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Cooling Rate Dependent Glass Transition in Thin Polymer Films and in Bulk

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Fast Scanning Calorimetry

Abstract

The glass transition is a well-known phenomenon marking the crossover from a liquid in metastable equilibrium to an out-of-equilibrium glass. In this chapter employing fast scanning calorimetry (FSC), we investigate the glass transition of bulk polystyrene (PS) and the corresponding films spin-coated on silicon oxide with thickness as low as \( \sim \) 10 nm. To do so, we employ a procedure based on determining the glass transition temperature (T g ) as that where non-equilibrium effects begin to be calorimetrically detectable. This provides a measure of the onset of the glass transition, that is the T g(on). This method allows obtaining the T g(on) in a wide range of cooling rates and with a precision generally not achievable by means of conventional methods. The main results of the study are that: (1) the cooling rate dependent T g(on) follows the Vogel–Fulcher–Tammann law for all thicknesses; (2) T g(on) decrease from bulk behaviour is observed for the smallest employed thickness (\( \sim \) 10 nm). For the investigated film configuration (supported on silicon oxide), the decrease in T g(on) becomes progressively large as the cooling rate is decreased. In particular, at the highest investigated cooling rates (\( \sim \) 1000 K/s) a decrease of several Kelvin is observed, whereas the T g(on) is depressed by \( \sim \) 15 K at a cooling rate of 0.1 K/s. This result is discussed in relation to the thickness dependence of the rate of spontaneous fluctuations in PS. This appears to be thickness independent for films configuration analogous to that of the present study. Hence, it is unequivocally shown how relaxational arguments, that is, those based on the effect of the rate of spontaneous fluctuations on the thermal glass transition, are insufficient to catch the T g(on) decrease from bulk behaviour.

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Notes

  1. 1.

    During equilibrium recovery the change of thermodynamic state of the glass implies a concomitant change of the relaxation time of spontaneous fluctuations.

  2. 2.

    It is worth to point out that cooling through its thermal glass transition is one of the numerous ways to bring a glass-forming liquid out-of-equilibrium. Among them, one is that based on applying non-linear dielectric perturbations to a metastable supercooled liquid [7, 92].

  3. 3.

    In the study of Efremov et al. [32], it was concluded that no appreciable T g deviations existed. This was corroborated by the fact that the thinnest films investigated in such work (\( \sim \) 1.5 nm) exhibited T g very close to bulk PS. However, when films of larger thickness are considered a clear trend to T g depression with decreasing film thickness was present.

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Acknowledgements

The authors acknowledge the University of the Basque Country and Basque Country Government (Ref. No. IT-654-13 (GV)), Depto. Educación, Universidades e Investigación and Spanish Government (Grant No. MAT2012-31088 and MAT2015-63704-P) for their financial support.

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Authors and Affiliations

  1. Centro de Física de Materiales (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018, San Sebastián, Spain

    Daniele Cangialosi, Angel Alegría & Juan Colmenero

  2. Departamento de Física de Materiales, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080, San Sebastián, Spain

    Angel Alegría & Juan Colmenero

  3. Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018, San Sebastián, Spain

    Juan Colmenero

Authors
  1. Daniele Cangialosi
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  2. Angel Alegría
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  3. Juan Colmenero
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Correspondence to Daniele Cangialosi .

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  1. Institute of Physics, University of Rostock, Rostock, Germany

    Christoph Schick

  2. SciTe B.V., Katholieke Universiteit Leuven, Geleen, The Netherlands

    Vincent Mathot

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Cangialosi, D., Alegría, A., Colmenero, J. (2016). Cooling Rate Dependent Glass Transition in Thin Polymer Films and in Bulk. In: Schick, C., Mathot, V. (eds) Fast Scanning Calorimetry. Springer, Cham. https://doi.org/10.1007/978-3-319-31329-0_13

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