2 research outputs found
Revealing the pure confinement effect in glass-forming liquids by dynamic mechanical analysis
Many molecular glass forming liquids show a shift of the glass transition Tg
to lower temperatures when the liquid is confined into mesoporous host
matrices. Two contrary explanations for this effect are given in literature:
First, confinement induced acceleration of the dynamics of the molecules leads
to an effective downshift of Tg increasing with decreasing pore size. Secondly,
due to thermal mismatch between the liquid and the surrounding host matrix,
negative pressure develops inside the pores with decreasing temperature, which
also shifts Tg to lower temperatures. Here we present novel dynamic mechanical
analysis measurements of the glass forming liquid salol in Vycor and Gelsil
with pore sizes of d = 2.6, 5.0 and 7.5 nm. The dynamic complex elastic
susceptibility data can be consistently described with the assumption of two
relaxation processes inside the pores: A surface induced slowed down relaxation
due to interaction with rough pore interfaces and a second relaxation within
the core of the pores. This core relaxation time is reduced with decreasing
pore size d, leading to a downshift of Tg in perfect agreement with recent DSC
measurements
Confinement effects on glass forming liquids probed by DMA
Many molecular glass forming liquids show a shift of the glass transition T-g
to lower temperatures when the liquid is confined into mesoporous host
matrices. Two contrary explanations for this effect are given in literature:
First, confinement induced acceleration of the dynamics of the molecules leads
to an effective downshift of T-g increasing with decreasing pore size. Second,
due to thermal mismatch between the liquid and the surrounding host matrix,
negative pressure develops inside the pores with decreasing temperature, which
also shifts T-g to lower temperatures. Here we present dynamic mechanical
analysis measurements of the glass forming liquid salol in Vycor and Gelsil
with pore sizes of d=2.6, 5.0 and 7.5 nm. The dynamic complex elastic
susceptibility data can be consistently described with the assumption of two
relaxation processes inside the pores: A surface induced slowed down relaxation
due to interaction with rough pore interfaces and a second relaxation within
the core of the pores. This core relaxation time is reduced with decreasing
pore size d, leading to a downshift of T-g proportional to 1/d in perfect
agreement with recent differential scanning calorimetry (DSC) measurements.
Thermal expansion measurements of empty and salol filled mesoporous samples
revealed that the contribution of negative pressure to the downshift of T-g is
small (<30%) and the main effect is due to the suppression of dynamically
correlated regions of size xi when the pore size xi approaches