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Hierarchical aging pathways and signatures of thermodynamic transition in molecular glasses

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  • ReceivedNov 3, 2018
  • AcceptedDec 13, 2018
  • PublishedJan 9, 2019

Abstract


Funding

the National Basic Research Program of China(2015CB856801)


Acknowledgment

This work was partially supported by the National Basic Research Program of China (2015CB856801). We are grateful to the Analytical and Testing Center, Huazhong University of Science and Technology for technical assistance.


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Liu S conducted the experiments. All authors contributed to experimental design, data analysis, and interpretation. Liu S, Yu Y, and Wu Y wrote the manuscript. Yu Y and Wu Y directed the research.


Author information

Shiyu Liu received his bachelor’s degree from Huazhong University of Science and Technology in 2011 and is pursuing PhD degree at Huazhong University of Science and Technology. His research interest mainly focuses on the liquid complexity, the nature of glass transition and melting.


Yao Yu is currently an associated professor in Huazhong University of Science and Technology. His research interest mainly focuses on the properties of liquid and liquid-related transitions, including glass transition, crystallization and melting, and applications of liquid, such as the application of electrolyte for energy storage.


Yue Wu is currently a Kenan distinguished Professor in the University of North Carolina at Chapel Hill. His current research interest includes understanding of the nature of glass transition and novel properties of nanoconfined liquids.


Supplementary data

Supplementary information

See supplementary material for specific details about the crystalline structure of SIBP, the stability of supercooled liquid, and the method of enthalpy measurement. All the supporting data are available in the online version of the paper.


References

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  • Figure 1

    The identification of the characteristic temperatures Tgonset, Tp and Tgend. Tgonset is the onset temperature of glass transition and acquired by the intersection point of the baseline before the glass transition and the tangent line at the inflection point with the maximum slope of the CP,norm(T) curve. Tp is at the maximum of the CP,norm(T) curve. Tgend is the intersection point of the baseline and the tangent line at the inflection point after the glass transition.

  • Figure 2

    Calorimetry measurements of glass transition in molecular liquids. (a) Plot of ln(q+) vs. 1000/Tgonset acquired by sixteen observation points for OTP. Plot of ln(q+) vs. 1000/Tgonset acquired by five observation points are shown in the inset with the sixteen observation points shown as faded background. Plots of ln(q+) vs. 1000/Tgonset acquired by sixteen observation points for serotonin (b), glycerol (c), (S)−(+)−ibuprofen (d), ketoprofen (e), and indomethacin (f).

  • Figure 3

    Calorimetry measurements of SIBP glass transition and numerical calculations. (a) The set of CP,norm(T) curves with q+ from 1.0 to 15.0 K min−1 with the initial GSs prepared under cooling rate q = 15.0 K min−1 (upper panel). The corresponding τavg versus 1000/Tp (lower panel). (b) The set of CP,norm(T) curves with q+ from 1.0 to 15.0 K min−1 with the initial GS prepared under the cooling rate q = 0.5 K min−1 (upper panel). The corresponding τavg versus 1000/Tp (lower panel). (c) The set of CP,norm(T) curves with q+ from 1.0 to 15.0 K min−1 with the initial GSs prepared under cooling rate q = q+ (upper panel). The corresponding τavg versus 1000/Tp (lower panel). Also shown are the corresponding results from numerical calculations with the initial GSs prepared under cooling rate q = 15.0 K min−1 (d), q = 0.5 K min−1 (e), and q = q+ (f).

  • Figure 4

    Enthalpy measurements of SIBP glass transition. (a) Enthalpy at T after held isothermally for 3,600 s represented by Hisotherm(T). (b) Hisotherm(T) acquired with tisotherm varying from 1,200 to 3,600 s.

  • Figure 5

    Raman measurements of SIBP glass transition. (a) A typical Raman spectrum acquired at 223.2 K. (b) The temperature dependence of the Raman shift of the band around 1,649.00 cm−1.

  • Figure 6

    Illustration of the free energy landscape. Upon heating, the GS firstly enters the TMSLS at an intermediate free energy minimum. The transition from TMSLS to SLS speeds up dramatically at Tsp~Tg above which the free energy local minimum disappears.

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