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Even if you are able to perfectly smooth the cake in buttercream before applying the fondant, you still are likely to get an air bubble or two. There are two main causes that I know of. Dips or divots in the buttercream will cause air to become trapped between the buttercream and fondant. Even a small one. Also, if you put the fondant on and do not smooth in the right order, you run a higher risk of trapping the air inside instead of pushing it out from under the fondant. If you start by smoothing the center moving outwards, then pushing the fondant downwards while smoothing the sides, you will push the majority of the air out and will have less bubbles. Nothing is fool-proof, however, because bubbles are a very common cake enemy!
Some people believe the temperature of the cake can cause bubbles as well and that if you cover a cold cake and then allow it to sit at room temperature, the air will expand as the cake warms and cause bubbles. I'm not sure about this because all of my cakes are chilled before covering and go back into the fridge afterwards, so since I don't do it any other way, I have nothing to compare it to. It's possible, though, that a room temperature cake may have less of a bubble issue vs. a chilled cake.
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