Crystallization of Polymers Under 1D Confinement
237
Fig. 10 Thickness dependence of the crystallization time of thin films of PLLA. Pink triangles
indicate the experimental points of Martinez-Tong et al. [24], the continuous black line is a fit of
the thickness dependence of the crystallization time to Eq. 5
larger sensitivity to the distance from the interface than the gradient in segmental
mobility. While we expect values of ξ < 1 would be measured in each sublayer of the
gradient, values of ξ larger than unity originate from a large drop in mass transport
coupled to an almost constant value of τ all across the film; see sketch in Fig. 11.
We expect that being able to modify this gradient would result in a change inξ, or
similarly by measuring ξ we would be able to provide information on the gradient.
In particular, in the case of identical forms of the gradients in mass transport and
mobility, the same value of ξ would be measured in temperature and spatial analysis.
In the case of slower mobility in proximity of the interfaces, values of ξ < 1 would
Fig. 11 Sketch of the gradients in segmental mobility and in mass transport in a thin slab of
thickness h, leading to the exotic condition ξ > 1
237
Fig. 10 Thickness dependence of the crystallization time of thin films of PLLA. Pink triangles
indicate the experimental points of Martinez-Tong et al. [24], the continuous black line is a fit of
the thickness dependence of the crystallization time to Eq. 5
larger sensitivity to the distance from the interface than the gradient in segmental
mobility. While we expect values of ξ < 1 would be measured in each sublayer of the
gradient, values of ξ larger than unity originate from a large drop in mass transport
coupled to an almost constant value of τ all across the film; see sketch in Fig. 11.
We expect that being able to modify this gradient would result in a change inξ, or
similarly by measuring ξ we would be able to provide information on the gradient.
In particular, in the case of identical forms of the gradients in mass transport and
mobility, the same value of ξ would be measured in temperature and spatial analysis.
In the case of slower mobility in proximity of the interfaces, values of ξ < 1 would
Fig. 11 Sketch of the gradients in segmental mobility and in mass transport in a thin slab of
thickness h, leading to the exotic condition ξ > 1