Senkov Oleg N, Miracle Daniel B
Air Force Research Laboratory, Materials and Manufacturing Directorate, 2230 Tenth Street, Wright-Patterson AFB, Ohio 45433-7817, USA.
J Chem Phys. 2008 Mar 28;128(12):124508. doi: 10.1063/1.2890726.
A phenomenological relationship between reduced excess heat capacity of supercooled liquid DeltaC(p)(exc)(T(g))DeltaS(m) at the glass transition temperature T(g), fragility index m, and reduced glass transition temperature T(rg)=T(g)T(m), where T(m) is the melting (liquidus) temperature, was derived for fragile nonpolymeric glass-forming liquids under the assumptions that the fragile behavior of these liquids is described by the Vogel-Fulcher-Tammann (VFT) equation; the excess heat capacity of liquid is inversely proportional to the absolute temperature and the VFT temperature T(0) is equal to the Kauzmann temperature T(K). It was found that DeltaC(p)(exc)(T(g))DeltaS(m) is a composite function of m and T(rg), which indicates that the empirical correlation DeltaC(p)(exc)(T(g))DeltaS(m)=0.025m recently identified by Wang et al. [J. Chem Phys. 125, 074505 (2006)] is probably valid only for liquids which have nearly the same values of T(rg).
对于易碎的非聚合物玻璃形成液体,在以下假设下推导了玻璃化转变温度(T(g))下过冷液体的约化过剩热容(\Delta C(p)(exc)(T(g))\Delta S(m))、脆性指数(m)和约化玻璃化转变温度(T(rg)=T(g)/T(m))(其中(T(m))是熔点(液相线温度))之间的唯象关系:这些液体的脆性由Vogel-Fulcher-Tammann(VFT)方程描述;液体的过剩热容与绝对温度成反比,且VFT温度(T(0))等于考兹曼温度(T(K))。结果发现,(\Delta C(p)(exc)(T(g))\Delta S(m))是(m)和(T(rg))的复合函数,这表明Wang等人[《化学物理杂志》125, 074505 (2006)]最近确定的经验关联(\Delta C(p)(exc)(T(g))\Delta S(m)=0.025m)可能仅对(T(rg))值几乎相同的液体有效。