First-order transitions in glasses and melts induced by solid superclusters nucleated and melted by homogeneous nucleation instead of surface melting

[Display omitted] Ethylbenzene enthalpy Δεig × ΔHm below Tm = 178.1 K. Undercooled Phase 3 enthalpy coefficient Δεig versus (T − 178.1)2/178.12 in a two-liquid model; Δεig × ΔHm being the enthalpy difference between those of Liquid 1 and Liquid 2. Phase 3 undergoes a first-order transition at TK2 = ...

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Published in:Chemical physics 2019-08, Vol.524, p.40-54
Main Author: Tournier, Robert F.
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description [Display omitted] Ethylbenzene enthalpy Δεig × ΔHm below Tm = 178.1 K. Undercooled Phase 3 enthalpy coefficient Δεig versus (T − 178.1)2/178.12 in a two-liquid model; Δεig × ΔHm being the enthalpy difference between those of Liquid 1 and Liquid 2. Phase 3 undergoes a first-order transition at TK2 = 104.7 K in the absence of glass transition at Tg = 114.5 K and its enthalpy coefficient cannot be lower than (−0.17855). An underlying first-order transition limits the relaxation enthalpy and fixes the first-order transition temperatures of ultrastable glasses. Phase 3 undergoes other first-order transitions at higher temperatures associated glacial, superheated and supercooled phases in various substances. •A renewed nucleation equation & a two-liquid model predict all sharp transitions.•The liquids 1 & 2 give rise to glass and ordered liquid Phase 3 below and above Tg.•Liquid Phase 3 is “ordered” up to Tn+ > Tm and nucleated by cooling at a new Tn+ 
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Undercooled Phase 3 enthalpy coefficient Δεig versus (T − 178.1)2/178.12 in a two-liquid model; Δεig × ΔHm being the enthalpy difference between those of Liquid 1 and Liquid 2. Phase 3 undergoes a first-order transition at TK2 = 104.7 K in the absence of glass transition at Tg = 114.5 K and its enthalpy coefficient cannot be lower than (−0.17855). An underlying first-order transition limits the relaxation enthalpy and fixes the first-order transition temperatures of ultrastable glasses. Phase 3 undergoes other first-order transitions at higher temperatures associated glacial, superheated and supercooled phases in various substances. •A renewed nucleation equation &amp; a two-liquid model predict all sharp transitions.•The liquids 1 &amp; 2 give rise to glass and ordered liquid Phase 3 below and above Tg.•Liquid Phase 3 is “ordered” up to Tn+ &gt; Tm and nucleated by cooling at a new Tn+ &lt; Tm.•Phase 3 undergoes an underlying first-order transition masked by the glass phase.•The glacial Phases 3 and their first-order transitions are predicted. Supercooled liquids give rise, by homogeneous nucleation, to solid superclusters acting as building blocks of glass, ultrastable glass, and glacial glass phases before being crystallized. Liquid-to-liquid phase transitions begin to be observed above the melting temperature Tm as well as critical undercooling depending on critical overheating ΔT/Tm. Solid nuclei exist above Tm and melt by homogeneous nucleation of liquid instead of surface melting. The Gibbs free energy change predicted by the classical nucleation equation is completed by an additional enthalpy which stabilize these solid entities during undercooling. A two-liquid model, using this renewed equation, predicts the new homogeneous nucleation temperatures inducing first-order transitions, and the enthalpy and entropy of new liquid and glass phases. These calculations are successfully applied to ethylbenzene, triphenyl phosphite, d-mannitol, n-butanol, Zr41.2Ti13.8Cu12.5Ni10Be22.5, Ti34Zr11Cu47Ni8, and Co81.5B18.5. A critical supercooling and overheating rate ΔT/Tm = 0.198 of liquid elements is predicted in agreement with experiments on Sn droplets.</description><identifier>ISSN: 0301-0104</identifier><identifier>DOI: 10.1016/j.chemphys.2019.02.006</identifier><language>eng</language><publisher>Elsevier B.V</publisher><subject>Physics</subject><ispartof>Chemical physics, 2019-08, Vol.524, p.40-54</ispartof><rights>2019</rights><rights>Attribution - NonCommercial</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c431t-f0207a62b826a4f441727d7b192f25996b65f8b6bee435222b8a26893168c9403</citedby><cites>FETCH-LOGICAL-c431t-f0207a62b826a4f441727d7b192f25996b65f8b6bee435222b8a26893168c9403</cites><orcidid>0000-0002-1135-1258</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,27903,27904</link.rule.ids><backlink>$$Uhttps://hal.science/hal-03484782$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Tournier, Robert F.