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Termination of crystallization or ordering of flexible, linear macromolecules

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Abstract

This review concerns the “termination of crystallization or ordering of flexible, linear macromolecules” before the transition from the amorphous phase reaches thermodynamic equilibrium. It makes use of the precision of hindsight in interpretation of old experiments and the back-integration of more recent experiments into the knowledge gained from the well-known older experiments which had led to the paradox: Once the semi-ordered sample is produced, its disordering frequently follows a zero-entropy-production path, i.e., its latent heat is linked to the free enthalpy of the non-equilibrium phase, while on ordering, there exists a metastable temperature region of the polymer melt which cannot be broken by nuclei of the ordered phase. The classic scheme of crystallization via nucleation and growth is used to set the stage for the discussion. This scheme has been used for many years to describe the motion of single motifs to crystallize small, rigid molecules and its slow-down when approaching the glass transition. For flexible macromolecules, the ordering mechanism needs to be expanded to the description of cooperative ordering schemes of more than one motif of the molecular segments and a more complicated, multiple-step slow down when approaching the much wider glass transition region. The structural features causing the incomplete ordering of flexible macromolecules are the three-dimensional defects created at the phase boundaries between ordered and disordered phases, initially called the amorphous defects. The matter contained in these amorphous defects possesses a much broader glass transition. If this glass transition lies above the glass transition of the unrestrained, amorphous phase, the amorphous defects represent a separate nanophase, called a rigid-amorphous fraction. Modern differential scanning calorimetry (DSC), temperature-modulated DSC, and differential fast scanning calorimetry permit the study of latent heats and heat-capacity changes involved in the liquid–solid transitions of amorphous phases, crystals, and mesophases. In this more complex framework, the “termination of crystallization of flexible, linear macromolecules” is described together with the possibility of molar mass segregation by long-range and local diffusion instead of a thermodynamic mechanism.

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Notes

  1. The idea about the atomic nature of matter appeared first in his notes covering 1802/04. The book is frequently reprinted; for example, see: The Science Classical Library. New York: Citadel Press; 1964.

  2. The first write-up of the suggested classification of molecules was given in [8] (vol 3, Sect. 8.1.2); 1980. For a detailed discussion of this topic, see also [9], Sect. 2.5.

  3. See, for example, Gibbs JW: On the equilibrium of heterogeneous substances. Trans Conn Acad 1875–78;III:108–248 and 343–524. An extended abstract was published in Am J Sci Ser 3 1878;16:441–458, all reprinted in Bumstead HA, Gibbs van Name R: The scientific papers of J. Willard Gibbs, vol 1, thermodynamics. New York: Dover Publ; 1961.

  4. One distinguishes a conformation (Latin conformātĭō, forming, fashioning) from a configuration (Latin configěre, to join together). Different conformations of a molecule can be attained by rotation about bonds. Configurations need breaking of chemical bonds, as in the attainment of stereo isomers. Wunderlich [1], Fig. 4.41, or [9], Appendix 14, Fig. 3. Note the frequent misuse of these two terms in the common polymer physics literature.

  5. Wunderlich [8], vol III, p. 191: “Another general observation is the occurrence of a small melting peak several degrees above the crystallization temperature. This melting peak has also been called “annealing peak” and is often interpreted as resulting from much poorer crystals growing between the larger crystals (polypropylene, polystyrene, nylons, and polyurethanes).” For examples see graphs of Figs. IX.22, 23, 24, 27, 31 in this reference.

  6. See: 1.3: chain statistics of macromolecules, and 1.4: size and shape measurement [9].

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Authors and Affiliations

  1. Department of Chemistry, The University of Tennessee, Knoxville, TN, 37996-1600, USA

    Bernhard Wunderlich

  2. 200 Baltusrol Road, Knoxville, TN, 37934-3707, USA

    Bernhard Wunderlich

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Additional information

The Figs. 1, 2, 3, 4, 5, 6, 7, 8 and 9 in this publication were redrawn and updated with permission from the copyright holder of [1]. The figures: 17-05; 28-54; 9-15; 26-07; 34-39, 49; 16-41, 38; 32-45, correspond to Figs. 1, 2, 3, 4, 5, 6, 7, 8 and 9, in sequence. Similarly, Fig. 10 was redrawn from [8], and Figs. 11 and 12 from [47].

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Wunderlich, B. Termination of crystallization or ordering of flexible, linear macromolecules. J Therm Anal Calorim 109, 1117–1132 (2012). https://doi.org/10.1007/s10973-012-2326-2

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