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    chain correlations in linear and ring polymer blends

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    research paper on polymers

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    © All Rights Reserved
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    18 views9 pages

    Chain Correlations in Linear and Ring Polymer Blends

    Uploaded by

    ggaras
    research paper on polymers

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    of 9
    “Chain correlations in linear and ring polymer blends George E. Garas Molecular Modelling of Materials Laboratory, nstitwce of Physical Chemitry, NRCPS “Democritas* 153 1 Ag. Paraskevi Ants, Greece Marios K. Kosmas Chemistry Department, Universicy of loamnina, 451 10 foatnina Greece (Received 6 June 1997; accepted 26 Septersber 1997) Our recent studies on linear-polymer blends are extended to include the linearriag and ring/ing polymer systems, By means of the free energies of mixing. ring-polymer blends are found to be the ‘most devisting from the Flory-Huggins theory presenting y-parameters (interaction pararacters) that depend more strongly on concentrations and molecular wcights, The (ree energies are found (2 ‘be smaller in the case of the ring-polymer blends, ie., these blends are predicted to be the most stable, in second with cloud-point experiments. The related nextron scattering, y.q parsmetes are found to present higher concestration dependence than the x-parameters of thes systems, By means (oF their mean-square radii of gyration, both ring and linear chains are found to contract When a binary polymer system approaches the phase separation limit. Close tothe spinodal, the contraction is telatively stronger for the chains of the smaller concentrations and lengths, while the three systems obtain an ideal behavior atthe large molecular ‘Institute of Physics. ($0021-9606(98)S1301-6] L INTRODUCTION In our recent work we have studied phase cquilbsiuin and chain size in binary polymer blends in a perturbation theory scheme by means of an excluded-volume model, In- vestigning binary polymer systems approaching the phase separation limit, we have anived at resuls according 10 ‘which chain correlations ignored by the Flory- Huggins theory both enhance the stability of polymer blends an re ‘dice the mean sizes of theie polymer coils. These results are consisent with experiments and simulations. We take ints accouat chain correlations averaging overall different con. formations, supposing that ehsns in single polymer systems (ets) exhibit an idea, «theta», behavier* A special class of diagrams, tne one-loop diagrams, is found to affect suongly the free energy difference AG of the A/B polymer blends as well as the mean-square end-to-end distances (Ry, f A.B, of their polymer coils. These diagrams nave been evaluated and summed upto all orders of concentration and ‘meraction, leading to closed expressions for both AG and (R), Tn this work we consider the case of ring chaits,extend- ing our previous studies of linear~polymer blends 0 include linearring and ring/ing binary polymer systems, describing 8 well the behavior of the chain size in these systems by means of the mean-square ras of gyration of polymet chains. The behavior of the cyclic polymers differentates, Since they presenta smaller number of confermations com. pared with the open ones, fact thats expected to affect the behavior oftheir blends as well. Ring polymers (monocyclic polymecs) are the simplest example of homopolymers with closed paths along the chain, andthe fst candidate for the study of the effect of the nonopen archieeture in polymer blends. They are also good representatives of polymer net. ‘works as far as their structure factors are concerned.) The 376 J. Chom. Phys. 108 (1), 1 January 1998 (02-9606/981081878715.00 weight, N=, limit. © 1998 American investigation of tng-polymer blends s very important, since closed and open polymer chains often coexist in equlibaurn in natral 5 well asin synthetic, materials as posts and byproducts of the various polymerization methods.“ In the last few years these sjsiems hive received notble ‘experimental* and theoretical”* interest, comparable to that ‘regarding isolated ring chains, solutions of ring polymers. and metts.??"” In this work we stdy the linasinear,lsearing, and ringing polymer bles, ing the same metiod”po- ‘sented in detail in our previous publications.’ We work in the canonical ensemble, employing an Edwards conigratical ‘Hamiltorian,"' formally the same for the three different Kinds of polymer systems feelers Rade, [teen x Oral rat) ay ‘The first term expresses the connectivity ofthe chains, while the second term stands for the interactions along the chain contours =, and zy at the spatial points tara) and t9( 79). y= SaRE1 ~exp(—U,(R)/kpT)] are the excluded volume Parameters or the binary integrals of the interacting parts of the chains of the kinds # and j. In what follows we will

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