Literature DB >> 12935148

Possible resolution of the Kauzmann paradox in supercooled liquids.

Hajime Tanaka1.   

Abstract

Generally, the entropy of the supercooled liquid decreases more rapidly than that of the crystal. Thus, the former, if we extrapolate it smoothly below the glass-transition temperature T(g), becomes equal to the latter at the so-called Kauzmann temperature T(K). Further extrapolation below T(K) leads to the unphysical situation that the entropy of disordered liquid is lower than the ordered crystal, which results in the violation of the third law of thermodynamics. This is known as the "Kauzmann paradox" which has been the key problem of liquid-glass transition for a long time. Here we propose a simple resolution of the Kauzmann paradox by answering a fundamental question of how deeply we can supercool a liquid. We argue that the lower metastable limit T(LML), below which a liquid should crystallize before its structural relaxation, is located above the Kauzmann temperature T(K). Thus, the entropy crisis at T(K) is naturally avoided by crystallization. We suggest that it is dynamic heterogeneity that destabilizes a deeply supercooled "equilibrium" liquid state as well as a glassy state against crystallization. This may have a significant implication on the stability of a glassy state, which is of industrial importance in relation to the storage of glassy material.

Entities:  

Year:  2003        PMID: 12935148     DOI: 10.1103/PhysRevE.68.011505

Source DB:  PubMed          Journal:  Phys Rev E Stat Nonlin Soft Matter Phys        ISSN: 1539-3755


  7 in total

1.  Structural transformation in supercooled water controls the crystallization rate of ice.

Authors:  Emily B Moore; Valeria Molinero
Journal:  Nature       Date:  2011-11-23       Impact factor: 49.962

Review 2.  Stability of amorphous pharmaceutical solids: crystal growth mechanisms and effect of polymer additives.

Authors:  Ye Sun; Lei Zhu; Tian Wu; Ting Cai; Erica M Gunn; Lian Yu
Journal:  AAPS J       Date:  2012-03-21       Impact factor: 4.009

3.  Formation of a crystal nucleus from liquid.

Authors:  Takeshi Kawasaki; Hajime Tanaka
Journal:  Proc Natl Acad Sci U S A       Date:  2010-07-27       Impact factor: 11.205

4.  Bond orientational order in liquids: Towards a unified description of water-like anomalies, liquid-liquid transition, glass transition, and crystallization: Bond orientational order in liquids.

Authors:  Hajime Tanaka
Journal:  Eur Phys J E Soft Matter       Date:  2012-10-31       Impact factor: 1.890

5.  Glasses crystallize rapidly at free surfaces by growing crystals upward.

Authors:  Ye Sun; Lei Zhu; Kenneth L Kearns; Mark D Ediger; Lian Yu
Journal:  Proc Natl Acad Sci U S A       Date:  2011-03-28       Impact factor: 11.205

6.  Experimental evidence of low-density liquid water upon rapid decompression.

Authors:  Chuanlong Lin; Jesse S Smith; Stanislav V Sinogeikin; Guoyin Shen
Journal:  Proc Natl Acad Sci U S A       Date:  2018-02-12       Impact factor: 11.205

7.  The microscopic origin of the extreme glass-forming ability of Albite and B2O3.

Authors:  Edgar D Zanotto; Daniel R Cassar
Journal:  Sci Rep       Date:  2017-02-27       Impact factor: 4.379

  7 in total

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