Thanks Kovid.
All calibre files/folders were already excluded from the antivirus and I have no sync programs running.
Just out of curiosity, I copied the library to another external drive, and the same thing happened.
Then I copied it to the C drive... and it works.
So, for now, let's say my problem is partially (because I don't understand why it happened so suddenly) solved. I will continue to investigate, I can't see/find anything running on my computer doing this thing to my library.
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