The 25-skill cap was removed in Publish 63. You can now gain all the way to 120 from Unraveling, but the gain chance per item is based on its intensity, so you about have to be getting a Guaranteed Gain / RoT gain to get a gain from an item that isn't relic-level, once you hit 100 skill.
Gains from residue items slow down, if not stop, in the high 60s, and you start going from 5-10 gains per bag of random loot, down to 0-3, once you get around 65-67.
Essence-giving items have their gains drop off in the 90s, to being rare above 100.