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Activation volume in superpressed glass-formers

Scientific Reports, ISSN: 2045-2322, Vol: 9, Issue: 1, Page: 13787
2019
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Article Description

In pressurized glass-forming systems, the apparent (changeable) activation volume V(P) is the key property governing the previtreous behavior of the structural relaxation time (τ) or viscosity (η), following the Super-Barus behavior: τ(P),η(P)∝exp(Va(P)/RT), T = const. It is usually assumed that V(P) = V(P), where V#(P)=RTdlnτ(P)/dP or V#(P)=RTdlnη(P)/dP. This report shows that V(P) ≪ V(P) for P → P, where P denotes the glass pressure, and the magnitude V(P) is coupled to the pressure steepness index (the apparent fragility). V(P) and V(P) coincides only for the basic Barus dynamics, where V(P) = V = const in the given pressure domain, or for P → 0. The simple and non-biased way of determining V(P) and the relation for its parameterization are proposed. The derived relation resembles Murnaghan - O’Connel equation, applied in deep Earth studies. It also offers a possibility of estimating the pressure and volume at the absolute stability limit. The application of the methodology is shown for diisobutyl phthalate (DIIP, low-molecular-weight liquid), isooctyloxycyanobiphenyl (8*OCB, liquid crystal) and bisphenol A/epichlorohydrin (EPON 828, epoxy resin), respectively.

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