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Volumn 31, Issue 4, 1998, Pages 1373-1385

Thermoreversible gelation in solutions of associative polymers. 1. Statics

Author keywords

[No Author keywords available]

Indexed keywords

FREE ENERGY; GELATION; MATHEMATICAL MODELS; MOLECULAR DYNAMICS; PHASE EQUILIBRIA; PHASE SEPARATION; SOLVENTS;

EID: 0032001610     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma970616h     Document Type: Article
Times cited : (509)

References (45)
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    • 1,15
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    • note
    • g) (see eq 4.14 of ref 10). However the two expressions disagree in the postgel regime, as discussed in section 2.3.
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    • note
    • 22 a second-order phase transition is predicted at a the gel point.
  • 25
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    • note
    • It is important that this equation is applicable both below and above the gel point.
  • 26
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    • note
    • Actually the condition of validity of the mean-field theory is even stronger than condition 2.31 (see section 4.2).
  • 27
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    • note
    • 6.)
  • 28
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    • note
    • This type of globule with saturated bonds was considered in refs 37 and 28 using different approaches. The results presented in this section are in agreement with the earlier results. The same problem was also considered in ref 29 using an incorrect assumption that the gel structure inside the globule is compressed. This is not true since the reversible gel structure automatically adjusts itself to any degree of compression of the globule, so that there is no reason for the gel to be strained at equilibrium.
  • 32
    • 85034276970 scopus 로고    scopus 로고
    • note
    • Note that nonlocal intrachain bonds must still exist and are important in the formation of the globule. Indeed, a chain with only local bonds does not collapse into a globule.
  • 33
    • 85034304777 scopus 로고    scopus 로고
    • note
    • cV/N, where cV/N is the total number of polymer chains.
  • 36
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    • Schaefer, L.; Kappeler, Ch. J. Phys. Fr. 1985, 46, 1853. Kosmas, M. J. Phys. Lett. 1984, 5, L889. Broseta, D.; Leibler, L.; Joanny, J. F. Macromolecules 1987, 20, 1935.
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  • 37
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    • Schaefer, L.; Kappeler, Ch. J. Phys. Fr. 1985, 46, 1853. Kosmas, M. J. Phys. Lett. 1984, 5, L889. Broseta, D.; Leibler, L.; Joanny, J. F. Macromolecules 1987, 20, 1935.
    • (1984) J. Phys. Lett. , vol.5
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  • 39
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    • note
    • Note that eq 4.3 is equally applicable to both intra- and interchain contacts provided that the chemical distances (contour lengths) between the monomers in question and the end monomers of the corresponding chain(s) are all long enough, i.e. longer than g.
  • 40
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    • note
    • mf
  • 41
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    • note
    • The sol and gel phases are often not completely separated due to kinetic restrictions. In this case a microgel structure appears and may persist for very long time.
  • 42
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    • note
    • g.
  • 44
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    • note
    • This effect is connected with the fact that the static screening length ξ in a marginal polymer solution decreases with increasing v. A shorter screening length means that the effective repulsion between two stickers on different chains becomes more screened in comparison with the repulsion between two neighboring stickers creating an intrachain bond. The latter interaction is not screened at all since the typical distance between neighboring stickers is much smaller than ξ.


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