These two words actually mean the same thing, namely that the item being described is liable to burst into flames under certain conditions. Inflammable really means "very flammable", but the two words tend to be used interchangeably.
However, it might be thought that "in" implies "non", as it does in words like "independent", which is the opposite of "dependent". Clearly it could be dangerous if the word is misunderstood, so it is safer to avoid using "inflammable" and prefer a clearer expression such as "highly flammable". For the negative, "non-flammable" is the clearest word to use.
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