</creatorcontrib><title>First-order transitions in glasses and melts induced by solid superclusters nucleated and melted by homogeneous nucleation instead of surface melting</title><title>Chemical physics</title><description>[Display omitted] Ethylbenzene enthalpy Δεig × ΔHm below Tm = 178.1 K. Undercooled Phase 3 enthalpy coefficient Δεig versus (T − 178.1)2/178.12 in a two-liquid model; Δεig × ΔHm being the enthalpy difference between those of Liquid 1 and Liquid 2. Phase 3 undergoes a first-order transition at TK2 = 104.7 K in the absence of glass transition at Tg = 114.5 K and its enthalpy coefficient cannot be lower than (−0.17855). An underlying first-order transition limits the relaxation enthalpy and fixes the first-order transition temperatures of ultrastable glasses. Phase 3 undergoes other first-order transitions at higher temperatures associated glacial, superheated and supercooled phases in various substances. •A renewed nucleation equation &amp; a two-liquid model predict all sharp transitions.•The liquids 1 &amp; 2 give rise to glass and ordered liquid Phase 3 below and above Tg.•Liquid Phase 3 is “ordered” up to Tn+ &gt; Tm and nucleated by cooling at a new Tn+ &lt; Tm.•Phase 3 undergoes an underlying first-order transition masked by the glass phase.•The glacial Phases 3 and their first-order transitions are predicted. Supercooled liquids give rise, by homogeneous nucleation, to solid superclusters acting as building blocks of glass, ultrastable glass, and glacial glass phases before being crystallized. Liquid-to-liquid phase transitions begin to be observed above the melting temperature Tm as well as critical undercooling depending on critical overheating ΔT/Tm. Solid nuclei exist above Tm and melt by homogeneous nucleation of liquid instead of surface melting. The Gibbs free energy change predicted by the classical nucleation equation is completed by an additional enthalpy which stabilize these solid entities during undercooling. A two-liquid model, using this renewed equation, predicts the new homogeneous nucleation temperatures inducing first-order transitions, and the enthalpy and entropy of new liquid and glass phases. These calculations are successfully applied to ethylbenzene, triphenyl phosphite, d-mannitol, n-butanol, Zr41.2Ti13.8Cu12.5Ni10Be22.5, Ti34Zr11Cu47Ni8, and Co81.5B18.5. 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Undercooled Phase 3 enthalpy coefficient Δεig versus (T − 178.1)2/178.12 in a two-liquid model; Δεig × ΔHm being the enthalpy difference between those of Liquid 1 and Liquid 2. Phase 3 undergoes a first-order transition at TK2 = 104.7 K in the absence of glass transition at Tg = 114.5 K and its enthalpy coefficient cannot be lower than (−0.17855). An underlying first-order transition limits the relaxation enthalpy and fixes the first-order transition temperatures of ultrastable glasses. Phase 3 undergoes other first-order transitions at higher temperatures associated glacial, superheated and supercooled phases in various substances. •A renewed nucleation equation &amp; a two-liquid model predict all sharp transitions.•The liquids 1 &amp; 2 give rise to glass and ordered liquid Phase 3 below and above Tg.•Liquid Phase 3 is “ordered” up to Tn+ &gt; Tm and nucleated by cooling at a new Tn+ &lt; Tm.•Phase 3 undergoes an underlying first-order transition masked by the glass phase.•The glacial Phases 3 and their first-order transitions are predicted. Supercooled liquids give rise, by homogeneous nucleation, to solid superclusters acting as building blocks of glass, ultrastable glass, and glacial glass phases before being crystallized. Liquid-to-liquid phase transitions begin to be observed above the melting temperature Tm as well as critical undercooling depending on critical overheating ΔT/Tm. Solid nuclei exist above Tm and melt by homogeneous nucleation of liquid instead of surface melting. The Gibbs free energy change predicted by the classical nucleation equation is completed by an additional enthalpy which stabilize these solid entities during undercooling. A two-liquid model, using this renewed equation, predicts the new homogeneous nucleation temperatures inducing first-order transitions, and the enthalpy and entropy of new liquid and glass phases. These calculations are successfully applied to ethylbenzene, triphenyl phosphite, d-mannitol, n-butanol, Zr41.2Ti13.8Cu12.5Ni10Be22.5, Ti34Zr11Cu47Ni8, and Co81.5B18.5. A critical supercooling and overheating rate ΔT/Tm = 0.198 of liquid elements is predicted in agreement with experiments on Sn droplets.</abstract><pub>Elsevier B.V</pub><doi>10.1016/j.chemphys.2019.02.006</doi><tpages>15</tpages><orcidid>https://orcid.org/0000-0002-1135-1258</orcidid><oa>free_for_read</oa></addata></record>
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title First-order transitions in glasses and melts induced by solid superclusters nucleated and melted by homogeneous nucleation instead of surface melting
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