seal between window sill and frame

I've cast a new sill and its about time I sealed it to the frame. Since both will be in a bare non-painted state I have several combinations of paint/primer/bare at which to apply the silicone sealant. As you know s. sealant is not overpaintable so perhaps the best is over the paint. But the frame paint is microporous which slowly disintegrates. So when should I apply? Does the wood need sealing with something first or can the silicone go straight on bare wood and what about bare concrete, I guess thats okay?

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visionset
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