Presence of two freezing-in processes concerning alpha-glass transition inthe new liquid phase of triphenyl phosphite and its consistency with "cluster structure" and "intracluster rearrangement for alpha process" models
M. Mizukami et al., Presence of two freezing-in processes concerning alpha-glass transition inthe new liquid phase of triphenyl phosphite and its consistency with "cluster structure" and "intracluster rearrangement for alpha process" models, J PHYS CH B, 103(20), 1999, pp. 4078-4088
Triphenyl phosphite was studied by powder X-ray diffractometry, adiabatic c
alorimetry, and dielectric relaxation measurements. The highly correlated l
iquid, denoted by L-C, phase corresponding with the glacial phase by Cohen
et al. was prepared by annealing the ordinary liquid, denoted by L-N, at 21
0 K, and different states in the L-C phase were formed by further annealing
the prepared L-C-phase sample at 215 and 220 K. After the temperature jump
from 210 to 215 K, two different processes first of heat absorption and th
en heat: evolution were found to exist in the L-C phase. The first process
showed reversible temperature dependence of the relaxation times near the t
emperature of L-C-phase formation as far as the process bringing the latter
heat evolution effect did not proceed any further. The glass transition te
mperatures were found to be 209.9, 212.6, and 214.0 K for the L-C-phase sam
ples formed at 210, 215, and 220 K, respectively. The fragility parameters
of the respective samples were 104, 99, and 94, comparable with 104 in the
L-N phase. The second process changed the relaxation times of the first pro
cess irreversibly to increase as the temperature of L-C-phase formation inc
reases in the order of 210, 215, and 220 K. The temperature dependences of
beta-relaxation times were found to coincide completely with each other bet
ween the L-N and L-C phases. Those results were interpreted by the "intracl
uster rearrangement for alpha process" model combined with the "cluster str
ucture for supercooled liquid and glass" model; the above second process co
rresponds to the increase/decrease in the size of the somehow "structurally
ordered" region (named a cluster) and the first one to the order/disorder
process of molecules within each cluster, namely the ordinary or process. T
he above second effect of heat evolution at 215 K is thus due to the develo
pment of ordering following the increase in the cluster size. The beta rela
xation would be attributed to the rearrangement of molecules between the cl
usters.