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Crystallization Kinetics

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Fundamental Polymer Science

Part of the book series: Graduate Texts in Physics ((GTP))

Abstract

The crystallization of flexible-chain polymers is a fascinating branch of fundamental polymer science. A central paradigm that is an essential part of the theories of polymer crystallization is chain folding, a structural term coined by Keller (1957) (cf. Sects. 7.3.1 and 7.3.2). The early theories of polymer crystallization stem from theories earlier developed for the crystallization of low-molar-mass substances. The principle of chain folding was first implemented in these theories. Some of the growth theories for polymer crystallization, e.g. the Lauritzen-Hoffman (LH) theory (Lauritzen and Hoffman 1960, 1973, Hoffman and Lauritzen 1961), have been in use for more than 50 years. A small molecule has a well-defined shape with only minor freedom to change shape by internal motion. Sometimes the single molecule can be represented by a sphere making crystalline packing simple. A critical nucleus is formed when a sufficiently large number of such molecules have aggregated in a regular fashion, and further growth of the crystal is then spontaneous, i.e. the Gibbs free energy decreases as more molecules are added to the nucleus. The LH theory describes the crystallization of polymer molecules in a simplified fashion. This is, from a textbook perspective, instructive and it is used as an introduction to the kinetic crystallization theories (Sect. 8.4). Lauritzen and Hoffman assumed that crystallization proceeds according to a particular path with well-defined subprocesses, with one of them being the creation of a regular chain fold. The LH theory allows three different growth scenarios, referred to as regimes I, II and III. The LH theory also includes diffusion of the crystallizable units to the growth front, in the later versions according to the reptation model (cf. Sect. 6.4.3). A strong feature of the LH theory is that it yields analytical expressions with a number of physical parameters that are in accordance with experimental data for the temperature dependence of the growth rates of superstructures (spherulites and axialites) and of the crystal thickness. Parallel to the development of LH theory, important experimental and theoretical research was conducted by other groups. Part of this was concerned with fundamental aspects of crystal growth based on different nucleation processes (Frank and Tosi 1961; Frank 1974; Point et al. 1986; Dosiere et al. 1986; Colet et al. 1986; Mansfield 1988, 1990; Point and Villars 1992). This body of findings that are being fundamentally critical for the LH theory is presented in Sect. 8.4.

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  1. Fibre and Polymer Technology School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, Stockholm, Sweden

    Ulf W. Gedde & Mikael S. Hedenqvist

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Gedde, U.W., Hedenqvist, M.S. (2019). Crystallization Kinetics. In: Fundamental Polymer Science. Graduate Texts in Physics. Springer, Cham. https://doi.org/10.1007/978-3-030-29794-7_8

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