Anomalous diffusion of a polymer chain in an unentangled melt.

نویسندگان

  • J Farago
  • H Meyer
  • A N Semenov
چکیده

Contrary to common belief, hydrodynamic interactions in polymer melts are not screened beyond the monomer length and are important in transient regimes. We show that viscoelastic hydrodynamic interactions (VHIs) lead to anomalous dynamics of a tagged chain in an unentangled melt at t<t(N), the Rouse time. The center-of-mass (c.m.) mean-square displacement is enhanced by a large factor increasing with chain length. We develop a theory of VHI-controlled chain dynamics yielding a negative c.m. velocity autocorrelation function which agrees with our molecular dynamics simulations without any fitting parameter. It is also shown that Langevin friction strongly affects the short-t c.m. dynamics, also captured by our theory. The transient VHI effects thus provide the dominant contribution to the subdiffusive c.m. motion universally observed in simulations and experiments.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

On the Anomalous Diffusion of a Polymer Chain in an Unentangled Melt

The dynamics of polymer chains in unentangled melts is commonly described by the Rouse model. However, various experimental and simulation studies show that certain dynamical phenomena in unentangled melts cannot be explained by the Rouse theory. One of the puzzling observations is the anomalous diffusion of the center-of-mass (CM) of a polymer chain for times t < tN , where tN ∝ N is the Rouse...

متن کامل

Influence of polymer architectures on diffusion in unentangled polymer melts.

Recent simulations have indicated that the thermodynamic properties and the glassy dynamics of polymer melts are strongly influenced by the average molecular shape, as quantified by the radius of gyration tensor of the polymer molecules, and that the average molecular shape can be tuned by varying the molecular topology (e.g., ring, star, linear chain, etc.). In the present work, we investigate...

متن کامل

On the non-Gaussianity of chain motion in unentangled polymer melts

We have investigated chain dynamics of an unentangled polybutadiene melt via molecular dynamics simulations and neutron spin echo experiments. Good short-time statistics allows for the first experimental confirmation of subdiffusive motion of polymer chains for times less than the Rouse time (tR) confirming behavior in this regime observed in simulations. Analysis of simulation trajectories obt...

متن کامل

Single-molecule study on polymer diffusion in a melt state: effect of chain topology.

We report a new methodology for studying diffusion of individual polymer chains in a melt state, with special emphasis on the effect of chain topology. A perylene diimide fluorophore was incorporated into the linear and cyclic poly(THF)s, and real-time diffusion behavior of individual chains in a melt of linear poly(THF) was measured by means of a single-molecule fluorescence imaging technique....

متن کامل

Stress relaxation in entangled polymer melts.

We present an extensive set of simulation results for the stress relaxation in equilibrium and step-strained bead-spring polymer melts. The data allow us to explore the chain dynamics and the shear relaxation modulus, G(t), into the plateau regime for chains with Z=40 entanglements and into the terminal relaxation regime for Z=10. Using the known (Rouse) mobility of unentangled chains and the m...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Physical review letters

دوره 107 17  شماره 

صفحات  -

تاریخ انتشار 2011