Publicação
Liquid pre-freezing percolation transition to equilibrium crystal-in-liquid mesophase
| dc.contributor.author | Woodcock, Leslie | |
| dc.date.accessioned | 2021-02-04T14:43:36Z | |
| dc.date.available | 2021-02-04T14:43:36Z | |
| dc.date.issued | 2018 | |
| dc.description.abstract | Pre-freezing anomalies are explained by a percolation transition that delineates the existence of a pure equilibrium liquid state above the temperature of 1st-order freezing to the stable crystal phase. The precursor to percolation transitions are hetero-phase fluctuations that give rise to molecular clusters of an otherwise unstable state in the stable host phase. In-keeping with the Ostwald’s step rule, clusters of a crystalline state, closest in stability to the liquid, are the predominant structures in pre-freezing hetero-phase fluctuations. Evidence from changes in properties that depend upon density and energy fluctuations suggests embryonic nano-crystallites diverge in size and space at a percolation threshold, whence a colloidal-like equilibrium is stabilized by negative surface tension. Below this transition temperature, both crystal and liquid states percolate the phase volume in an equilibrium state of dispersed coexistence. We obtain a preliminary estimate of the prefreezing percolation line for water determined from higher-order discontinuities in Gibbs energy that derivatives the isothermal rigidity [(dp/dρ)T] and isochoric heat capacity [(dU/dT)v] respectively. The percolation temperature varies only slightly with pressure from 51.5°C at 0.1 MPa to around 60°C at 100 MPa. We conjecture that the predominant dispersed crystal structure is a tetrahedral ice, which is the closest of the higher-density ices (II to XV) to liquid water in configurational energy. Inspection of thermodynamic and transport properties of liquid argon also indicate the existence of a similar prefreezing percolation transition at ambient pressures (0.1 MPa) around 90 K, ~6% above the triple point (84 K). These findings account for many anomalous properties of equilibrium and supercooled liquids generally, and also explain Kauzmann’s “paradox” at a “glass” transition. | pt_PT |
| dc.description.version | info:eu-repo/semantics/publishedVersion | pt_PT |
| dc.identifier.doi | 10.4236/ns.2018.107026 | pt_PT |
| dc.identifier.uri | http://hdl.handle.net/10400.1/15037 | |
| dc.language.iso | eng | pt_PT |
| dc.peerreviewed | yes | pt_PT |
| dc.rights.uri | http://creativecommons.org/licenses/by-nc/4.0/ | pt_PT |
| dc.subject | Liquid state | pt_PT |
| dc.subject | Percolation | pt_PT |
| dc.subject | Phase transition | pt_PT |
| dc.subject | Pre-freezing mesophase | pt_PT |
| dc.title | Liquid pre-freezing percolation transition to equilibrium crystal-in-liquid mesophase | pt_PT |
| dc.type | journal article | |
| dspace.entity.type | Publication | |
| oaire.citation.endPage | 262 | pt_PT |
| oaire.citation.issue | 07 | pt_PT |
| oaire.citation.startPage | 247 | pt_PT |
| oaire.citation.title | Natural Science | pt_PT |
| oaire.citation.volume | 10 | pt_PT |
| person.familyName | Woodcock | |
| person.givenName | Leslie | |
| person.identifier.orcid | 0000-0003-2350-559X | |
| rcaap.rights | openAccess | pt_PT |
| rcaap.type | article | pt_PT |
| relation.isAuthorOfPublication | b550a18f-b4d3-4d68-8b8d-84f3373024aa | |
| relation.isAuthorOfPublication.latestForDiscovery | b550a18f-b4d3-4d68-8b8d-84f3373024aa |
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