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Ive made (ok, almost made) a canopy out of sanded plywood and molding. Now I want to cover the inside in something to protect it. Any ideas on what would be best? Silicone, paint, etc?
And you think the paint will be safe to be above the water?

BTW your stand looks awesome! Ive been following the thread for ideas on mine.
That has to be one of the most beautiful and crafted stands I have seen. Wish I had that talent. Congratulations!
Marine Grade paint works best most likely, but it is probably overkill. You could also use Epoxy paint since it practically indistructable once it sets but that is likely way overkill. Personally, I would use a nice coat of primer and then an exterior paint. It will hold up just fine. People who live near the ocean basically use the same thing when they have to paint and it will usually last 20+ years. You might need to touch it up in 10 or so years, but I doubt it. Sun and temperature variation is usually what does in paint. You will likely have neither. The paint and primer will be a great moisture barrier for the wood so I doubt you will ever have to do anything.
I would be remiss if I did not mention lacquer, varnish/polyurethene and shellac. You could do a really nice clear coat and save some of that beautiful wood coloring.
Nice work BigD! I would recommend exterior grade latex paint over a couple of layers of exterior latex primer. It is easy to work with, easy to clean, and being exterior grade, it is very water resistant. Before you paint it, I would also recommend getting the paintable latex/silicone caulk and seal all of your edges, corners, and nail holes prior ro painting. That will help keep the wood from warping and the nails/screws from rusting and failing. BTW, using white semigloss for the interior of the hood is best since it will halp reflect as much light into the tank as possible.
<span style="font-family: Comic Sans MS;">Here's a pic of the stand,
That stand is so good it must be evil. I think I would just nail it above the fire place as art.</span>
I would put down a coat of Kilz primer followed by 2-3 coats of behr high gloss ultra pure white from HD.

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The white paint, in addition to protecting the wood, will also help with reflectivity.