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Obviously poly won't absorb the moisture from the steam (or rain for that matter) so if the moist steam doesn't help by providing some lubricity to the surface of the poly then dry heat should work just fine.You certainly could be right about that; I will be the first to tell you I’ve never shaped a poly hat and so am just thinking out loud. I’ve been trying to decide between a hemp or poly hat for durable summer wear, but can’t find much in either material with a taller crown and a 3” or so brim.
In your own search if you prefer poly you should be able to find one of the trooper style hats from Stratton or Lawman but you might have to live with a cloth sweat. Keep in mind they are heavy so don't get the "double" poly.