scholarly journals Transition in coupled replicas may not imply a finite-temperature ideal glass transition in glass-forming systems

2014 ◽  
Vol 89 (3) ◽  
Author(s):  
Juan P. Garrahan
Keyword(s):  
Glass Transition ◽  
Finite Temperature ◽  
Glass Forming

LOOKING AT THE GLASS TRANSITION: CHALLENGES OF EXTREME TIME SCALES AND OTHER INTERESTING PROBLEMS

2020 ◽  
Vol 93 (1) ◽  
pp. 79-120 ◽  
Author(s):  
Gregory B. McKenna
Keyword(s):  
Glass Transition ◽  
Time Scales ◽  
Finite Temperature ◽  
Glassy State ◽  
Metastable Equilibrium ◽  
Arrhenius Behavior ◽  
Fictive Temperature ◽  
Major Question ◽  
Kauzmann Temperature ◽  
Glass Forming

ABSTRACT The behavior of glass-forming materials is examined with emphasis on the below-glass transition behavior. A major question that is related to the super-Arrhenius behavior of the dynamics of glass-forming systems is whether the apparent divergence at finite temperature continues below the kinetic or laboratory glass transition that is related to the limits of measurement and is standardized so that the material relaxation time is near 100 s. The problem arises because as the temperature decreases, the time scales required to reach equilibrium (or metastable equilibrium) become geologically long. Yet the apparent finite temperature divergence is fundamental to many theories of glasses; therefore, it becomes essential to find ways to finesse the extreme time scales related to the so-called Kauzmann paradox to bring new information to the ongoing conversation concerning the existence or not of an ideal glass transition at either the Kauzmann temperature or the Vogel–Fulcher–Tammann temperature. After describing the framework of the glassy state that is formed by the early ideas of a fictive temperature, we examine the use of extremely low fictive temperature glasses as a means to potentially get around the long time-scale problem. The challenge is to find ways to create such glasses and measure their properties. In addition to looking at the dynamic behavior of a 20-million-year-old amber and a vapor-deposited amorphous perfluoropolymer whose fictive temperature was the same as the Kauzmann temperature for the material, we also examine the possibility of directly testing the thermodynamics of an ideal glass transition by making athermal solutions of a poly(α-methyl styrene) and its pentamer, where we find that the entropy surface determined from extrapolation of the heat capacity to zero pentamer shows no distinct transition at as much as 180 K below the Kauzmann temperature. The significance of the dynamics of the stable glasses and the thermodynamics of the polymer solutions is discussed in terms that challenge the idea of an ideal glass transition. We also look in more detail at the ability to use vapor deposition to make ethylbenzene, a small-molecule organic, into an ultra-stable glass with a fictive temperature that is possibly below the Kauzmann temperature of this material. We end with remarks on the question of decoupling of different relaxation mechanisms as something not treated by current theories of glass, and we consider some open questions related to the fact that the glass transition remains an unresolved and important problem.

scholarly journals Physical Aging Behavior of a Glassy Polyether

Polymers ◽  
2021 ◽  
Vol 13 (6) ◽  
pp. 954
Author(s):  
Xavier Monnier ◽  
Sara Marina ◽  
Xabier Lopez de Pariza ◽  
Haritz Sardón ◽  
Jaime Martin ◽  
...  
Keyword(s):  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Physical Aging ◽  
Glassy State ◽  
Aging Behavior ◽  
Scanning Calorimetry ◽  
Narrow Temperature Range ◽  
Glass Forming ◽  
Fast Scanning Calorimetry

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.

Glass Formation and Glass Forming Ability of Alloys Near Eutectic Composition

2000 ◽  
Vol 644 ◽  
Author(s):  
Y. Li
Keyword(s):  
Glass Transition ◽  
Glass Formation ◽  
Eutectic Composition ◽  
Glass Forming Ability ◽  
Critical Section ◽  
Bulk Glass ◽  
Melting Behaviour ◽  
Eutectic Alloys ◽  
Section Thickness ◽  
Glass Forming

AbstractOnset temperature, Tm and offset temperature (liquidus) Tl of melting of a series of bulk glass forming alloys based on La, Mg, and Pd have been measured by studying systematically the melting behaviour of these alloys using DTA or DSC. Bulk metallic glass formation has been found to be most effective at or near their eutectic points and less effective for off-eutectic alloys. Reduced glass transition temperature Trg given by Tg/Tl is found to show a stronger correlation with critical cooling rate or critical section thickness for glass formation than Trg given by Tg/Tm.

