Hardening the tooth enamel by fluoride is exactly like an anti-corrosive treatment of a steel surface.
If someone would propose that instead of applying the anti-rust layer on the external steel surface, a hole should be made in the steel, then the anti-corrosive coating should be put inside, then the hole should be plugged, enclosing inside the anti-corrosive material, and after all this they would expect that the external untreated steel surface will not rust, they would be laughed at. But this is equivalent with the theory that one should drink fluoridated water to harden the tooth enamel.