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Silicone will harden as it's exposed to oxygen. You can hurry it along a little with some low heat or blowing air on it, like from a hair dryer or fan, but for the most part, you just have to let it do what it's going to do. However, you can buy fast-cure silicone caulk that's water-ready in 30 minutes, and it's not really more expensive than any other silicone caulk.
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