Strong Liquid Behavior of Zr-Ti-Cu-Ni-Be Bulk Metallic Glass Forming Alloys

1996 ◽  
Vol 455 ◽  
Author(s):  
Ralf Busch ◽  
Andreas Masuhr ◽  
Eric Bakke ◽  
William L. Johnson
Keyword(s):  
Glass Transition ◽  
Melting Point ◽  
Metallic Glass ◽  
Bulk Metallic Glass ◽  
Supercooled Liquid ◽  
Glass Transition Region ◽  
Glass Forming ◽  
Liquid Behavior ◽  
Metallic Liquids ◽  
Microscopic Origin

ABSTRACTThe viscosities of the Zr46.75Ti8.25Cu7.5Ni10Be27.5 and the Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass forming liquids was determined from the melting point down to the glass transition in the entire temperature range of the supercooled liquid. The temperature dependence of the viscosity in the supercooled liquid obeys the Vogel-Fulcher-Tammann (VFT) relation. The fragility index D is about 20 for both alloys and the ratio between glass transition temperature and VFT temperature is found to be 1.5. A comparison with other glass forming systems shows that these bulk metallic glass formers are strong liquids comparable to sodium silicate glass. Furthermore, they are the strongest among metallic glass forming liquids. This behavior is a main contributing factor to the glass forming ability since it implicates a higher viscosity from the melting point down to the glass transition compared to other metallic liquids. Thus, the kinetics in the supercooled liquid is sluggish and yields a low critical cooling rate for glass formation. The relaxation behavior in the glass transition region of the alloys is consistent with their strong glassy nature as reflected by a stretching exponent that is close to 0.8. The microscopic origin of the strong liquid behavior of bulk metallic glass formers is discussed.

Experimental Study of the Liquid-Glass Transition in an Inorganic Polymer Li0.5Na0.5PO3

1995 ◽  
Vol 407 ◽  
Author(s):  
B. Rufflé ◽  
S. Beaufils ◽  
Y. Délugeard ◽  
G. Coddens ◽  
J. Etrillard ◽  
...  
Keyword(s):  
Experimental Study ◽  
Glass Transition ◽  
Raman Scattering ◽  
Viscous Flow ◽  
Liquid Glass ◽  
Low Frequency ◽  
Glass Forming ◽  
Scattering Spectra ◽  
Temperature Ranges ◽  
Raman Scattering Spectra

ABSTRACTNew experimental results obtained with various techniques on a less-studied glass-forming system are presented. At low frequency, a secondary βslow-process, decoupled from the viscous flow, is observed by 3 1P NMR. Raman scattering spectra and coherent neutron scattering spectra has been obtained in wide frequency and temperature ranges showing the same qualitative features for the Boson peak while the quasielastic contribution seems to differ markedly.

Comments on “Fabrication of ternary Mg–Cu–Gd bulk metallic glass with high glass-forming ability under air atmosphere” [H. Men and D.H. Kim, J. Mater. Res. 18, 1502 (2003)]

2004 ◽  
Vol 19 (2) ◽  
pp. 427-428 ◽  
Author(s):  
Z.P. Lu ◽  
C.T. Liu
Keyword(s):  
Glass Transition ◽  
Metallic Glasses ◽  
Supercooled Liquid ◽  
Supercooled Liquid Region ◽  
Glass Forming Ability ◽  
Bulk Amorphous Alloy ◽  
Liquid Region ◽  
Glass Forming ◽  
Air Atmosphere ◽  
Acta Mater

A new Mg-based bulk amorphous alloy (i.e., Mg65Cu25Gd10) has successfully been developed by Men and Kim [H. Men and D.H. Kim, J. Mater. Res. 18, 1502 (2003)]. They showed that this alloy exhibits significantly improved glass-forming ability (GFA) in comparison with Mg65Cu25Y10 alloy. However, this improved GFA cannot be indicated by the supercooled liquid region ΔT and the reduced glass-transition temperature Trg. As shown in the current comment, the new parameter γ, Tx/(Tg + Tl) defined in our recent papers [Z.P. Lu and C.T. Liu, Acta Mater. 50, 3501 (2002); Z.P. Lu and C.T. Liu, Phys. Rev. Lett. 91, 115505 (2003)] can well gauge GFA for bulk metallic glasses, including the current Mg-based alloys.

