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I understand the concept of being "available" because my employer has a rule of core hours that one can be expected to be available for questions/meetings/whatever.

At the same time though, sometimes you can learn a lot by not being available. There's documentation that can be written, and sometimes users need to actually read the manual instead of interrupting you to answer a question you've already answered to them three times before.

Sigh. That last one is the worst. Especially if you've written documentation, pointed it out to them before, and been told "I don't have time to read that".