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Sort of. It does block the users, but only on your specific instance. If you’re interacting with a post on another instance and that instance is federated with them, you’ll still see them on that third instance.
Defederating basically takes the three instances from a closed triangle ◺ (where all users can see and post on all three instances) to an open triangle ∟ (where your instance and the defederated instance are blocked from each other, but the third instance can still see and interact with both.)
Very interesting, thank you for the explanation.
Edit: is that just for defederation or also when I block an instance on my account?
That’s only for defederating. Blocking is local, and basically just hides the instance from your feed.