Hi Rom,
Not exactly sure what you mean by "treatment of data massive", but once you have a properly formatted input file (did you use the CalcZAF export menu from Probe for EPMA?), just use the CalcZAF Open Input Data File and Calculate/Export All menu. Then you can calculate your 100 k-ratio measurements and export to Excel in a couple of mouse clicks. If you want to compare the different matrix correction methods, just perform this operation for each matrix correction method and save to a different file.
In both CalcZAF and PFE you can also select the Use All Matrix Corrections checkbox option. But in CalcZAF it will do the quant calculation for each data point for each matrix correction, while in Probe for EPMA it will perform each matrix correction calculation for all data points and give you the averages also. Are you working with Ron Rasch? The point being that it would be easier to do this comparison in Probe for EPMA which he can provide to you for data reprocessing.
Also please keep in mind that CalcZAF doesn't perform spectral interference, time dependent intensity (TDI), or area peak factor (APF) corrections, so again, Probe for EPMA would be better for reprocessing. See the Use All Matrix Corrections checkbox in the Analyze! window.