Endothermic features on heating of glasses show that the second glass to liquid transition of water was phenomenologically-mistaken
10.1016/j.tca.2016.11.011
Crossref journal-article
Elsevier BV
Thermochimica Acta (78)
Bibliography

Righetti, M. C., Tombari, E., & Johari, G. P. (2017). Endothermic features on heating of glasses show that the second glass to liquid transition of water was phenomenologically-mistaken. Thermochimica Acta, 647, 101–110.

Authors 3
  1. Maria Cristina Righetti (first)
  2. Elpidio Tombari (additional)
  3. G.P. Johari (additional)
References 46 Referenced 3
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  11. G.P. Johari, Comment on “Water’s second glass transition, K. Amann-Winkel, C. Gainaru, P.H. Handle, M. Seidl, H. Nelson, R. Böhmer, T. Loerting, Proc. Natl. Acad. Sci. (U.S.) 110 (2013) 17720.”, and the Sub-Tg Features of Pressure-Densified Glasses. Thermochim. Acta, 617 (2015) 208–218. See also, J. Stern, M. Seidl, C. Gainaru, V. Fuentes-Landete, K. Amann-Winkel, P.H. Handle, K.W. Köster, H. Nelson, R. Böhmer, T. Loerting, “Experimental Evidence for Two Distinct Deeply Supercooled Liquid States of Water-Response to“Comment on ‘Water’s Second Glass Transition”, by G. P. Johari, Thermochim. Acta (2015). Thermochim. Acta, 617 (2015) 200–207. This Response reported data on water obtained by a yet different protocol and did not address the issue of Fig. 1 inset or the purported “signature” of a glass transition, whose validity is investigated here.
  12. It should be noted that Simatos et al’s [D. Simatos, G. Blond, G. Roudaut, G. Champion, J. Perez, A.L. Faivre, J. Therm. Analysis, 47 (1996) 1419] findings for sorbitol may appear to be consistent with those of Amann-Winkel et al’s [9], but the following analysis shows that they are the opposite. Simatos et al. used three protocols, (i) cooling of the liquid and heating of the glass at the same rate by using qc=qh of 20, 10, 5 or 1.25Kmin−1 (Fig. 3), (ii) cooling of the liquid at 1.25Kmin−1 min and heating the glass formed at 20, 10, 5, 2.5 or 1.25Kmin−1 rate (Fig. 4), and (iii) cooling the liquid at 20, 10, 5, 2.5 and 1.25Kmin−1 rate and heating the glass at 10Kmin−1 rate (Fig. 5). One cannot determine how the DSC heating scans shifted and/or the shape of the endotherms changed with change in qc, or in qh because Samotos et al. did not provide the DSC scans for different heating-cooling-heating conditions. They denoted the endotherm’s onset temperature as To, which is Tg→l here, and showed by filled circles in their Fig. 5 containing log qc against 103/To (or 103/Tg→l plots for the glass samples formed by cooling at rates of 20, 10, 5, 2.5 and 1.25Kmin−1 were heated at 10Kmin−1. The plots show that when qc, was decreased from 20K to10Kmin−1, Tg→l slightly decreased (negative slope of the line connecting these two data); when qc was decreased from 10K to 5K/min, Tg→l either did not change or slightly increased (a positive slope of the line connecting these two data points); when qc was further decreased from 5K to 2.5Kmin−1, Tg→l increased and lastly, when qc was decreased from 2.5K to 1.25Kmin−1, Tg→l did not change. In terms of their Eq. (5), dln(qc)≈−Δh/RT, with T=Tg→l, this means that Δh changed sign; first it was negative then almost infinite and then positive and then again almost infinite. Thus the data in their Fig. 5 show that 103/Tg→l is lower for qc =1.25Kmin−1, and higher for qc =10K/min, i.e., Tg→l is higher when qc (=1.25Kmin−1) is lower and Tg→l was lower when qc (=10Kmin−1) was higher, which is the opposite of Amann-Winkel et al’s finding in Fig. 1 inset.
  13. By using the Amann-Winkel et al’s premise of the signature and hallmark of Tg→l, J.J. Shephard, C.G. Salzmann, J. Phys. Chem. Lett. 7 (2016) 2281–2285) reported that Tg→l of their eHDA heated at the rate of 10Kmin−1 is 2K lower than Amann-Winkel et al’s. They found about half as much increase in Cp and a correspondingly different Tmdp of the Cp-endotherm, and the shape of the endotherm observed by them differ from the shape reported by Amman-Winkel et al. [9]. This shows that their respective e-HDAs were different, affirming the ill-defined state of e-HDA itself. Shephard and Salzmann also did not report data for other qc and qh which could allow one to determine the shift of the endotherm in the T-plane with change in qc and qh, and they did not investigate the thermal hysteresis that characterize a glass-liquid-glass transition endotherm.
  14. All HDAs are ill-defined states because they are formed by collapsing ice under a uniaxial load. They are not a glassy state of water because they are not formed by cooling liquid water and their structure is not one of structures of liquid water. (A glass inherits the structure of its liquid.) Moreover, properties of HDAs have not shown hysteresis of the cooling and heating paths that characterizes a glass. (Details were given in Ref. [8].) We do not know what the metastable minimum energy state of pressure collapsed ice is, but we do know that the metastable equilibrium state of a glass is its supercooled liquid.
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Dates
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Created 8 years, 9 months ago (Nov. 21, 2016, 9:19 a.m.)
Deposited 5 years, 11 months ago (Sept. 15, 2019, 12:38 p.m.)
Indexed 11 months ago (Sept. 16, 2024, 2:43 p.m.)
Issued 8 years, 7 months ago (Jan. 1, 2017)
Published 8 years, 7 months ago (Jan. 1, 2017)
Published Print 8 years, 7 months ago (Jan. 1, 2017)
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@article{Righetti_2017, title={Endothermic features on heating of glasses show that the second glass to liquid transition of water was phenomenologically-mistaken}, volume={647}, ISSN={0040-6031}, url={http://dx.doi.org/10.1016/j.tca.2016.11.011}, DOI={10.1016/j.tca.2016.11.011}, journal={Thermochimica Acta}, publisher={Elsevier BV}, author={Righetti, Maria Cristina and Tombari, Elpidio and Johari, G.P.}, year={2017}, month=jan, pages={101–110} }