline slab, and free chains. We observe large structural differences between the different systems. We show that average and local density depend on defect types which in turn affect the dynamical properties. This explicit simulation of a crystalline-amorphous interfacial region thus gives a possible picture of intercrystalline regions that can serve to understand and predict penetrant gases transport in such materials.
Defect-mediated curvature and twisting in polymer crystals
2000
Crystalline polymer solids almost inevitably exhibit defects due to chain ends, chain folding and the limited molecular mobility. The defects result in local (dislocations, grain boundaries) or global (bending, twisting) distortions of the molecular symmetry with pronounced implications on materials properties. Depending on the localization of the deformation, continuous molecular distortions or chain scission are expected, resulting in distinct differences for the mechanical (crack formation) and optoelectronic properties ( ...
Self-assembly of domain wall of molecular twist defects in polyethylene crystal
Macromolecular Symposia, 1996
Two-dimensional structural defects in a polyethylene crystal (twist domain walls) are investigated by means of analytic treatment and molecular dynamics simulation. The formation of the domain wall as a result of relaxation of the crystal from different initial states is studied and parameters of this type of defects are calculated.
Molecular dynamics simulation for polyethylene crystallization: Effect of long chain branches
Polyolefins Journal, 2021
The influence of long branches on crystallization behavior has been studied by means of molecular dynamics simulations. Using two systems: polyethylene (PE) with long branches (LCB-PE) and PE without long branches (linear-PE) with the same molecular weight, we have examined the crystallization behavior of the two systems by molecular dynamics simulation. This paper explains the influence of long branches on the isothermal crystallization process and the non-isothermal crystallization process with similar initial interchain contact fraction (ICF) in terms of final ICF, crystal regions, crystallinity, concentration of tie chains and energy. It is found that the crystallization process is classified as two stages: the nucleation stage and the crystal growth stage. The existence of long branches is favorable for the first stage while unfavorable for the second stage. Knots that act as crystalline defects are excluded from the lamella, resulting in decreasing in regularity and crystallinity of molecular chains. From the perspective of potential energy and non-bond energy, LCB-PE has lower energy than linear-PE in the nucleation stage while the energy of linear-PE is lower than that of LCB-PE in the second stage. In short, the long branched chains inhibit the crystallization process.