How to add multiple materials to different faces of the same geometry?

Just as the title says, I have a single piece of geometry of  a metal bolt and I have created 2 materials: 1 for the head and another for the thread. I don't seem able to apply the materials to the faces I want and have the material display. All I can do is attach it to the entire element. Any idea why?

p.s. The materials are purely for display in a 3D PDF, not for rendering purposes.

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