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You can assign a material in several ways.
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Drag selected material(s) to the objects. -
On the toolbar, click  (Assign Material To Selection).
If more than one material is selected, materials will be converted to one multi-material
Also you can drag/assign a material to selected face(s).
Also you can drag a material(s) to Material Editor (Standart or Slate)
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 to the objects.
On the toolbar, click (Assign Material To Selection).
If more than one material is selected, materials will be converted to one multi-material "Pin It")