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If that were so, then one would at least expect the word to appear under "tags and topics," which it doesn't, whereas both anarchy and anarchism do.

Strange, there's plenty of topics tagged with it: https://steemit.com/trending/voluntaryism

Maybe it's because no one uses it first because everyone's more familiar with anarchy?

My point is that almost everyone is familiar with anarchy, and it's the last thing they ever want to have happen to them. So why dig a hole at the outset by trying to sell it to them as something they would want?

Right, which is why a lot of people here are using Voluntaryism...