Getting there!
I had trouble with remembering to save and accidentally creating loads of empty images for baking to.
Not sure if anyone knows how to get rid of them?
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Blender behavior is to delete materials, images, when not in use, at the moment of opening the .blend file.
That’s is why blender has a ‘Fake user’ option. If a material has the option ‘Fake user’ switch one, Blender logically says, object is used by a ’ fake user’, so don’t delete at loading document.
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As FedPete says Blender will not save the ones you are not using. Just do not worry about them. No need actively to delete them.