Excluding MIP and CT, primarily considering capillary with diameter larger than 100nm. We are working on building a dynamic bilateral relationship between pore structure and durability of concrete.
For pores above 100nm MIP would be the best option
Appropriate BET nitrogen adsorption measurements will allow the pore size distribution to be deduced using the BJH (Barret, Joynner, Halenda) method. The concrete must be dry, which may rule this technique out if you are planning to monitor development in a continually hydrating specimen.
As standardized by ISO, the upper limit of BJH method based on nitrogen adsorption is 100nm. Thus it cannot be used for characterization of capillary pores larger than 100nm. You are advised to use numerical method to solve this problem, and use experimental methods to test the degree of hydration. Please see my paper "realistic pore structure of cement paste..."
You could also try to develop desorption isotherms and relate each RH (%) to the pore size (i.e., radius) through the Kelvin-Laplace equation. This is a more accurate and consistent way of doing it, although time-consuming due to the long drying times especially for the smallest pore sizes. Hope this helps. Best.
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