scholarly journals Long-Term Physical (In)Stability of Spray-Dried Amorphous Drugs: Relationship with Glass-Forming Ability and Physicochemical Properties

Pharmaceutics ◽  
2019 ◽  
Vol 11 (9) ◽  
pp. 425 ◽  
Author(s):  
Edueng ◽  
Bergström ◽  
Gråsjö ◽  
Mahlin
Keyword(s):  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Physicochemical Properties ◽  
Physical Stability ◽  
Glass Forming Ability ◽  
Melt Quenching ◽  
Glass Forming ◽  
Spray Dried

This study shows the importance of the chosen method for assessing the glass-forming ability (GFA) and glass stability (GS) of a drug compound. Traditionally, GFA and GS are established using in situ melt-quenching in a differential scanning calorimeter. In this study, we included 26 structurally diverse glass-forming drugs (i) to compare the GFA class when the model drugs were produced by spray-drying with that when melt-quenching was used, (ii) to investigate the long-term physical stability of the resulting amorphous solids, and (iii) to investigate the relationship between physicochemical properties and the GFA of spray-dried solids and their long-term physical stability. The spray-dried solids were exposed to dry (<5% RH) and humid (75% RH) conditions for six months at 25 °C. The crystallization of the spray-dried solids under these conditions was monitored using a combination of solid-state characterization techniques including differential scanning calorimetry, Raman spectroscopy, and powder X-ray diffraction. The GFA/GS class assignment for 85% of the model compounds was method-dependent, with significant differences between spray-drying and melt-quenching methods. The long-term physical stability under dry condition of the compounds was predictable from GFA/GS classification and glass transition and crystallization temperatures. However, the stability upon storage at 75% RH could not be predicted from the same data. There was no strong correlation between the physicochemical properties explored and the GFA class or long-term physical stability. However, there was a slight tendency for compounds with a relatively larger molecular weight, higher glass transition temperature, higher crystallization temperature, higher melting point and higher reduced glass transition temperature to have better GFA and better physical stability. In contrast, a high heat of fusion and entropy of fusion seemed to have a negative impact on the GFA and physical stability of our dataset.

scholarly journals Observation of an apparent first-order glass transition in ultrafragile Pt–Cu–P bulk metallic glasses

2020 ◽  
Vol 117 (6) ◽  
pp. 2779-2787 ◽  
Author(s):  
Jong H. Na ◽  
Sydney L. Corona ◽  
Andrew Hoff ◽  
William L. Johnson
Keyword(s):  
Glass Transition ◽  
Configurational Entropy ◽  
Freezing Temperature ◽  
Thin Wall ◽  
First Order ◽  
Cu Content ◽  
Kauzmann Temperature ◽  
Entropy Of Fusion ◽  
Glass Forming ◽  
Third Law Of Thermodynamics

An experimental study of the configurational thermodynamics for a series of near-eutectic Pt80-xCuxP20 bulk metallic glass-forming alloys is reported where 14 < x < 27. The undercooled liquid alloys exhibit very high fragility that increases as x decreases, resulting in an increasingly sharp glass transition. With decreasing x, the extrapolated Kauzmann temperature of the liquid, TK, becomes indistinguishable from the conventionally defined glass transition temperature, Tg. For x < 17, the observed liquid configurational enthalpy vs. T displays a marked discontinuous drop or latent heat at a well-defined freezing temperature, Tgm. The entropy drop for this first-order liquid/glass transition is approximately two-thirds of the entropy of fusion of the crystallized eutectic alloy. Below Tgm, the configurational entropy of the frozen glass continues to fall rapidly, approaching that of the crystallized eutectic solid in the low T limit. The so-called Kauzmann paradox, with negative liquid entropy (vs. the crystalline state), is averted and the liquid configurational entropy appears to comply with the third law of thermodynamics. Despite their ultrafragile character, the liquids at x = 14 and 16 are bulk glass formers, yielding fully glassy rods up to 2- and 3-mm diameter on water quenching in thin-wall silica tubes. The low Cu content alloys are definitive examples of glasses that exhibit first-order melting.

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