Metal sheathing for wood hulls gave way to "bottom paint" sometime in the late nineteenth century. I don't know an exact date.
I'm aware of two protective paints that were in common use on wood hulls in the nineteenth and early twentieth centuries (and, I suppose, still are). One is the green that Mr. Stauffer referred to. The other looked like metallic copper in the can, and when initially applied, but a it dried it turned dark red on the outer surface. (I guess that was the oxidation process working on the copper particles that were mixed in with the paint.) I have the impression that most, or many, of the great New England and Canadian fishing schooners were painted that way.
At the museum where I used to work I had the job of restoring an old model of an American lightship that had been built (the model, that is) for the great Centennial Exhibition at Philadelphia in 1876. The model was built by a local boatbuilder, who quite obviously had painted its bottom with "full-size" bottom paint. It was dark red - but pretty beat up. I bought a can of copper-based bottom paint from a marine paint dealer. Sure enough, it looked like bright metallic paint when it was fresh, but when it dried it matched the 1876 red paint perfectly.
So I guess I can say with confidence that dark red (when dry) bottom paint existed in 1876. How much earlier it could be bought, or how common its use was, I have no idea.
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