scholarly journals Calorimetric Study of the Glassy State. XIV. Calorimetric Study on Unusual Glass Transition Phenomena in CFCl2–CFCl2

1978 ◽  
Vol 51 (6) ◽  
pp. 1691-1696 ◽  
Author(s):  
K\={o}ji Kishimoto ◽  
Hiroshi Suga ◽  
Syûzô Seki
Polymers ◽  
2021 ◽  
Vol 13 (6) ◽  
pp. 954
Author(s):  
Xavier Monnier ◽  
Sara Marina ◽  
Xabier Lopez de Pariza ◽  
Haritz Sardón ◽  
Jaime Martin ◽  
...  

The present work aims to provide insights on recent findings indicating the presence of multiple equilibration mechanisms in physical aging of glasses. To this aim, we have investigated a glass forming polyether, poly(1-4 cyclohexane di-methanol) (PCDM), by following the evolution of the enthalpic state during physical aging by fast scanning calorimetry (FSC). The main results of our study indicate that physical aging persists at temperatures way below the glass transition temperature and, in a narrow temperature range, is characterized by a two steps evolution of the enthalpic state. Altogether, our results indicate that the simple old-standing view of physical aging as triggered by the α relaxation does not hold true when aging is carried out deep in the glassy state.


1995 ◽  
Vol 266 ◽  
pp. 79-95 ◽  
Author(s):  
Minoru Hanaya ◽  
Tomoyasu Okubayashi ◽  
Toshio Sakurai ◽  
Masaharu Oguni

2018 ◽  
Vol 18 (21) ◽  
pp. 15841-15857 ◽  
Author(s):  
Jörn Lessmeier ◽  
Hans Peter Dette ◽  
Adelheid Godt ◽  
Thomas Koop

Abstract. 2-Methylbutane-1,2,3,4-tetraol (hereafter named tetraol) is an important oxidation product of isoprene and can be considered as a marker compound for isoprene-derived secondary organic aerosols (SOAs). Little is known about this compound's physical phase state, although some field observations indicate that isoprene-derived secondary organic aerosols in the tropics tend to be in a liquid rather than a solid state. To gain more knowledge about the possible phase states of tetraol and of tetraol-containing SOA particles, we synthesized tetraol as racemates as well as enantiomerically enriched materials. Subsequently the obtained highly viscous dry liquids were investigated calorimetrically by differential scanning calorimetry revealing subambient glass transition temperatures Tg. We also show that only the diastereomeric isomers differ in their Tg values, albeit only by a few kelvin. We derive the phase diagram of water–tetraol mixtures over the whole tropospheric temperature and humidity range from determining glass transition temperatures and ice melting temperatures of aqueous tetraol mixtures. We also investigated how water diffuses into a sample of dry tetraol. We show that upon water uptake two homogeneous liquid domains form that are separated by a sharp, locally constrained concentration gradient. Finally, we measured the glass transition temperatures of mixtures of tetraol and an important oxidation product of α-pinene-derived SOA: 3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA). Overall, our results imply a liquid-like state of isoprene-derived SOA particles in the lower troposphere at moderate to high relative humidity (RH), but presumably a semisolid or even glassy state at upper tropospheric conditions, particularly at low relative humidity, thus providing experimental support for recent modeling calculations.


1967 ◽  
Vol 40 (12) ◽  
pp. 2984-2984 ◽  
Author(s):  
Masayasu Sugisaki ◽  
Hiroshi Suga ◽  
Syûzô Seki

Materials ◽  
2021 ◽  
Vol 14 (21) ◽  
pp. 6509
Author(s):  
Robert F. Tournier ◽  
Michael I. Ojovan

A second melting temperature occurs at a temperature Tn+ higher than Tm in glass-forming melts after heating them from their glassy state. The melting entropy is reduced or increased depending on the thermal history and on the presence of antibonds or bonds up to Tn+. Recent MD simulations show full melting at Tn+ = 1.119Tm for Zr, 1.126Tm for Ag, 1.219Tm for Fe and 1.354Tm for Cu. The non-classical homogeneous nucleation model applied to liquid elements is based on the increase of the Lindemann coefficient with the heating rate. The glass transition at Tg and the nucleation temperatures TnG of glacial phases are successfully predicted below and above Tm. The glass transition temperature Tg increases with the heating rate up to Tn+. Melting and crystallization of glacial phases occur with entropy and enthalpy reductions. A universal law relating Tn+ and TnG around Tm shows that TnG cannot be higher than 1.293Tm for Tn+= 1.47Tm. The enthalpies and entropies of glacial phases have singular values, corresponding to the increase of percolation thresholds with Tg and TnG above the Scher and Zallen invariant at various heating and cooling rates. The G-phases are metastable up to Tn+ because the antibonds are broken by homogeneous nucleation of bonds.


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