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Logias cannot be hit by physical attacks. Period. It's got nothing to do with whether you hit them unaware or not, you cannot hit Kizaru in a state where he's 'normal' because he's a logia, it'll go through him no matter what, unless you use haki.
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I think they have to master their ability to a certain point to be like that. I know you say comic relief, but I say training. Luffy did catch Ace and Smoker off guard and put them through a wall. Now I don't think this applies with Enel and Kizaru because they both probably mastered theirs. I do think that people who haven't mastered their fruit have an 'off' mode because otherwise Ace would burn whatever he touches.