Electrolytic purification is most preferred for ore, but smelting is also an option (especially when dealing with alloys or scrap)
I believe that you mean recrystallization of previously deformed copper. In this case EBSD may be helpful to observe the number of recrystallized grains with respect to non-recrystallized ones.
If you mean the crystal to amorphous percentages, XRD analysis can give you that by using certain software.
In comparison to direct observation of the microstructure by light microscope or SEM-EBSD, DSC is both faster and cheaper.
Recrystallization as a solid state transformation can be studied by non-isothermal experiments conducted in a constant heating rate such as investigations by differential scanning calorimetry (DSC). By DSC analysis, the recrystallized fraction X at temperature T is given by X=AT/A where A is the total area of the exothermal peak and AT is the area under the curve between the temperature of beginning of peak(T0) and the temperature TX.
For more information see this paper : Physica B 417 (2013) 33–38
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