I got the TM Moss Custom Hat for the Warlock dropped twice, but it doesn't show up in the ornaments. I quadruple checked that. The hat is listed in my armor collection.
I dismantled the hat, hoping that would make it available as ornament, but that didn't help.
The hunter and titan hats on the other hand are available as ornaments.
I have enough Synthweave bolts (14), so that's not the issue here either.
It's obviously just another darn bug in this bug riddled PoS (Piece of S...oftware ...).
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Did you get the armor from the Master version? Artificer armor doesn't unlock pieces of armor in the Synthesis menu, you need to get the regular version.