The
rate of diffusion of small molecules within polymer matrices
is important in an enormous scope of practical scenarios. However,
it is challenging to perform direct measurements of each system of
interest under realistic conditions. Free volume theories have proven
capable of predicting diffusion coefficients in polymers but often
require large amounts of physical constants as input. Therefore, we
adapted a version of the Vrentas–Duda free volume theory of
diffusion such that the necessary parameters may be obtained from
a limited set of diffusion data collected at the temperature of interest
using commercially available and automated sorption equipment. This
approach correlates the size and shape of molecules to their trace
diffusion coefficient, D, such that D of very large, solid diffusants can be predicted based on properties
measured for condensable vapor diffusants. Our analysis was based
on the volume-averaged transport properties of polyaromatic color
additives within segmentally arranged poly(ether-block-amide) (PEBAX) block copolymer matrices. At very high polyamide
content the considerable plasticization effects due to absorbed water
can be accommodated by increasing the available hole free volume as
a function of water content. Alternatively, if the release rate of
additives is measured for very high polyether content and degree of
swelling, the release rate in the unswollen elastomer may be anticipated
using the tortuosity model of Mackie and Meares. Agreement of these
physical models to new experimental data provides a scientific basis
for accurately predicting the in vivo leaching of
aromatic additives from medical device polymers using accelerated
and/or simplified in vitro methodologies.
A study was made of the relationship between ion current migrating through anodic oxide films on vanadium and the electrostatic field across the dielectric over a potential range of some 100V utilizing the open‐circuit transient method. The results show that the relationship between the formation current density,
i
, and the formation potential,
V
, is of the form
i=io
exp
false(V/Vofalse)
, where
io
and
Vo
are parameters resulting from analysis.
Vo
was found to be a linear function of the formation voltage. The quantity, θ, was found to be essentially equal to zero, a result which departs from results previously reported for other metals, for example tantalum, iron, and bismuth.
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