When I'm sizing my conductors do I start with wire type. I.E.
THWN is in the 75 degree column
XHHW-2 is in the 90 degree column
Or do I start with the terminal rating.
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It is rare to have terminations that are rated 90C or more, especially those inside equipment. Not just the lug needs the temperature rating, but the entire piece of equipment needs it, unless it is a field-installed termination that is installed outside of equipment. Genearlly speaking, most terminations are rated 75C. For 100A and less, you do have the onus of proof to see that they are listed and labeled for 75C on both ends, because the default is 60C for 100A and less.
So it is a good habit to first check the column for termination rating first, knowing that the wire will be no smaller than that, and then think about the wire's rating. Correction & adjustment factors do not apply to terminations, only to wire ampacity. This is the part of your calculations where taking credit for a 90C wire's rating is most common, when 75C terminations are present. Both conditions must be met, termination ampacity without derates, and wire ampacity with derates, and whichever conductor is larger is the one you use.
Another place you would take credit for a 90C rating, is if you install a separate enclosure for a splice at each end, and then use 90C wire with 75C sizing to connect to the equipment. You might do this to remediate a mistake, or as a value engineering decision.