Shear-Thinning in Polymer Melts
Polymer melts are considered complex fluids because the details of the atomistic structure of the polymers impact their flow (or rheological) properties, such as the viscosity. In simple (or Newtonian) fluids, the viscosity is constant, no matter how fast the fluid is flowing. In complex (or non-Newtonian) fluids, the viscosity is not constant. Shear-thinning is the term given to the rheological phenomenon observed when the viscosity decreases with increased shear rate. Shear flow occurs when a fluid is sheared, such as typical pressure driven flow down a pipe. On this page, we provide visualizations of the atomic-level origin of shear-thinning behavior. We also show the analogous structure for tension-thinning, which occurs in extensional flow, when a material is stretched, such as when one pulls a rubber band.
These materials are all dense fluids. In the visualizations below, only a few polymer chains are shown so that one is better able to visualize the conformation of the polymers. Visualizations of the same snapshots that include all chains are available here. The chains are given different colors in order to distinguish them from each other. All of these polymers are short linear polyethylene (C128H258). Only the carbon atoms are shown in the visualization.
Interactive Structures
C128H258 at equilibrium at 450 K. |
C128H258 under planar Couette flow at a dimensionless shear rate of 0.8 and 450 K. |
C128H258 under planar elongational flow at a dimensionless elongation rate of 0.2 and 450 K. |
Color Legend: All atoms are colored by chain.
To see the snapshots containing all chains, click: Visualizations of Shear-Thinning in Polymer (All Chains)
References
These structures were created by former graduate students at the University of Tennessee, Dr. Chunggi Baig and Dr. Jun Mo Kim, coadvised by by Dr. David Keffer (MSE) and Dr. Brian Edwards (CBE). References to several relevant papers are provided below.
Baig, C., Edwards, B.J., Keffer, D.J., Cochran, H.D., "Rheological and structural studies of liquid decane, hexadecane,
and tetracosane under planar elongational flow using nonequilibrium molecular dynamics simulations", J. Chem. Phys., 122 2005 article # 184906. doi: 10.1063/1.1897373.
Ionescu, T. C., Baig, C., Edwards, B. J., Keffer, D. J., Habenschuss, A., "Structure formation under steady-state isothermal planar elongational flow of n-eicosane:
A comparison between simulation and experiment", Phys. Rev. Lett 96(3).2006 article # 037802; reprinted in Virtual Journal of Biological Physics Research 11(3) 2006. doi: 10.1103/PhysRevLett.96.037802.
Baig, C., Edwards, B.J., Keffer, D.J., Cochran, H.D., Harmandaris, V.A., "Rheological and structural studies of linear polyethylene
melts under planar elongational flow using nonequilibrium molecular dynamics simulations", J. Chem. Phys., 124 2006 article # 084902. doi: 10.1063/1.2174006.
Baig, C., Edwards, B.J., Keffer, D.J., "A molecular dynamics study of the stress-optical behavior of a
linear short-chain polyethylene melt under shear", Rheologica Acta 46 2007 p. 1171-1186. doi: 10.1007/s00397-007-0199-2.
Kim, J.M., Keffer, D.J., Edwards, B.J., "Visualization of Conformational Changes of Linear Alkanes & Short
Polyethylenes under Shear and Elongational Flows", J. Mol. Graph. Mod. 26(7) 2008 pp. 1046-1056. doi: 10.1016/j.jmgm.2007.09.001.
Kim, J.M., Edwards, B.J., Khomami, B., Keffer, D.J., "Single-chain dynamics of linear
polyethylene liquids under shear flow", Phys. Lett. A 373(7) 2009 pp. 769-772. doi: 10.1016/j.physleta.2008.12.062.
Kim, J.M., Edwards, B.J., Keffer, D.J., Khomami, B., "Dynamics of individual molecules of
linear polyethylene liquids under shear: Atomistic simulation and comparison with a free-draining bead-rod chain", J. Rheol., 54(2) 2010 pp. 283-310. doi: 10.1122/1.3314298.
posted: July 2104.
updated: July 2014.