you can have unlimited materials in a scene, the material can only edit 24 at a time, if there is a material in the scene that yo dont see in any material slot in the editor, just select a slot and use the eyedropper to select a material in the scene by clicking on the object with the material you want to edit and the material editor will switch out the material, but dont worry the other material is still there just not listed in the editor slots anymore.
If you want a copy of the users Reference ill put it on my website for you to download, at your leisure, it is 30mb.
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