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Possessed have BS 3+, WS 3+, S5, T5, W3, A5, AP -2

Does Master of Union +1 S and +1 AP work well with Possessed? Will S6 actually be that much more since it will only benefit vs T5. And if not, would the +1 AP be worth it alone?

S6 is also a benefit against T3 as well making them work pretty good against horde units with their 5 attacks though their AP -3 will likely be wasted against them.

Having an AP -3 works well against units with Armor of Contempt. The S6 likely won't help too much against the majority of Space Marines but it will against the t5 stuff like Gravis or Centurions. This loadout would also work against Deathguard or Sisters units.

So in conclusion, it depends on who you are facing and what units they go up against.