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Flow-induced crystallization studied in the RheoDSC device: Quantifying the importance of edge effects

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Abstract

Flow-induced crystallization is investigated through short-term shear flow experiments on poly(1-butene) in the RheoDSC device. We demonstrate that the DSC signal shows contributions from spherulitic morphology in the center of the sample and oriented structures at the edge of the sample, the latter being induced by edge effects at the free surface. It is shown that, although small in terms of volume, the crystallization at the edge has a dominating influence on the measured rheology. We show how these kinds of effects can be recognized in stand-alone rheometric studies of flow-induced crystallization.

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Acknowledgments

The European Soft Matter Infrastructure project (ESMI) is gratefully acknowledged for funding our measurement time at the Katholieke Universiteit Leuven (project no. E131100446). This project is supported by the Dutch Technology Foundation (STW), grant no. 08083.

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Authors and Affiliations

  1. Department of Mechanical Engineering, Eindhoven University of Technology, P.O. Box 513, 5600MB, Eindhoven, The Netherlands

    Peter C. Roozemond, Martin van Drongelen & Gerrit W. M. Peters

  2. DSM Ahead, P.O. Box 18, 6160 BB, Geleen, Geleen, The Netherlands

    Peter C. Roozemond

  3. Laboratory of Applied Rheology and Polymer Processing, Department of Chemical Engineering, Leuven Material Research Centre, Katholieke Universiteit Leuven, W. de Croylaan 46, B-3001, Leuven, Belgium

    Leander Verbelen & Peter Van Puyvelde

Authors
  1. Peter C. Roozemond
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  2. Martin van Drongelen
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  3. Leander Verbelen
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  4. Peter Van Puyvelde
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  5. Gerrit W. M. Peters
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Corresponding author

Correspondence to Gerrit W. M. Peters.

Appendix A: Average crystallization kinetics

Appendix A: Average crystallization kinetics

Because the shear rate is not homogeneous throughout the sample, neither is the flow-induced nucleation density. Therefore, the crystallization kinetics measured with DSC are actually an average over the whole sample. Consequently, the Avrami equation for spherulites (Eq. 1) does not give a good representation of crystallization kinetics measured with DSC. In this Appendix, we qualitatively show how this can result in exponents smaller than 3 in an Avrami plot.

The average crystallization kinetics of a cylindrical sample in which the nucleation density depends on shear rate, with crystallization kinetics in each point given by the Avrami equation for spherulites (Eq. 1) are given by

$$ \xi_{\text{avg}}(t)=\frac{2\pi}{\pi R^{2}}\int\limits_{0}^{R} \left[1-\exp\left(-\frac{4\pi}{3}N(r)G^{3}t^{3}\right)\right] r\, \mathrm{d} r, $$
(11)

where N(r) is the nucleation density distribution in radial direction. For different distribution functions, the average space filling and its corresponding Avrami plot are shown in Fig. 8. Indeed, the slope in the Avrami plot is smaller than 3. This is quite easy to understand: material near the edge of the sample, with high nucleation density, already reaches impingement whereas material in the center of the sample is just starting to crystallize. Therefore, the average crystallization kinetics cannot be described with a simple equation.

Fig. 8
figure 8

(a) Average crystallization kinetics for a sample with a distribution of nucleation density across radial direction. (b) Corresponding Avrami plot

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Roozemond, P.C., van Drongelen, M., Verbelen, L. et al. Flow-induced crystallization studied in the RheoDSC device: Quantifying the importance of edge effects. Rheol Acta 54, 1–8 (2015). https://doi.org/10.1007/s00397-014-0820-0

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