For building materials like concrete, burnt brick, mortars, etc...
A details heat transfer analysis is required if possible (Conduction, Convection, & Radiation through pores and solid matrix)
I think that apparent thermal proprieties (they matter) can be measured with standard techniques. steady state apparent thermal conductivity, for instance, and maybe transient test to reveal influence of vapor evaporation-migration -condensation. If the use is for building materials it appears reasonable to investigate properties in conditions similar to the actual ones , that is from an apparent , averaged, macroscpoic perspective.
Agree with Mr Scarpa, it exists classical methods and also normalized experiments where, temperature difference between each side of the material is controlled such as humidity, radiative transfer etc.
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