I try to get on a few times a week. I just changed chat servers that allow long usernames, MeHT has helped by setting up a bot (t34), and was working on getting concurrent users to show up on the main page, but couldnt get it working.
Anyhow, to answer your question, the best time to be in chat is when theres alot of people on the forums. I have been there all alone for an hour at a time, or sometimes with half a dozen other members.
I'll try to integrate chat more into the site as i add and work on the forums.